CN116253965A - Environment-adaptive 3D printing hydrogel ink and printing and application thereof - Google Patents
Environment-adaptive 3D printing hydrogel ink and printing and application thereof Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/13—Phenols; Phenolates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to the technical field of hydrogels, and discloses an environmentally-adaptive 3D printing hydrogel ink and printing and application thereof, wherein the ink comprises the following components: hydrogel monomer, water-soluble photoinitiator, cross-linking agent, stabilizer, light absorber and solvent; wherein the stabilizer is any one or more than two of p-methoxyphenol, hydroquinone, p-tert-butylcatechol and phenothiazine; the concentration of the hydrogel monomer in the ink is 3-8 mol/L, and the addition amount of the stabilizer is 50-500 mg/L. The invention solves the problem that the printing cannot be performed due to polymerization at high temperature in the prior art. The environment-adaptive photo-curing 3D printing hydrogel ink provided by the invention has stability and high temperature resistance, and can be used for printing samples with high printing precision and fidelity.
Description
Technical Field
The invention relates to the technical field of hydrogels, in particular to an environmentally-adaptive 3D printing hydrogel ink and printing and application thereof.
Background
Hydrogels are a class of soft materials composed of a hydrophilic three-dimensional polymer cross-linked network and a large amount of water. In recent years, by combining the advantages of a Digital Light Processing (DLP) 3D printing technology or a digital projection lithography (SLA) technology in the aspects of high precision, customized manufacturing, self-supporting performance, complex structure construction and the like, the photo-curing 3D printing hydrogel has good application prospects in the fields of artificial soft tissue organ models, flexible soft robots, flexible electronic sensors and the like. Nevertheless, the geometric complexity of such 3D printing hydrogels, the printing resolution and the environmental flexibility of photosensitive hydrogel inks are currently inadequate, which greatly limits the application of this technology in many fields.
Photo-curable 3D printing hydrogels typically involve formulation of photosensitive hydrogel inks, setting of printing parameters and structural printing, post-printing treatments, and the like. Wherein the preparation of the photosensitive hydrogel ink generally comprises the steps of active monomer component selection, monomer proportion optimization, initiator type, light absorption selection, ink preparation, storage method and the like; setting printing parameters and printing structures generally comprise three-dimensional object slicing, exposure time optimization, light source intensity and wavelength optimization, z-direction manufacturing precision optimization and the like; post-printing treatments typically include removal of remaining uncrosslinked ink, extended shelf life, and the like. However, since photo-curing 3D printing is a region-selective curing shaping of the light source within the material. Therefore, the photosensitive ink of the hydrogel is generally difficult to be directly used for 3D printing in practical application, and the curing dynamics are regulated and the printing high resolution is improved by regulating the photosensitive ink of the hydrogel and the photocrosslinking process. For example, the photoinitiator determines the time required for the hydrogel photosensitive ink to initiate crosslinking and the degree of crosslinking, and the light absorber can effectively prevent ultraviolet light from penetrating through the depth of the whole layer of material, thereby improving the printing precision of the hydrogel. Therefore, for the photo-curing 3D printing hydrogel, the self characteristics of the photosensitive ink and the printing parameters are closely related to the printing precision of the hydrogel structure, and how to relate the blending parameters of a printer and the photo-crosslinking chemical process of the photosensitive ink to realize the environment-adaptive controllable printing of the hydrogel photosensitive ink, so that the regulation and control of the crosslinking rate and the crosslinking strength of the hydrogel photosensitive ink has important significance. However, the presence of the reactive monomer in the hydrogel photosensitive ink presents a challenge for environmentally-adaptive printing, because most of the monomers of the existing hydrogel photosensitive inks are mainly vinyl monomers, tend to self-polymerize due to factors such as light and heat, consume the reactive monomer, and even initiate destructive polymerization.
Therefore, it is important to find an ink stabilizer that converts photoinitiated primary radicals or chain radicals into stable molecules or forms ink that is very reactive and insufficient to allow polymerization to proceed without compromising printing efficiency and maintaining its functionality, for high precision photocurable 3D printing hydrogels.
Disclosure of Invention
The invention aims to provide the environment-adaptive 3D printing hydrogel ink and the printing and application thereof, and solves the problem that the printing cannot be performed due to polymerization at high temperature in the prior art.
In order to achieve the above object, the present invention provides an environmentally-friendly photo-curable 3D printing hydrogel ink comprising the following components:
hydrogel monomer, water-soluble photoinitiator, cross-linking agent, stabilizer, light absorber and solvent; the hydrogel monomer is one or more than two of acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, vinylimidazole, methacrylic acid, 4-acryloylmorpholine, N-vinylpyrrolidone, hydroxyethyl acrylamide, hydroxyethyl methacrylate, dimethylacrylamide, methacryloylated gelatin, methacryloylated silk fibroin, methacryloylated sodium alginate, methacryloylated hyaluronic acid, polyether F127 diacrylate, methacryloylated chondroitin sulfate, polyethylene glycol diacrylate, methacryloylated dextran, methacryloylated heparin, N-acryloylglycinamide and N-acryloylamide semicarbazide; the stabilizer is any one or more than two of p-methoxyphenol, hydroquinone, p-tert-butylcatechol and phenothiazine; the concentration of the hydrogel monomer in the ink is 3-8 mol/L, and the addition amount of the stabilizer is 50-500 mg/L.
Preferably, the water-soluble photoinitiator is phenyl-2, 4, 6-trimethyl benzoyl lithium phosphate (LAP) or azo-diisobutylamidine hydrochloride (V-50), and the mass of the water-soluble photoinitiator is 0.1-1.0% of the mass of the hydrogel monomer.
Preferably, the light absorber is lemon yellow; the addition amount of the lemon yellow in the ink is 50-300 mg/L.
Preferably, the cross-linking agent is any one or more than two of N, N '-methylene bisacrylamide, polyethylene glycol dimethacrylate, N' -hexamethylene bis (methacrylamide), tri (2-acryloyloxyethyl) isocyanurate and triallyl isocyanurate; the amount of the cross-linking agent is 0.1-1.0% of the amount of the hydrogel monomer material.
Preferably, the solvent is deionized water, dimethyl sulfoxide or dimethyl sulfoxide aqueous solution.
The invention provides an application of the ink in photo-curing 3D printing.
Preferably, the application comprises:
(1) Dissolving the hydrogel monomer, the water-soluble photoinitiator, the cross-linking agent, the stabilizing agent and the light absorber into a solvent to prepare the environment-adaptive photo-curing 3D printing hydrogel ink;
(2) Utilizing three-dimensional software or three-dimensional scanning reconstruction to establish a three-dimensional digital model structure;
(3) And (3) placing the environment-adaptive photo-curing 3D printing hydrogel ink prepared in the step (1) in a printer material box, and performing photo-curing 3D printing to obtain a photo-curing hydrogel structure.
Preferably, the photo-curing 3D printing is performed in a dark place and exposed to air.
Preferably, the temperature of the photo-curing 3D printing is 20-50 ℃ and the humidity is 20-80%.
Preferably, the wavelength of the light source for the photo-curing 3D printing is 365-405 nm; the intensity of the light source is 100-1000 mW; the exposure time of the single layer is 5-30 s; the thickness of the monolayer slice layer is 0.05-0.2 nm.
The invention also provides an application of the ink in photo-curing 3D printing.
The environment-adaptive 3D printing hydrogel ink and the printing and application thereof solve the problem that the printing cannot be performed due to polymerization at high temperature in the prior art, and have the following advantages:
1. compared with the prior art, the environment-adaptive photo-curing 3D printing hydrogel ink prepared by adding and adjusting the using amount of the stabilizer has stability, is high-temperature resistant and does not undergo thermal polymerization.
2. The environment-adaptive high-precision 3D printing hydrogel ink not only solves the problem that printing cannot be performed due to polymerization at high temperature in the prior art, but also has high printing precision and fidelity in a printed hydrogel structure.
Drawings
Fig. 1 is a graph showing stability of the environmentally-friendly photo-curable 3D printing hydrogel ink prepared in example 1 of the present invention, which is not protected from light and is exposed to visible light.
FIG. 2 is a high-precision hydrogel microneedle image printed in example 1 of the present invention.
FIG. 3 is a graph showing the mechanical properties of the high-precision hydrogel microneedle printed in example 1 of the present invention.
FIG. 4 is a graph of a hydrogel microneedle printed in comparative example 1 of the present invention.
FIG. 5 is a graph showing the mechanical properties of hydrogel microneedles printed in comparative example 1 of the present invention.
FIG. 6 is a graph of a hydrogel vascular network printed in example 2 of the present invention.
FIG. 7 is a diagram of a porous scaffold printed in example 3 of the present invention.
FIG. 8 is a diagram of a porous scaffold printed in comparative example 2 of the present invention.
FIG. 9 is a block diagram of a printed hydrogel according to example 4 of the present invention.
FIG. 10 is a graph of a hydrogel vascular network printed in example 5 of the present invention.
FIG. 11 is a graph of a hydrogel vascular network printed in example 6 of the present invention.
FIG. 12 is a graph of a hydrogel vascular network printed in example 7 of the present invention.
FIG. 13 is a graph of a hydrogel vascular network printed in example 8 of the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A method of preparing an environmentally-friendly photo-curable 3D printing hydrogel ink, the method comprising:
an environmentally-friendly photocurable 3D printing hydrogel ink (total monomer concentration 6 mol/L) was prepared from 35.54g acrylamide and 7.21g acrylic acid, 0.22g water-soluble photoinitiator LAP, 0.46g N, N' -methylenebisacrylamide, 30mg p-methoxyphenol, 20mg lemon Huang Rongjie to 100mL deionized water.
The method for 3D printing by using the ink comprises the following steps:
(1) Utilizing three-dimensional software or three-dimensional scanning reconstruction to establish a microneedle structure of the three-dimensional digital model;
(2) Placing the environment-adaptive photo-curing 3D printing hydrogel ink prepared in the step (1) into a printer material box, and printing by using a photo-curing 3D printer under the conditions of no light shielding, exposure to air, printing humidity of 20-80% and printing temperature of 35 ℃ to obtain a photo-curing hydrogel microneedle structure; wherein the printing parameters are set as follows: light source wavelength: 405nm; the intensity of the light source is 500mW; single layer exposure time 10s; the thickness of the monolayer slice layer is 0.1nm.
Comparative example 1
A method for preparing a photo-curable 3D printing hydrogel ink, which is substantially the same as example 1, except that:
30mg of p-methoxyphenol was not added.
The method of 3D printing using the above ink is the same as that of example 1.
Example 2
The preparation method of the environment-adaptive photo-curing 3D printing hydrogel ink is basically the same as that of the embodiment 1, except that:
the same operations as in example 1 were carried out to obtain an environmentally-friendly photocurable 3D printing hydrogel ink (total monomer concentration: 5 mol/L) having a mass of 0.18g of water-soluble photoinitiator LAP, a mass of 0.39g of N, N' -methylenebisacrylamide, and a volume of 15mg of lemon yellow.
The method of 3D printing using the above ink is basically the same as that of example 1, except that:
in the step (1), a complex vascular network structure of a three-dimensional digital model is established by utilizing three-dimensional software or three-dimensional scanning reconstruction;
in step (2), the same operation as in example 1 was performed to obtain a complex vascular network structure of the photocurable hydrogel.
Example 3
The preparation method of the environment-adaptive photo-curing 3D printing hydrogel ink is basically the same as that of the embodiment 1, except that:
7.21g of acrylic acid was changed to 9.41g of vinylimidazole, and N, N' -methylenebisacrylamide was 0.19g in mass and p-methoxyphenol was 20mg in mass.
The method of 3D printing using the above ink is basically the same as that of example 1, except that:
in step (1), a porous scaffold structure of a three-dimensional digital model is established by utilizing three-dimensional software or three-dimensional scanning reconstruction;
in step (2), the same operation as in example 1 was performed to obtain a photocurable hydrogel porous scaffold structure.
Comparative example 2
The preparation method of the photo-curable 3D printing hydrogel ink is basically the same as example 3, except that:
20mg of p-methoxyphenol was not added.
The method of 3D printing using the above ink was the same as in example 3.
Example 4
The preparation method of the environment-adaptive photo-curing 3D printing hydrogel ink is basically the same as that of the embodiment 3, except that:
9.41g of vinylimidazole were exchanged for 20.72g of 2-acrylamido-2-methylpropanesulfonic acid and 20mg of p-methoxyphenol were exchanged for 20mg of hydroquinone.
The method of 3D printing using the above ink was the same as in example 3.
Example 5
A method of preparing an environmentally-friendly photo-curable 3D printing hydrogel ink was the same as example 1.
The method of 3D printing using the above ink is basically the same as that of example 1, except that:
in step (2), the printing temperature was 45 ℃.
Example 6
A method of preparing an environmentally-friendly photo-curable 3D printing hydrogel ink was the same as example 1.
The method of 3D printing using the above ink is basically the same as that of example 1, except that:
in step (2), the printing temperature is 25 ℃.
Example 7
The preparation method of the environment-adaptive photo-curing 3D printing hydrogel ink is basically the same as that of the embodiment 1, except that:
30mg of p-methoxyphenol was changed to 30mg of hydroquinone.
The method of 3D printing using the above ink is the same as that of example 1.
Example 8
The preparation method of the environment-adaptive photo-curing 3D printing hydrogel ink is basically the same as that of the embodiment 1, except that:
30mg of p-methoxyphenol was changed to 30mg of phenothiazine.
The method of 3D printing using the above ink is the same as that of example 1.
Example 9
The preparation method of the environment-adaptive photo-curing 3D printing hydrogel ink is basically the same as that of the embodiment 1, except that:
acrylamide and acrylic acid are replaced by one or more than two of 2-acrylamide-2-methylpropanesulfonic acid, vinylimidazole, methacrylic acid, 4-acryloylmorpholine, N-vinylpyrrolidone, hydroxyethyl acrylamide, hydroxyethyl methacrylate, dimethylacrylamide, methacryloylated gelatin, methacryloylated silk fibroin, methacryloylated sodium alginate, methacryloylated hyaluronic acid, polyether F127 diacrylate, methacryloylated chondroitin sulfate, polyethylene glycol diacrylate, methacryloylated dextran, methacryloylated heparin, N-acryloylglycinamide and N-acryloylamide, and the concentration of the selected hydrogel monomer in the prepared environment-adaptive photo-curing 3D printing hydrogel ink is 3-8 mol/L.
The method of 3D printing using the above ink is the same as that of example 1.
Example 10
The preparation method of the environment-adaptive photo-curing 3D printing hydrogel ink is basically the same as that of the embodiment 1, except that:
n, N '-methylene bisacrylamide is changed into any one or more than two of polyethylene glycol dimethacrylate, N' -hexamethylene bis (methacrylamide), tri (2-acryloyloxyethyl) isocyanurate and triallyl isocyanurate (cross-linking agent); and the amount of the crosslinking agent is (0.1-1.0)% of the hydrogel monomer material.
The method of 3D printing using the above ink is the same as that of example 1.
Example 11
The preparation method of the environment-adaptive photo-curing 3D printing hydrogel ink is basically the same as that of the embodiment 1, except that:
the deionized water is changed into dimethyl sulfoxide aqueous solution or dimethyl sulfoxide, and the mass fraction of the dimethyl sulfoxide in the dimethyl sulfoxide aqueous solution is 10-90%.
The method of 3D printing using the above ink is the same as that of example 1.
Example 12
The preparation method of the environment-adaptive photo-curing 3D printing hydrogel ink is basically the same as that of the embodiment 1, except that:
phenyl-2, 4, 6-trimethylbenzoyl lithium phosphate (LAP) was exchanged for azobisisobutyrimidine hydrochloride (V-50).
The method of 3D printing using the above ink is the same as that of example 1.
Example 13
A method of preparing an environmentally-friendly photo-curable 3D printing hydrogel ink was the same as example 1.
The method of 3D printing using the above ink is basically the same as that of example 1, except that:
in the step (2), the printing temperature is 50 ℃ and the printing humidity is 80%; the wavelength of the light source is 366nm; the intensity of the light source is 1000mW or 120mW; the exposure time of the single layer is 5s or 30s; the monolayer slice layer thickness was 0.05nm.
Experimental example 1 test of the Properties of the environmentally-friendly photo-curable 3D printing hydrogel ink prepared in example 1
The stability of the environmentally-friendly photo-curable 3D printing hydrogel ink prepared in example 1 was tested, and the specific test procedure was: curing and crosslinking will not occur when the glass is exposed to air for a long time (more than one week).
As shown in FIG. 1, according to the stability graph of the environment-adaptive photo-curing 3D printing hydrogel ink prepared in the embodiment 1 of the invention, the hydrogel photo-sensitive ink can not be cured after being exposed to the air for a long time under the condition of not being protected from light, and has good stability as can be seen from FIG. 1.
Experimental example 2 mechanical Property test
The hydrogel structures prepared in example 1 and comparative example 1 were tested for mechanical properties.
As shown in fig. 3, the mechanical performance diagram of the high-precision hydrogel microneedle printed in example 1 of the present invention shows that when the strain of the 3D printed hydrogel microneedle structure prepared in the present invention is 621±67%, the tensile strength reaches 0.13±0.04MPa, and the elastic modulus is 66.1±2.1kPa.
As shown in FIG. 5, the mechanical properties of the hydrogel microneedle printed in comparative example 1 of the present invention are shown in FIG. 5, and it can be seen from FIG. 5 that the soft tissue-like elastic hydrogel of the present invention has a tensile strength of 0.32.+ -. 0.03MPa and an elastic modulus of 78.9.+ -. 10.4kPa when the strain is 630.+ -. 34%.
Experimental example 3 analysis of the accuracy of finished products printed in examples and comparative examples
As shown in fig. 2, the high-precision hydrogel microneedle image printed in example 1 of the present invention, and it can be seen from fig. 2 that the hydrogel microneedle structure printed in example 1 has good fidelity and precision.
As shown in fig. 4, the hydrogel microneedle image printed in comparative example 1 of the present invention, it can be seen from fig. 4 that the hydrogel microneedle of comparative example 1 has poor printing accuracy. Analysis was performed in conjunction with fig. 2 (compared with example 1), since the stabilizer (p-methoxyphenol) was not added to comparative example 1, the printed hydrogel microneedle structure underwent a cursory phenomenon, resulting in poor printing accuracy.
As shown in fig. 6, the hydrogel vascular network diagram printed in example 2 of the present invention, it can be seen from fig. 6 that the vascular network structure printed in example 2 has a clear and penetrating vascular vein structure, which indicates that the vascular network printed in example 2 has high printing accuracy and fidelity.
As shown in fig. 7, a porous scaffold printed in example 3 of the present invention, it can be seen from fig. 7 that the hydrogel porous scaffold printed in example 3 has a very regular and uniform network structure, indicating that the porous scaffold printed in example 3 has very high printing accuracy and fidelity.
As shown in fig. 8, a porous scaffold printed in comparative example 2 of the present invention. As can be clearly seen from comparison of fig. 7 and 8, the top of the porous hydrogel scaffold printed in comparative example 2 has obvious shrinkage deformation, and the printed filaments have obvious bursting phenomenon, which indicates that the porous scaffold printed in comparative example 2 does not have good printing performance and printing precision without adding a stabilizer (p-methoxyphenol).
As shown in fig. 9, the hydrogel structure printed in example 4 of the present invention, it can be seen from fig. 9 that the hydrogel structure printed in example 4 has a very regular and uniform hierarchical structure, indicating that the hydrogel printed in example 4 has very high printing accuracy and fidelity.
As shown in fig. 10, in the hydrogel vascular network diagram printed in embodiment 5 of the present invention, it can be seen from fig. 10 that the complex vascular network structure of the hydrogel printed in embodiment 5 has a clear and penetrating vascular vein structure, which indicates that the vascular network printed in embodiment 5 has high printing accuracy and fidelity.
As shown in fig. 11, a hydrogel vascular network diagram printed in example 6 of the present invention, and it can be seen from fig. 11 that the hydrogel complex vascular network structure printed in example 6 has a clear and penetrating vascular vein structure. Therefore, the environment-adaptive photo-curing 3D printing hydrogel ink prepared in the embodiment 5 is high in temperature resistance (the printing temperature is 45 ℃), and the printed vascular network has high printing precision and fidelity.
As shown in fig. 12, in the hydrogel vascular network diagram printed in embodiment 7 of the present invention, it can be seen from fig. 12 that the complex vascular network structure of the hydrogel printed in embodiment 7 has a clear and penetrating vascular vein structure, which indicates that the vascular network printed in embodiment 7 has high printing accuracy and fidelity.
As shown in fig. 13, in the hydrogel vascular network diagram printed in embodiment 8 of the present invention, it can be seen from fig. 13 that the complex vascular network structure of the hydrogel printed in embodiment 8 has a clear and penetrating vascular vein structure, which indicates that the vascular network printed in embodiment 8 has high printing accuracy and fidelity.
In summary, none of the hydrogel structures printed in comparative examples 1-2 had good printing performance and printing accuracy, while none of the hydrogel structures printed in examples 1-8 had high printing accuracy and fidelity, and none of the hydrogel structures printed in examples 9-13 had high printing accuracy and fidelity.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Many modifications and substitutions of the present invention will become apparent to those of ordinary skill in the art upon reading the foregoing. Accordingly, the scope of the invention should be limited only by the attached claims.
Claims (10)
1. An environmentally-friendly photo-curable 3D printing hydrogel ink, comprising the following components:
hydrogel monomer, water-soluble photoinitiator, cross-linking agent, stabilizer, light absorber and solvent;
the hydrogel monomer is one or more than two of acrylamide, acrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, vinylimidazole, methacrylic acid, 4-acryloylmorpholine, N-vinylpyrrolidone, hydroxyethyl acrylamide, hydroxyethyl methacrylate, dimethylacrylamide, methacryloylated gelatin, methacryloylated silk fibroin, methacryloylated sodium alginate, methacryloylated hyaluronic acid, polyether F127 diacrylate, methacryloylated chondroitin sulfate, polyethylene glycol diacrylate, methacryloylated dextran, methacryloylated heparin, N-acryloylglycinamide and N-acryloylamide semicarbazide;
the stabilizer is any one or more than two of p-methoxyphenol, hydroquinone, p-tert-butylcatechol and phenothiazine;
the concentration of the hydrogel monomer in the ink is 3-8 mol/L, and the addition amount of the stabilizer is 50-500 mg/L.
2. The ink of claim 1, wherein the water-soluble photoinitiator is phenyl-2, 4, 6-trimethylbenzoyl lithium phosphate (LAP) or azobisisobutylammonium hydrochloride (V-50); the mass of the water-soluble photoinitiator is 0.1-1.0% of the mass of the hydrogel monomer.
3. The ink of claim 1 wherein the light absorber is lemon yellow; the addition amount of the lemon yellow in the ink is 50-300 mg/L.
4. The ink according to claim 1, wherein the crosslinking agent is one or more of N, N '-methylenebisacrylamide, polyethylene glycol dimethacrylate, N' -hexamethylenebis (methacrylamide), tris (2-acryloyloxyethyl) isocyanurate, triallyl isocyanurate;
the amount of the cross-linking agent is 0.1-1.0% of the amount of the hydrogel monomer material.
5. The ink of claim 1, wherein the solvent is deionized water, dimethylsulfoxide, or an aqueous solution of dimethylsulfoxide.
6. Use of an ink according to any one of claims 1-5 in photo-curable 3D printing.
7. The use according to claim 6, comprising:
(1) Dissolving the hydrogel monomer, the water-soluble photoinitiator, the cross-linking agent, the stabilizing agent and the light absorber into a solvent to prepare the environment-adaptive photo-curing 3D printing hydrogel ink;
(2) Utilizing three-dimensional software or three-dimensional scanning reconstruction to establish a three-dimensional digital model structure;
(3) And (3) placing the environment-adaptive photo-curing 3D printing hydrogel ink prepared in the step (1) in a printer material box, and performing photo-curing 3D printing to obtain a photo-curing hydrogel structure.
8. The use of claim 7, wherein the photo-curing 3D printing is performed in a dark place and exposed to air.
9. The use according to claim 7, wherein the temperature of the photo-curing 3D printing is 20-50 ℃ and the humidity is 20-80%.
10. The use according to claim 7, wherein the light source wavelength of the photo-curing 3D printing is 365-405 nm; the intensity of the light source is 100-1000 mW; the exposure time of the single layer is 5-30 s; the thickness of the monolayer slice layer is 0.05-0.2 nm.
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