Self-healing blue light-cured hydrogel material

Abstract

This invention discloses a self-healing, blue-light-curable hydrogel material. The hydrogel comprises an acrylamide compound, a metal salt, an alcohol, water, hydrophilic fibers, and a photoinitiator. The double bonds of the acrylamide compound can polymerize under ultraviolet light. The hydrogen bonds and the support of the hydrophilic fibers enhance the overall strength, thus meeting the strength requirements for 3D printing in a blue-light environment. Abundant hydrogen bonds endow the hydrogel with rapid self-healing capabilities. The hydrogel material of this invention can be applied in medical devices, biomedicine, electronic devices, and industrial packaging.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a self-healing blue light curing hydrogel material and its raw material composition. Background Technology

[0002] Hydrogels are highly designable materials that have attracted widespread attention and extensive research in recent years, showing broad application prospects in the fields of biology, medicine, and electronics. 3D printing (Three Dimensional Printing) is a rapid prototyping technology that creates solid models through the discrete / accumulated deposition of materials. It differs significantly from traditional material removal processes and is a comprehensive processing technology that integrates many cutting-edge technologies and knowledge. 3D printing offers advantages such as short manufacturing cycles, ease of forming complex structures, and material and energy savings. In particular, it breaks through the limitations of traditional parts design and processing techniques, theoretically enabling the production of parts of any shape.

[0003] Compared to other types of 3D printing, photopolymer 3D printing offers higher precision, lower printing temperatures, and shorter printing times, leading to its rapid development in recent years. However, using blue light in photopolymer 3D printing presents a significant challenge because blue light has a longer wavelength, lower frequency, and lower energy compared to ultraviolet light, resulting in lower hydrogel strength and an inability to form precise structures. Yet, in modern biomedical research, a crucial area for hydrogel research, such as printing living cells, organs, and drug delivery systems, it is essential to avoid the negative impacts of ultraviolet light on cells, organs, and drugs. Therefore, it is necessary to upgrade hydrogels from ultraviolet-printed to blue-light-printed hydrogels. Currently, there are very few materials available for blue-light printing, and to meet printing process requirements, the high flexibility and absorbency of hydrogels are often sacrificed. Acrylamide compounds are commonly used to prepare absorbent dressings, but due to their blue light sensitivity and insufficient cross-linking strength, they also fail to meet the requirements of blue-light 3D printing processes.

[0004] Meanwhile, since hydrogels inevitably suffer damage and destruction during application, hydrogel materials with self-healing capabilities have greater value. Summary of the Invention

[0005] This invention addresses the shortcomings of existing technologies by introducing coordination bonds and hydrophilic fibers into photosensitive hydrophilic materials based on polymer material design and 3D printing technologies. Through hydrogen bonding, a multi-molecular network structure is formed, which enhances the mechanical strength of the hydrogel during blue light-induced polymerization and helps the resin to form rapidly. This overcomes the problems of low forming strength and inability to form precise structures in blue light-cured hydrogels, thus meeting the requirements of 3D printing processes. At the same time, the introduced hydrogen bonds also endow the hydrogel with self-healing capabilities.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] A self-healing blue light-curable hydrogel raw material composition, comprising the following components in parts by weight:

[0008] The acrylamide compound is 1 to 99 parts, preferably 20 to 80 parts, and more preferably 30 to 70 parts;

[0009] The alcohol is 1 to 99 parts, preferably 20 to 80 parts, and more preferably 30 to 70 parts;

[0010] Water: 1-99 parts, preferably 20-80 parts, more preferably 30-70 parts;

[0011] The hydrophilic cellulose is 1 to 30 parts, preferably 2 to 20 parts, and more preferably 3 to 10 parts;

[0012] The photoinitiator is 1 to 30 parts, preferably 2 to 20 parts, and more preferably 3 to 10 parts.

[0013] The acrylamide compound is selected from one or more of acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, sodium 2-acrylamido-2-methylpropanesulfonate, 1-(2,4,6-trichlorophenyl)-3-acrylamido-5-pyrazolone, dimethyldiallylammonium chloride-acrylamide, 1-(2,5-dichlorophenyl)-3-acrylamido-5-pyrazolone, N-(1,1-dimethylethyl)-2-acrylamide, N-(hydroxymethyl)-2-acrylamide, N-(butoxymethyl)-2-acrylamide, N-(1,1,3,3-tetramethylbutyl)-2-acrylamide, N-(2-hydroxyethyl)-2-methyl-2-acrylamide, N,N-diethyl-2-acrylamide, 3-acrylamidopropyl)trimethylammonium chloride, and 3-acrylamido-3-methylbutyric acid. Preferably, it is one or more of acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, sodium 2-acrylamido-2-methylpropanesulfonate, N-(hydroxymethyl)-2-acrylamide, and N-(2-hydroxyethyl)-2-methyl-2-acrylamide.

[0014] When the acrylamide compound is two or more of the specific choices mentioned above, the present invention does not impose any special limitation on the ratio of the specific substances mentioned above, and they can be mixed in any ratio.

[0015] The alcohol can be a C1-C10 alcohol, preferably one or more of methanol, ethanol, ethylene glycol, glycerol, isopropanol, tert-butanol, n-butanol, and octanol. Ethanol, ethylene glycol, glycerol, isopropanol, and octanol are preferred.

[0016] When the alcohol is two or more of the specific choices mentioned above, the present invention does not impose any special limitation on the ratio of the specific substances mentioned above, and they can be mixed in any ratio.

[0017] The water used is commonly used deionized water, which meets the national standard GB / T 1146.

[0018] The hydrophilic fiber is selected from one or more of hydroxypropyl methylcellulose, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, sodium carboxymethylcellulose, sodium methylcarbohydrate, and alginate cellulose. Preferably, it is selected from one or more of hydroxypropyl methylcellulose, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and sodium carboxymethylcellulose.

[0019] When the hydrophilic cellulose is two or more of the specific choices mentioned above, the present invention does not impose any special limitation on the ratio of the specific substances mentioned above, and they can be mixed in any ratio.

[0020] The photoinitiator is selected from benzoin and its derivatives, benzoyl derivatives, dialkoxyacetophenone, α-hydroxyalkyl phenyl ketone, α-aminealkyl phenyl ketone, lithium phenyl-2,4,6-trimethylbenzoylphosphonate, acylphosphine oxides, benzophenone and its derivatives, thioxanthones, anthraquinones, trimethylbenzoyl-diphenylphosphine oxide, and ethyl 2,4,6-trimethylbenzoylphenylphosphine. Preferably, it is dialkoxyacetophenone, lithium phenyl-2,4,6-trimethylbenzoylphosphine, benzophenone and its derivatives, trimethylbenzoyl-diphenylphosphine oxide, or ethyl 2,4,6-trimethylbenzoylphenylphosphine.

[0021] When the photoinitiator is two or more of the specific selections mentioned above, the present invention does not impose any special limitation on the ratio of the specific substances mentioned above, and they can be mixed in any ratio.

[0022] In a preferred embodiment of the present invention, the self-healing blue light curable hydrogel raw material composition comprises the following components in parts by weight:

[0023] Acrylamide compound 30-70 parts;

[0024] 30-70 parts alcohol;

[0025] 30-70 parts water;

[0026] 3-10 parts of hydrophilic fiber;

[0027] 3 to 10 parts of photoinitiator.

[0028] This invention also provides a self-healing blue light curable material, which is formed by curing the self-healing blue light curable hydrogel raw material composition of this invention with UV light or blue light. Specifically:

[0029] After mixing acrylamide compound, 30-70 parts alcohol, 30-70 parts water, 3-10 parts hydrophilic fiber, and 3-10 parts photoinitiator evenly, the mixture is cured using 3D printing equipment or UV or blue light curing equipment.

[0030] The present invention does not impose any special limitations on the mixing method; any mixing method known to those skilled in the art can be used.

[0031] The present invention also provides the application of the self-healing blue light curable hydrogel raw material composition or the self-healing blue light curable hydrogel in the preparation of 3D printing materials.

[0032] The present invention also provides the application of the self-healing blue light curable hydrogel raw material composition or the self-healing blue light curable hydrogel in the preparation of biopharmaceutical materials, medical materials, electronic device materials, and industrial packaging materials.

[0033] Advantages of this invention:

[0034] This invention addresses the shortcomings of existing technologies by introducing hydrogen bonds and hydrophilic fibers into a photosensitive hydrophilic material based on polymer material design and 3D printing technologies. This forms a multi-layered molecular network structure, enhancing the mechanical strength of the hydrogel during blue light-induced polymerization. This solves the technical problem of traditional hydrogels being unable to form properly in blue light 3D printing, thus meeting the requirements of 3D printing processes. Furthermore, the introduced hydrogen bonds endow the hydrogel with excellent self-healing capabilities. Attached Figure Description

[0035] Figure 1 The hydrogel device obtained from the material prepared in Example 1 was 3D printed using a DLP 3D printer in the blue light band.

[0036] Figure 2 The images show a comparison of the hydrogel porous structure 3D printing performed using a DLP 3D printer in the blue light band on the materials prepared in Example 2 and Comparative Example 1.

[0037] Figure 3 This is a schematic diagram of the hydrogel self-healing after 3 seconds of printing and curing of the material prepared in Example 2.

[0038] Figure 4 The graph shows the relationship between the self-healing strength and the repair time of the hydrogel after printing and curing the material prepared in Example 2. Detailed Implementation

[0039] The following detailed description, in conjunction with embodiments, illustrates a self-healing blue light-curing hydrogel material, its preparation method, and its applications provided by the present invention. However, these descriptions should not be construed as limiting the scope of protection of the present invention.

[0040] A method for preparing a rapidly self-healing blue light 3D printing hydrogel as described in Examples 1-10:

[0041] Acrylamide compounds, alcohols, water, hydrophilic fibers, and photoinitiators are mixed uniformly and then molded using a blue light curing 3D printer. The printing process varies depending on the activity of the hydrogel raw material composition. The printed hydrogel devices have self-healing capabilities.

[0042] Test method: Stress-strain curves were tested using a tensile testing machine.

[0043] Self-healing efficiency calculation method: tensile strength after repair / tensile strength before repair × 100%

[0044] Example 1

[0045] The acrylamide compound is: 2-acrylamido-2-methylpropanesulfonic acid.

[0046] The alcohol is: ethanol

[0047] The water is: deionized water

[0048] The hydrophilic fiber is: carboxymethyl cellulose

[0049] The photoinitiator is lithium phenyl-2,4,6-trimethylbenzoylphosphonate.

[0050] The proportions of the above ingredients are as follows:

[0051] weight fraction 76 30 30 5 4

[0052] Printing method: DLP printer, printing parameters: wavelength 450nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 20s.

[0053] Example 2

[0054] The acrylamide compound is: sodium 2-acrylamido-2-methylpropanesulfonate.

[0055] The alcohol is: ethylene glycol

[0056] The water is: deionized water

[0057] The hydrophilic fiber is: alginate cellulose.

[0058] The photoinitiator is: trimethylbenzoyl-diphenylphosphine oxide

[0059] The proportions of the above ingredients are as follows:

[0060]

[0061]

[0062] Printing method: DLP printer, printing parameters: wavelength 450nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 15s.

[0063] Example 3

[0064] The acrylamide compound is: N-(hydroxymethyl)-2-acrylamide

[0065] The alcohol is: glycerol

[0066] The water is: deionized water

[0067] The hydrophilic fiber is: hydroxyethyl cellulose

[0068] The photoinitiator is: trimethylbenzoyl-diphenylphosphine oxide

[0069] The proportions of the above ingredients are as follows:

[0070] weight fraction 53 40 40 10 3

[0071] Printing method: DLP printer, printing parameters: wavelength 450nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 25s.

[0072] Example 4

[0073] The acrylamide compound is: N-(2-hydroxyethyl)-2-methyl-2-acrylamide.

[0074] The alcohol is: isopropanol

[0075] The water is: deionized water

[0076] The hydrophilic fiber is sodium carboxymethyl cellulose.

[0077] The photoinitiator is lithium phenyl-2,4,6-trimethylbenzoylphosphonate;

[0078] The proportions of the above ingredients are as follows:

[0079] weight fraction 61 30 40 5 4

[0080] Printing method: DLP printer, printing parameters: wavelength 450nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 20s.

[0081] Example 5

[0082] The acrylamide compound is: acrylamide

[0083] The metal salt is: calcium chloride

[0084] The alcohol is: Octyl alcohol

[0085] The water is: deionized water

[0086] The hydrophilic fiber is: alginate cellulose.

[0087] The photoinitiator is: dialkoxyacetophenone

[0088] The proportions of the above ingredients are as follows:

[0089] weight fraction 51 45 35 6 5

[0090] Printing method: DLP printer, printing parameters: wavelength 450nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 25s.

[0091] Example 6

[0092] The acrylamide compound is: 2-acrylamido-2-methylpropanesulfonic acid.

[0093] The alcohol is: ethanol

[0094] The water is: deionized water

[0095] The hydrophilic fiber is: hydroxypropyl methyl fiber

[0096] The photoinitiator is lithium phenyl-2,4,6-trimethylbenzoylphosphonate.

[0097] The proportions of the above ingredients are as follows:

[0098] weight fraction 73 30 40 5 4

[0099] Printing method: DLP printer, printing parameters: wavelength 450nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 15s.

[0100] Example 7

[0101] The acrylamide compound is: sodium 2-acrylamido-2-methylpropanesulfonate.

[0102] The alcohol is: ethylene glycol

[0103] The water is: deionized water

[0104] The hydrophilic fiber is: carboxymethyl cellulose

[0105] The photoinitiator is: trimethylbenzoyl-diphenylphosphine oxide

[0106] The proportions of the above ingredients are as follows:

[0107] weight fraction 73 35 45 7 7

[0108] Printing method: DLP printer, printing parameters: wavelength 450nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 18s.

[0109] Example 8

[0110] The acrylamide compound is: N-(hydroxymethyl)-2-acrylamide

[0111] The alcohol is: isopropanol

[0112] The water is: deionized water

[0113] The hydrophilic fiber is sodium carboxymethyl cellulose.

[0114] The photoinitiator is benzophenone.

[0115] The proportions of the above ingredients are as follows:

[0116] weight fraction 51 33 35 7 7

[0117] Printing method: DLP printer, printing parameters: wavelength 450nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 25s.

[0118] Example 9

[0119] The acrylamide compound is: N-(2-hydroxyethyl)-2-methyl-2-acrylamide.

[0120] The alcohol is: ethanol

[0121] The water is: deionized water

[0122] The hydrophilic fiber is: alginate cellulose.

[0123] The photoinitiator is lithium phenyl-2,4,6-trimethylbenzoylphosphonate.

[0124] The proportions of the above ingredients are as follows:

[0125] weight fraction 64 40 45 3 3

[0126] Printing method: DLP printer, printing parameters: wavelength 450nm, UV light power 10mW / cm² 2The layer thickness is 0.05mm and the exposure time is 20s.

[0127] Example 10

[0128] The acrylamide compound is: 2-acrylamido-2-methylpropanesulfonic acid.

[0129] The alcohol is: Octyl alcohol

[0130] The water is: deionized water

[0131] The hydrophilic fiber is: methylcellulose

[0132] The photoinitiator is ethyl 2,4,6-trimethylbenzoylphenylphosphonate.

[0133] The proportions of the above ingredients are as follows:

[0134] weight fraction 64 30 52 2 6

[0135] Printing method: DLP printer, printing parameters: wavelength 450nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 18s.

[0136] Comparative example:

[0137] Remove the hydrophilic fibers from Example 2.

[0138] The acrylamide compound is: sodium 2-acrylamido-2-methylpropanesulfonate.

[0139] The alcohol is: ethylene glycol

[0140] The water is: deionized water

[0141] The photoinitiator is: trimethylbenzoyl-diphenylphosphine oxide

[0142] The proportions of the above ingredients are as follows:

[0143] weight fraction 60 20 30 0 5

[0144] Printing method: DLP printer, printing parameters: wavelength 450nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 15s.

[0145] Comparative Example 2

[0146] The acrylamide compound is: sodium 2-acrylamido-2-methylpropanesulfonate.

[0147] The alcohol is: ethylene glycol

[0148] The water is: deionized water

[0149] The hydrophilic fiber is: alginate cellulose.

[0150] The photoinitiator is: trimethylbenzoyl-diphenylphosphine oxide

[0151] The proportions of the above ingredients are as follows:

[0152] weight fraction 85 0 30 8 5

[0153] Printing method: DLP printer, printing parameters: wavelength 450nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 15s.

[0154] The tensile strength and self-healing efficiency data of the above embodiments and comparative examples are shown in the table below.

[0155]

[0156] Figure 1 The image shows a physical object printed using a Blu-ray 3D printer, based on the material composition prepared according to Example 1. The dimensions are shown in the right-hand image, and it can be seen that the 3D printed structure is relatively clear, with micropores having a diameter of less than 1 mm.

[0157] Figure 2 The left image shows a physical object printed using a Blu-ray 3D printer according to the material composition prepared in Example 2, while the right image shows a physical object printed using the material composition prepared in the comparative example. It can be seen that the introduction of metal ions and hydrophilic fibers helps 3D printing, while the absence of these elements prevents printing.

[0158] Figure 3 This demonstrates the self-healing properties of the material composition prepared according to Example 2 after curing. A noticeable self-healing effect is observed after contact with the material for 3 seconds following cutting.

[0159] Figure 4 The self-healing efficiency of the material composition prepared according to Example 2 is shown to be related to time after curing. It can be seen that more than 90% of the strength can be restored after 24 hours.

[0160] By comparing the examples and comparative examples, it can be seen that the fiber-reinforced hydrogel exhibits high strength after 20 seconds of blue light irradiation, reaching over 80% of the strength after 5 minutes of irradiation. Therefore, it can rapidly generate strength under blue light 3D printing technology. In contrast, the non-fiber-reinforced hydrogel (Comparative Example 1) shows low strength after both 20 seconds and 5 minutes of blue light irradiation, failing to meet the requirements of the 3D printing process.

[0161] By comparing Comparative Example 2 and Example 2, the self-repair efficiency was only 11% after removing the hydrogen-bonded alcohol, but the self-repair efficiency reached 93% after adding the alcohol.

[0162] Therefore, through comparative embodiments and examples, it is found that the method of the present invention can be used to print complex structural parts using Blu-ray 3D printing, and it has rapid self-healing capabilities. The above description is merely a preferred embodiment of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A self-healing blue light curing material, characterized in that... The self-healing blue light curable hydrogel raw material composition is cured by blue light 3D printing. The self-healing blue light curable hydrogel raw material composition consists of the following components in parts by weight: Acrylamide compound 20-80 parts 20-80 parts of alcohol 20-80 parts water 2-20 parts of hydrophilic cellulose 3-10 parts of photoinitiator The acrylamide compound is selected from one or more of acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, sodium 2-acrylamido-2-methylpropanesulfonic acid, N-(hydroxymethyl)-2-acrylamide, N-(2-hydroxyethyl)-2-methyl-2-acrylamide, and 3-acrylamido-3-methylbutyric acid; The alcohol is a C1-C10 alcohol; The hydrophilic cellulose is selected from one or more of hydroxypropyl methylcellulose, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and sodium carboxymethylcellulose; The photoinitiator is selected from one or more of the following: benzoin, dialkoxyacetophenone, α-hydroxyalkyl phenyl ketone, α-aminealkyl phenyl ketone, lithium phenyl-2,4,6-trimethylbenzoylphosphonate, acylphosphine oxide, benzophenone, thioxanthones, anthraquinones, trimethylbenzoyl-diphenylphosphine oxide, and ethyl 2,4,6-trimethylbenzoylphenylphosphine.

2. The self-healing blue light curing material as described in claim 1, characterized in that... The alcohol is selected from one or more of methanol, ethanol, ethylene glycol, glycerol, isopropanol, tert-butanol, n-butanol, and octanol.

3. The application of the self-healing blue light curing material as described in claim 1 or 2 in the preparation of biopharmaceutical materials, medical materials, electronic device materials, and industrial packaging materials.

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