Lipoic acid-based ink, 3D material and preparation method thereof

Abstract

The invention relates to a lipoic acid-based ink, a 3D material and a preparation method thereof, the lipoic acid-based ink comprises lipoic acid, linear acrylate and a photoinitiator, the molar ratio of the linear acrylate to the lipoic acid is greater than or equal to 0.1: 1, and the molecular weight of the linear acrylate is less than or equal to 2000. In the lipoic acid-based ink disclosed by the invention, the linear acrylate can effectively break a hydrogen bond network in a lipoic acid oligomer and avoid the formation of the lipoic acid oligomer, so that the viscosity of the lipoic acid-based ink can be effectively reduced and the stability of the lipoic acid-based ink can be improved, and therefore, the lipoic acid-based ink disclosed by the invention is suitable for preparing a 3D material through additive manufacturing.

Description

Technical Field

[0001] The present invention relates to the technical field of additive manufacturing, and in particular to lipoic acid-based ink, 3D materials and preparation methods thereof. Background Art

[0002] Lipoic acid-based polymers (TA polymers) have the advantages of being green, high-strength and toughness, degradable, recyclable, biocompatible and self-healing. However, their dynamic disulfide bonds and carboxyl groups often cause instability and high viscosity (>10000mPa·s), making TA polymers unsuitable for additive manufacturing. Summary of the invention

[0003] Based on this, it is necessary to provide a lipoic acid-based ink, a 3D material and a preparation method thereof to address the above problems. The lipoic acid-based ink has low viscosity and good stability and is suitable for additive manufacturing.

[0004] A thioctic acid-based ink comprises thioctic acid, linear acrylate and a photoinitiator, wherein the molar ratio of the linear acrylate to the thioctic acid is greater than or equal to 0.1:1, and the molecular weight of the linear acrylate is less than or equal to 2000.

[0005] In one embodiment, the linear acrylate is selected from at least one of polyethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, ethoxylated bisphenol A diacrylate, and ethoxylated bisphenol fluorene diacrylate;

[0006] And / or, the molar ratio of the linear acrylate to the lipoic acid is 0.1:1-1:1.

[0007] In one embodiment, the molar ratio of the lipoic acid to the photoinitiator is 20:1-80:1.

[0008] In one embodiment, the lipoic acid-based ink further includes a cross-linking agent and / or an ester compound, the molar ratio of the lipoic acid to the cross-linking agent is 1:0.2-1:1.5, and the molar ratio of the lipoic acid to the ester compound is 0.1:1-10:1.

[0009] In one embodiment, the cross-linking agent is selected from at least one of pentaerythritol tetraacrylate, methacrylated gelatin, four-arm polyethylene glycol acrylate, and methacrylated hyaluronic acid.

[0010] In one embodiment, the ester compound is selected from at least one of dodecyl acetate, decyl acetate, and undecyl acetate.

[0011] A 3D material prepared using the lipoic acid-based ink.

[0012] A method for preparing the 3D material comprises printing lipoic acid-based ink with a 3D printer to obtain the 3D material.

[0013] In one embodiment, the printing speed is 0.01 mm / s-1 mm / s.

[0014] In the lipoic acid-based ink of the present invention, linear acrylate can effectively break the hydrogen bond network in the lipoic acid oligomer, avoid the formation of lipoic acid oligomers, thereby effectively reducing the viscosity of the lipoic acid-based ink and improving the stability of the lipoic acid-based ink. Therefore, the lipoic acid-based ink of the present invention is suitable for additive manufacturing to prepare 3D materials. At the same time, lipoic acid has abundant reaction sites, and the ink composed of linear acrylate can be copolymerized to form a high-strength network structure through a chemical click reaction. Moreover, the dynamic disulfide bond in the lipoic acid molecular structure can give the 3D material excellent toughness and degradability, etc., and the molecular segment of the linear acrylate can also improve the toughness and biocompatibility of the 3D material, etc., thereby providing a new solution for the development of tissue engineering and biomedical implants.

[0015] In addition, the lipoic acid-based ink of the present invention may also be compounded with a crosslinking agent and an ester compound. The introduction of the crosslinking agent is beneficial to further improve the toughness of the 3D material, and the introduction of the ester compound can both further reduce the viscosity of the lipoic acid-based ink and adjust the porosity and permeability of the 3D material. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the conventional technology, the drawings required for use in the embodiments or the conventional technology descriptions are briefly introduced below. 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 creative work.

[0017] Figure 1 is a compressive stress curve of 3D materials prepared using the lipoic acid-based inks of Examples 3 and 8-11 of the present invention;

[0018] Figure 2 These are SEM images of 3D materials prepared with lipoic acid-based ink, wherein a is the SEM image of the 3D material prepared with lipoic acid-based ink of Example 8, and b is the SEM image of the 3D material prepared with lipoic acid-based ink of Example 12. DETAILED DESCRIPTION

[0019] For ease of understanding of the present invention, the present invention will be described in more detail below. However, it should be understood that the present invention can be implemented in many different forms and is not limited to the embodiments or examples described herein. On the contrary, the purpose of providing these embodiments or examples is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0020] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific implementation methods or embodiments, and are not intended to limit the present invention. The optional scope of the term "and / or" used herein includes any one of two or more related listed items, and also includes any and all combinations of related listed items, and the combinations include any two related listed items, any more related listed items, or all related listed items.

[0021] In the present invention, when it comes to numerical ranges, unless otherwise specified, the above numerical ranges are deemed to be continuous and include the minimum and maximum values ​​of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0022] The lipoic acid-based ink provided by the present invention includes lipoic acid, linear acrylate and photoinitiator, wherein the molar ratio of the linear acrylate to the lipoic acid is greater than or equal to 0.1:1, such as 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, etc., and the molecular weight of the linear acrylate is less than or equal to 2000, such as 2000, 1800, 1500, 1200, 1000, 750, 500, etc., or the range composed of any two of these values. Then, linear acrylate can effectively break the hydrogen bond network in lipoic acid oligomers, avoid the formation of lipoic acid oligomers, thereby effectively reducing the viscosity of lipoic acid-based ink and improving the stability of lipoic acid-based ink, therefore, the lipoic acid-based ink of the present invention is suitable for additive manufacturing to prepare 3D materials.

[0023] At the same time, lipoic acid has abundant reaction sites. The ink composed of linear acrylate can be copolymerized through chemical click reaction to form a high-strength network structure. Moreover, the dynamic disulfide bonds in the molecular structure of lipoic acid can give 3D materials excellent toughness and degradability. The molecular chain segments of linear acrylate can also improve the toughness and biocompatibility of 3D materials, thereby providing new solutions for the development of tissue engineering and biomedical implants.

[0024] Preferably, the molar ratio of the linear acrylate to the lipoic acid is 0.1:1-1:1, and more preferably 0.2:1-0.6:1. Such a setting is more conducive to reducing the viscosity of the lipoic acid-based ink and improving the stability of the lipoic acid-based ink, while ensuring the strength of the 3D material obtained by additive manufacturing.

[0025] The present invention does not make any special requirements for the selection of linear acrylates. For example, the linear acrylate can be selected from at least one of polyethylene glycol diacrylate (PEGDA), diethylene glycol diacrylate (DEGDA), triethylene glycol diacrylate (TEGDA), ethoxylated bisphenol A diacrylate (EO-BPA DA), and ethoxybisphenol fluorene diacrylate (BPFDA). In some embodiments, the linear acrylate is preferably polyethylene glycol diacrylate. Furthermore, the molecular weight of the polyethylene glycol diacrylate is preferably 500-1500, which is beneficial to reduce the viscosity of the lipoic acid-based ink.

[0026] The photoinitiator can ensure that the lipoic acid-based ink undergoes a cross-linking reaction and solidifies under light conditions. The present invention does not limit the selection of the photoinitiator, and Irgacure 819 and the like are preferred. Optionally, the molar ratio of the lipoic acid to the photoinitiator is 20:1-80:1, for example, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, etc., or a range consisting of any two of these values, thereby enabling the lipoic acid-based ink to be rapidly and evenly solidified.

[0027] In some embodiments, the lipoic acid-based ink of the present invention further includes a crosslinking agent and / or an ester compound, for example, the lipoic acid-based ink further includes a crosslinking agent, or the lipoic acid-based ink further includes an ester compound, or the lipoic acid-based ink further includes a crosslinking agent and an ester compound. Furthermore, the introduction of a crosslinking agent can further improve the toughness of the 3D material, and the introduction of an ester compound can further reduce the viscosity of the lipoic acid-based ink and adjust the porosity of the 3D material.

[0028] Further, the molar ratio of the thioctic acid to the cross-linking agent is preferably 1:0.2-1:1.5, for example 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, etc., or a range consisting of any two of these values. Further preferably, the thioctic acid to the cross-linking agent is 1:0.2-1:1.5, for example 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, etc., or a range consisting of any two of these values. The molar ratio of the cross-linking agent is 1:0.5-1:1; the molar ratio of the thioctic acid to the ester compound is 0.1:1-10:1, for example 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, etc., or a range consisting of any two of these values. Further preferably, the molar ratio of the thioctic acid to the ester compound is 1:1-5:1.

[0029] For the selection of cross-linking agents, the present invention preferably uses a cross-linking agent with three or more double bonds, which can increase the cross-linking sites and improve the performance of the 3D material, such as at least one of pentaerythritol tetraacrylate (PETA), methacryloyl gelatin (GelMA), four-arm polyethylene glycol acrylate (4-arm PEG), and methacryloyl hyaluronic acid (HAMA); for the selection of ester compounds, the present invention preferably uses C6-C 12 An ester compound, such as at least one of dodecyl acetate, decyl acetate, and undecyl acetate.

[0030] Since the lipoic acid-based ink of the present invention has low viscosity and good stability, it is suitable for preparing 3D materials by additive manufacturing. Therefore, the present invention also provides a 3D material prepared by using the lipoic acid-based ink.

[0031] It can be understood that the desired product can be directly manufactured by additive manufacturing using the lipoic acid-based ink of the present invention. Since lipoic acid is a coenzyme with excellent antioxidant and antibacterial properties, and linear acrylates can improve the biocompatibility of 3D materials, tissue engineering materials and biomedical implants, such as bioscaffolds, can be directly manufactured by additive manufacturing. Preferably, when the lipoic acid-based ink of the present invention is used to manufacture bioscaffolds by additive manufacturing, ester compounds are preferably introduced into the lipoic acid-based ink to improve the pore structure.

[0032] Specifically, the present invention also provides a method for preparing the 3D material, wherein the preparation method uses a 3D printer to print lipoic acid-based ink to obtain the 3D material.

[0033] Among them, the present invention is not limited to the method of 3D printing. For example, using DLP (digital light processing) printing technology, the printing speed is preferably 0.01mm / s-1mm / s, such as 0.01mm / s, 0.05mm / s, 0.1mm / s, 0.5mm / s, 1mm / s, etc., or a range consisting of any two of these values.

[0034] It is understandable that after printing, it is first soaked in a solvent such as isopropyl alcohol to remove the uncured components.

[0035] Hereinafter, the lipoic acid-based ink, 3D material and preparation method thereof will be further described through the following specific examples.

[0036] Example 1

[0037] 1 mmol of lipoic acid (TA) and 0.1 mmol of polyethylene glycol diacrylate (PEGDA, molecular weight 575) were added to a sample bottle, which was then placed on a heated stirrer and heated to 90°C for 10 min to allow the lipoic acid and polyethylene glycol diacrylate to be fully dissolved and mixed evenly, and then 0.0125 mmol of photoinitiator Irg 819 was added to obtain lipoic acid-based ink.

[0038] The lipoic acid-based ink obtained above was placed on a circular PDMS transparent substrate, and 405nm ultraviolet light was used to expose the lipoic acid-based ink layer by layer at a printing speed of 0.2mm / s. After exposure, it was soaked in isopropanol for 10min to remove uncured components, slightly stirred, and then allowed to stand and dry to obtain a 3D material.

[0039] Example 2

[0040] 1 mmol of lipoic acid (TA) and 0.3 mmol of polyethylene glycol diacrylate (PEGDA, molecular weight 575) were added to a sample bottle, and then placed on a heated stirrer and heated to 90°C for 10 minutes to allow lipoic acid and polyethylene glycol diacrylate to fully dissolve and mix evenly, and then 0.015 mmol of photoinitiator Irg 819 was added to obtain lipoic acid-based ink.

[0041] The lipoic acid-based ink obtained above was placed on a circular PDMS transparent substrate, and 405nm ultraviolet light was used to expose the lipoic acid-based ink layer by layer at a printing speed of 0.2mm / s. After exposure, it was soaked in isopropanol for 10min to remove uncured components, slightly stirred, and then allowed to stand and dry to obtain a 3D material.

[0042] Example 3

[0043] 1 mmol lipoic acid (TA) and 0.5 mmol polyethylene glycol diacrylate (PEGDA, molecular weight 575) were added to a sample bottle, and then placed on a heated stirrer and heated to 90°C for 10 min to allow lipoic acid and polyethylene glycol diacrylate to fully dissolve and mix evenly, and then 0.025 mmol photoinitiator Irg 819 was added to obtain lipoic acid-based ink, recorded as TAA-0.

[0044] The lipoic acid-based ink obtained above was placed on a circular PDMS transparent substrate, and 405nm ultraviolet light was used to expose the lipoic acid-based ink layer by layer at a printing speed of 0.2mm / s. After exposure, it was soaked in isopropanol for 10min to remove uncured components, slightly stirred, and then allowed to stand and dry to obtain a 3D material.

[0045] Example 4

[0046] 1 mmol lipoic acid (TA) and 0.8 mmol polyethylene glycol diacrylate (PEGDA, molecular weight 575) were added to a sample bottle, and then placed on a heated stirrer and heated to 90°C for 10 min to allow lipoic acid and polyethylene glycol diacrylate to fully dissolve and mix evenly, and then 0.035 mmol photoinitiator Irg 819 was added to obtain lipoic acid-based ink.

[0047] The lipoic acid-based ink obtained above was placed on a circular PDMS transparent substrate, and 405nm ultraviolet light was used to expose the lipoic acid-based ink layer by layer at a printing speed of 0.2mm / s. After exposure, it was soaked in isopropanol for 10min to remove uncured components, slightly stirred, and then allowed to stand and dry to obtain a 3D material.

[0048] Example 5

[0049] 1 mmol of lipoic acid (TA) and 1 mmol of polyethylene glycol diacrylate (PEGDA, molecular weight 575) were added to a sample bottle, which was then placed on a heated stirrer and heated to 90°C for 10 min to allow the lipoic acid and polyethylene glycol diacrylate to be fully dissolved and mixed evenly, and then 0.05 mmol of photoinitiator Irg 819 was added to obtain lipoic acid-based ink.

[0050] The lipoic acid-based ink obtained above was placed on a circular PDMS transparent substrate, and 405nm ultraviolet light was used to expose the lipoic acid-based ink layer by layer at a printing speed of 0.2mm / s. After exposure, it was soaked in isopropanol for 10min to remove uncured components, slightly stirred, and then allowed to stand and dry to obtain a 3D material.

[0051] Comparative Example 1

[0052] 1 mmol lipoic acid (TA) and 0.05 mmol polyethylene glycol diacrylate (PEGDA, molecular weight 575) were added to a sample bottle, and then placed on a heated stirrer and heated to 90°C for 10 min to allow lipoic acid and polyethylene glycol diacrylate to fully dissolve and mix evenly, and then 0.025 mmol photoinitiator Irg 819 was added to obtain lipoic acid-based ink.

[0053] The lipoic acid-based ink obtained above was placed on a circular PDMS transparent substrate, and 405nm ultraviolet light was used to expose the lipoic acid-based ink layer by layer at a printing speed of 0.2mm / s. After exposure, it was soaked in isopropanol for 10min to remove uncured components, slightly stirred, and then allowed to stand and dry to obtain a 3D material.

[0054] Comparative Example 2

[0055] 1mmol lipoic acid (TA) and 0.5mmol polyether F127 diacrylate (F127DA, molecular weight 12.6kDa) were added to a sample bottle, and then placed on a heated stirrer and heated to 90°C for 10 minutes to fully dissolve and mix lipoic acid and polyethylene glycol diacrylate, and then 0.025mmol photoinitiator Irg 819 was added to obtain lipoic acid-based ink. Due to the large molecular weight of F127DA, it has little effect on the hydrogen bond network of lipoic acid. The viscosity of lipoic acid-based ink is as high as 20000mPa·s, which is not suitable for 3D printing.

[0056] The lipoic acid-based inks of Examples 1 to 5 and Comparative Example 1 and the 3D materials printed using the lipoic acid-based inks were subjected to performance tests, and the results are shown in Table 1. The viscosity test standard is GB / T 22235-2008, the shelf life is determined based on whether it is a gel, the toughness test standard is ASTM F2512-20a, and the porosity test standard is the hydrogel porosity using the ethanol weighing method.

[0057] Table 1

[0058]

[0059] Example 6

[0060] 1 mmol of lipoic acid (TA) and 0.5 mmol of polyethylene glycol diacrylate (PEGDA) were added to a sample bottle, which was then placed on a heated stirrer and heated to 90°C for 10 min to allow the lipoic acid and polyethylene glycol diacrylate to be fully dissolved and mixed evenly, and then 0.2 mmol of pentaerythritol tetraacrylate (PETA) and 0.025 mmol of photoinitiator Irg 819 were added to obtain lipoic acid-based ink.

[0061] The lipoic acid-based ink obtained above was placed on a circular PDMS transparent substrate, and 405nm ultraviolet light was used to expose the lipoic acid-based ink layer by layer at a printing speed of 0.2mm / s. After exposure, it was soaked in isopropanol for 10min to remove uncured components, slightly stirred, and then allowed to stand and dry to obtain a 3D material.

[0062] Example 7

[0063] 1 mmol lipoic acid (TA) and 0.5 mmol polyethylene glycol diacrylate (PEGDA) were added to a sample bottle, which was then placed on a heated stirrer and heated to 90°C for 10 min to allow lipoic acid and polyethylene glycol diacrylate to fully dissolve and mix evenly. Then, 0.5 mmol four-arm polyethylene glycol acrylate (4-arm PEG) and 0.025 mmol photoinitiator Irg819 were added to obtain lipoic acid-based ink.

[0064] The lipoic acid-based ink obtained above was placed on a circular PDMS transparent substrate, and 405nm ultraviolet light was used to expose the lipoic acid-based ink layer by layer at a printing speed of 0.2mm / s. After exposure, it was soaked in isopropanol for 10min to remove uncured components, slightly stirred, and then allowed to stand and dry to obtain a 3D material.

[0065] Example 8

[0066] 1 mmol lipoic acid (TA) and 0.5 mmol polyethylene glycol diacrylate (PEGDA) were added to a sample bottle, which was then placed on a heated stirrer and heated to 90°C for 10 min to allow lipoic acid and polyethylene glycol diacrylate to fully dissolve and mix evenly, and then 0.5 mmol pentaerythritol tetraacrylate (PETA) and 0.025 mmol photoinitiator Irg 819 were added to obtain a lipoic acid-based ink, recorded as TAA-2.

[0067] The lipoic acid-based ink obtained above was placed on a circular PDMS transparent substrate, and 405nm ultraviolet light was used to expose the lipoic acid-based ink layer by layer at a printing speed of 0.2mm / s. After exposure, it was soaked in isopropanol for 10min to remove uncured components, slightly stirred, and then allowed to stand and dry to obtain a 3D material.

[0068] Example 9

[0069] 1 mmol lipoic acid (TA) and 0.5 mmol polyethylene glycol diacrylate (PEGDA) were added to a sample bottle, which was then placed on a heated stirrer and heated to 90°C for 10 min to allow lipoic acid and polyethylene glycol diacrylate to be fully dissolved and mixed evenly. Then, 1 mmol pentaerythritol tetraacrylate (PETA) and 0.025 mmol photoinitiator Irg 819 were added to obtain a lipoic acid-based ink, which was recorded as TAA-4.

[0070] The lipoic acid-based ink obtained above was placed on a circular PDMS transparent substrate, and 405nm ultraviolet light was used to expose the lipoic acid-based ink layer by layer at a printing speed of 0.2mm / s. After exposure, it was soaked in isopropanol for 10min to remove uncured components, slightly stirred, and then allowed to stand and dry to obtain a 3D material.

[0071] Example 10

[0072] 1 mmol of lipoic acid (TA) and 0.5 mmol of polyethylene glycol diacrylate (PEGDA) were added to a sample bottle, which was then placed on a heated stirrer and heated to 90°C for 10 min to allow lipoic acid and polyethylene glycol diacrylate to be fully dissolved and mixed evenly, and then 1.5 mmol of pentaerythritol tetraacrylate (PETA) and 0.025 mmol of photoinitiator Irg 819 were added to obtain a lipoic acid-based ink, which was recorded as TAA-6.

[0073] The lipoic acid-based ink obtained above was placed on a circular PDMS transparent substrate, and 405nm ultraviolet light was used to expose the lipoic acid-based ink layer by layer at a printing speed of 0.2mm / s. After exposure, it was soaked in isopropanol for 10min to remove uncured components, slightly stirred, and then allowed to stand and dry to obtain a 3D material.

[0074] Embodiment 11

[0075] 1 mmol lipoic acid (TA) and 0.5 mmol polyethylene glycol diacrylate (PEGDA) were added to a sample bottle, which was then placed on a heated stirrer and heated to 90°C for 10 min to allow lipoic acid and polyethylene glycol diacrylate to be fully dissolved and mixed evenly, and then 2 mmol pentaerythritol tetraacrylate (PETA) and 0.025 mmol photoinitiator Irg 819 were added to obtain a lipoic acid-based ink, which was recorded as TAA-8.

[0076] The lipoic acid-based ink obtained above was placed on a circular PDMS transparent substrate, and 405nm ultraviolet light was used to expose the lipoic acid-based ink layer by layer at a printing speed of 0.2mm / s. After exposure, it was soaked in isopropanol for 10min to remove uncured components, slightly stirred, and then allowed to stand and dry to obtain a 3D material.

[0077] The lipoic acid-based inks of Examples 6 to 11 and the 3D materials printed using the lipoic acid-based inks were subjected to performance tests, and the results are shown in Table 2.

[0078] Table 2

[0079]

[0080]

[0081] As shown in Table 1, the increase in the amount of crosslinking agent will affect the shelf life of lipoic acid-based ink and the toughness of 3D materials, but has little effect on the viscosity of lipoic acid-based ink; Figure 1 It can be seen that with the increase in the amount of the cross-linking agent, the toughness of the 3D material first increases and then decreases, so the molar ratio of lipoic acid to the cross-linking agent is preferably 1:0.2-1:1.5, and more preferably 1:0.5-1:1.

[0082] Example 12

[0083] 1 mmol of lipoic acid (TA) and 0.5 mmol of polyethylene glycol diacrylate (PEGDA) were added to a sample bottle, which was then placed on a heated stirrer and heated to 90°C for 10 min to allow lipoic acid and polyethylene glycol diacrylate to be fully dissolved and mixed evenly, and then 0.5 mmol of pentaerythritol tetraacrylate (PETA), 0.025 mmol of photoinitiator Irg 819 and 2.88 mmol of dodecyl acetate were added to obtain lipoic acid-based ink.

[0084] The lipoic acid-based ink obtained above was placed on a circular PDMS transparent substrate, and 405nm ultraviolet light was used to expose the lipoic acid-based ink layer by layer at a printing speed of 0.2mm / s. After exposure, it was soaked in isopropanol for 10min to remove uncured components, slightly stirred, and then allowed to stand and dry to obtain a 3D material.

[0085] from Figure 2 It can be seen that a nanoporous structure is formed in the 3D material after the porogen is added.

[0086] Embodiment 13

[0087] 1 mmol of lipoic acid (TA) and 0.5 mmol of polyethylene glycol diacrylate (PEGDA) were added to a sample bottle, which was then placed on a heated stirrer and heated to 90°C for 10 min to allow lipoic acid and polyethylene glycol diacrylate to be fully dissolved and mixed evenly, and then 0.5 mmol of pentaerythritol tetraacrylate (PETA), 0.025 mmol of photoinitiator Irg 819 and 1 mmol of dodecyl acetate were added to obtain lipoic acid-based ink.

[0088] The lipoic acid-based ink obtained above was placed on a circular PDMS transparent substrate, and 405nm ultraviolet light was used to expose the lipoic acid-based ink layer by layer at a printing speed of 0.2mm / s. After exposure, it was soaked in isopropanol for 10min to remove uncured components, slightly stirred, and then allowed to stand and dry to obtain a 3D material.

[0089] Embodiment 14

[0090] 1 mmol of lipoic acid (TA) and 0.5 mmol of polyethylene glycol diacrylate (PEGDA) were added to a sample bottle, which was then placed on a heated stirrer and heated to 90°C for 10 min to allow lipoic acid and polyethylene glycol diacrylate to be fully dissolved and mixed evenly, and then 0.5 mmol of pentaerythritol tetraacrylate (PETA), 0.025 mmol of photoinitiator Irg 819 and 0.5 mmol of dodecyl acetate were added to obtain lipoic acid-based ink.

[0091] The lipoic acid-based ink obtained above was placed on a circular PDMS transparent substrate, and 405nm ultraviolet light was used to expose the lipoic acid-based ink layer by layer at a printing speed of 0.2mm / s. After exposure, it was soaked in isopropanol for 10min to remove uncured components, slightly stirred, and then allowed to stand and dry to obtain a 3D material.

[0092] Embodiment 15

[0093] 1 mmol of lipoic acid (TA) and 0.5 mmol of polyethylene glycol diacrylate (PEGDA) were added to a sample bottle, which was then placed on a heated stirrer and heated to 90°C for 10 min to allow lipoic acid and polyethylene glycol diacrylate to be fully dissolved and mixed evenly, and then 0.5 mmol of pentaerythritol tetraacrylate (PETA), 0.025 mmol of photoinitiator Irg 819 and 0.2 mmol of dodecyl acetate were added to obtain lipoic acid-based ink.

[0094] The lipoic acid-based ink obtained above was placed on a circular PDMS transparent substrate, and 405nm ultraviolet light was used to expose the lipoic acid-based ink layer by layer at a printing speed of 0.2mm / s. After exposure, it was soaked in isopropanol for 10min to remove uncured components, slightly stirred, and then allowed to stand and dry to obtain a 3D material.

[0095] Example 16

[0096] 1 mmol of lipoic acid (TA) and 0.5 mmol of polyethylene glycol diacrylate (PEGDA) were added to a sample bottle, which was then placed on a heated stirrer and heated to 90°C for 10 min to allow lipoic acid and polyethylene glycol diacrylate to be fully dissolved and mixed evenly, and then 0.5 mmol of pentaerythritol tetraacrylate (PETA), 0.025 mmol of photoinitiator Irg 819 and 0.1 mmol of dodecyl acetate were added to obtain lipoic acid-based ink.

[0097] The lipoic acid-based ink obtained above was placed on a circular PDMS transparent substrate, and 405nm ultraviolet light was used to expose the lipoic acid-based ink layer by layer at a printing speed of 0.2mm / s. After exposure, it was soaked in isopropanol for 10min to remove uncured components, slightly stirred, and then allowed to stand and dry to obtain a 3D material.

[0098] Comparative Example 3

[0099] 1 mmol of lipoic acid (TA) was added to a sample bottle, which was then placed on a heated stirrer and heated to 90°C for 10 min. Then, 0.5 mmol of pentaerythritol tetraacrylate (PETA), 0.025 mmol of photoinitiator Irg 819 and 2.88 mmol of dodecyl acetate were added, and a gelation reaction occurred, and no lipoic acid ink could be obtained.

[0100] Comparative Example 4

[0101] 1 mmol of lipoic acid (TA) was added to a sample bottle, which was then placed on a heated stirrer and heated to 90°C for 10 min. Then, 0.1 mmol of pentaerythritol tetraacrylate (PETA), 0.025 mmol of photoinitiator Irg 819 and 2.88 mmol of dodecyl acetate were added, and a gelation reaction occurred, and no lipoic acid ink could be obtained.

[0102] The lipoic acid-based inks of Examples 12 to 16 and the 3D materials printed using the lipoic acid-based inks were subjected to performance tests, and the results are shown in Table 3.

[0103] Table 3

[0104]

[0105] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0106] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A lipoic acid-based ink, characterized in that The lipoic acid-based ink comprises lipoic acid, linear acrylate and a photoinitiator, wherein the molar ratio of the linear acrylate to the lipoic acid is greater than or equal to 0.1:1, and the molecular weight of the linear acrylate is less than or equal to 2000.

2. The lipoic acid-based ink according to claim 1, characterized in that The linear acrylate is selected from at least one of polyethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, ethoxylated bisphenol A diacrylate, and ethoxylated bisphenol fluorene diacrylate; And / or, the molar ratio of the linear acrylate to the lipoic acid is 0.1:1-1:

1.

3. The lipoic acid-based ink according to claim 1, characterized in that The molar ratio of the lipoic acid to the photoinitiator is 20:1-80:

1.

4. The lipoic acid-based ink according to any one of claims 1 to 3, characterized in that The lipoic acid-based ink further comprises a cross-linking agent and / or an ester compound, the molar ratio of the lipoic acid to the cross-linking agent is 1:0.2-1:1.5, and the molar ratio of the lipoic acid to the ester compound is 0.1:1-10:

1.

5. The lipoic acid-based ink according to claim 4, characterized in that The cross-linking agent is selected from at least one of pentaerythritol tetraacrylate, methacrylated gelatin, four-arm polyethylene glycol acrylate, and methacrylated hyaluronic acid.

6. The lipoic acid-based ink according to claim 4, characterized in that The ester compound is selected from at least one of dodecyl acetate, decyl acetate and undecyl acetate.

7. A 3D material prepared using the lipoic acid-based ink as claimed in any one of claims 1 to 6.

8. The 3D material according to claim 7, characterized in that: The 3D material is a biological scaffold.

9. A method for preparing a 3D material as claimed in claim 7 or 8, characterized in that: The lipoic acid-based ink is printed using a 3D printer to obtain a 3D material.

10. The method for preparing the 3D material according to claim 9, characterized in that: The printing speed is 0.01mm / s-1mm / s.

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