Eugenol-based recyclable photocuring 3D printing material as well as preparation method and application thereof

Abstract

The invention discloses an eugenol-based recyclable light-cured 3D printing material as well as a preparation method and application thereof. The preparation method comprises the following steps: firstly, adding eugenol, a polythiol compound, a photoinitiator and an organic solvent into a reactor, uniformly stirring, irradiating with an ultraviolet lamp, then adding isocyanate methacrylate and a catalyst, and reacting to obtain an eugenol-based dynamic phenol urethane acrylate photosensitive prepolymer; adding a diluting monomer and a photoinitiator into the synthesized photosensitive prepolymer, uniformly stirring, and removing bubbles to obtain the eugenol-based recyclable photocuring 3D printing material. The obtained resin can be converted into photocuring 3D printing resin again through chemical recovery after 3D printing molding. The obtained resin has the advantages of good thermal / mechanical properties, excellent chemical recycling property, moderate transmission depth coefficient and the like, and is expected to be used for printing handicrafts, sacrificial molds, biological scaffold materials and the like. Therefore, the method has great significance in promoting sustainable development of the photocuring 3D printing material.

Description

Technical Field

[0001] The present invention belongs to the field of recyclable light-curable 3D printing materials, and in particular relates to a eugenol-based recyclable light-curable 3D printing material and an application thereof. Background Art

[0002] 3D printing, also known as additive manufacturing, is a cutting-edge technology that constructs three-dimensional objects layer by layer based on digital model files. It is hailed as one of the hallmark technologies of the "Fourth Industrial Revolution." With its significant advantages of free design, rapid prototyping, and material conservation, 3D printing has gained widespread application in fields such as tissue engineering, soft robotics, aerospace, transportation, and consumer goods. Among photocurable 3D printing technologies, stereolithography, digital light processing, and liquid crystal display (LCD) have attracted significant attention for their high-precision printing results. As the cornerstone of this technology, photocurable resins, whose performance directly determines the final quality of 3D printed products, are essential. However, current photocurable resins primarily consist of a mixture of difunctional (or multifunctional) photosensitive prepolymers, diluent monomers, photoinitiators, and a small amount of additives. After printing, these resins transform into infusible and insoluble thermosetting polymers, making them difficult to recycle and reuse. This not only wastes resources but also poses environmental risks.

[0003] Recyclable photocurable 3D printing materials refer to materials whose liquid resins, after being formed through photocuring 3D printing, can be converted back into photocurable 3D printing liquid resins. Due to their closed-loop recycling and high recycling value, these materials are becoming a hot topic in research on recyclable photocurable 3D printing materials. Based on the type of chemical bond utilized, these materials can be divided into dynamic covalent bonds (DCB) and non-DCB types (such as van der Waals forces and hydrogen bonds). DCB is a type of covalent bond that can restructure in response to external stimuli (such as light, heat, force, and pH), inducing dynamic adjustments in the polymer network structure, thereby endowing the material with self-healing, recyclable processing, and plasticity. Compared to non-DCB types, DCB-based recyclable photocurable materials are more popular due to their superior thermal and mechanical properties, greater dimensional stability, and improved solvent resistance. At present, many DCBs such as thioester bonds, β-hydroxyester bonds, β-carbonyl ester bonds, hindered urea bonds, etc. have been used to prepare this type of resin materials (Materials Horizons 2018, 5 (6), 1042; Advanced Materials 2023, 35 (20), 2211417; Materials & Design 2021, 197, 109189; Chemical Engineering Journal 2023, 475, 146080.). However, an important problem with this type of resin is that it is difficult to achieve both high performance (strong mechanical properties and good heat resistance) and easy recycling (mild recycling conditions, fast speed, and high recycling efficiency). This issue is related to whether such materials can be truly applied.

[0004] On the other hand, biomass resources have the advantages of being naturally renewable, widely available, inexpensive, and biodegradable. Therefore, their effective utilization can alleviate major problems such as fossil resource depletion, greenhouse effect, and environmental pollution from the source. Lignin is the second largest natural renewable resource after cellulose and is considered to be the only biomass source that is promising for large-scale extraction of benzene ring compounds. Natural phenolic compounds derived from lignin, such as vanillin and eugenol, are ideal raw materials for the preparation of high-performance polymers due to their rigid benzene ring structure. However, there are currently no reports on the use of lignin and natural phenols to prepare recyclable photocurable materials (including 3D printing materials). Summary of the Invention

[0005] Technical problem to be solved: The present invention aims to overcome the shortcomings of current recyclable light-curable 3D printing resin materials, such as the difficulty in achieving both high performance and easy recycling, and the environmentally unfriendly raw material sources, and to provide a eugenol-based recyclable light-curable 3D printing material and its preparation method and application.

[0006] Technical solution: A method for preparing a eugenol-based recyclable photocurable 3D printing material, comprising the following steps: (1) adding eugenol, a polythiol compound, a photoinitiator, and an organic solvent into a reactor, stirring the mixture evenly, and irradiating the mixture with ultraviolet light for 1 to 4 hours; then adding a methacrylate isocyanate monomer and a dynamic phenolurethane directional bonding catalyst; and continuing the reaction at a temperature of 50 to 100° C. for 3 to 9 hours to obtain a eugenol-based dynamic phenolurethane photosensitive prepolymer, wherein eugenol: polythiol compound: methacrylate isocyanate monomer The molar ratio of the raw materials is (2-4):1:(2-4), the amount of the catalyst is 0.5%-2% of the total weight of the raw materials, the amount of the photoinitiator is 1-5% of the total weight of the raw materials, and the amount of the organic solvent is 100%-200% of the total weight of the raw materials; (2) adding the diluent monomer and the photoinitiator to the photosensitive prepolymer obtained in step 1, the amount of the diluent monomer is 20%-50% of the total resin system, the amount of the photoinitiator is 1-5% of the total weight of the obtained resin, stirring evenly, removing bubbles, and obtaining a eugenol-based recyclable light-curable 3D printing material.

[0007] The polythiol compound in step (1) is at least one of tetrakis(3-mercaptopropionic acid) pentaerythritol ester, pentaerythritol tetrakismercaptoacetate, 2,3-dithio(2-mercapto)-1-propanethiol, trimethylolpropane tris(3-mercaptopropionate), 2-2'-(1,2-ethylenedioxy)bis(ethylenethiol), and mercapto-polyethylene glycol-thiol.

[0008] The organic solvent is at least one of acetone, tetrahydrofuran, ethyl acetate and toluene, and the amount used is 100% of the total weight of the raw materials.

[0009] The methacrylate isocyanate monomer is at least one of methyl methacrylate isocyanate and ethyl methacrylate isocyanate.

[0010] The dynamic phenol urethane directional bonding catalyst is at least one of dibutyltin dilaurate, 1,4-diazabicyclo[2.2.2]octane, and triethylenediamine, and the amount used is 1.0% of the total weight of the raw materials.

[0011] The molar ratio of the raw materials of eugenol: polythiol compound: methacrylate isocyanate is 4:1:4.

[0012] The diluting monomer in step (2) is at least one of methyl acrylate, vinyl acetate, isobornyl acrylate, tetrahydrofuran methacrylate, isobornyl methacrylate, and pentaerythritol tetraacrylate, and the amount used is 40% of the total resin system.

[0013] In step (1) and step (2), the photoinitiator is at least one of benzoin dimethyl ether, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, chlorobenzophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone and methyl benzoylformate, and the amount used is 2% of the total weight of the obtained photocurable resin.

[0014] The eugenol-based recyclable photocurable 3D printing material prepared by the above method.

[0015] The application of the above-mentioned eugenol-based recyclable light-curable 3D printing material in the preparation of handicrafts, sacrificial molds, dental materials and biological scaffold material products.

[0016] During the above printing process, the light-curing 3D printing resin transmission depth coefficient is 0.11-0.29mn.

[0017] Beneficial effects: (1) The eugenol-based photocurable 3D printing material synthesized by the present invention has excellent recyclability and high recycling efficiency, and can be used as a main resin for handicrafts, sacrificial molds, dental materials, biological scaffold materials, etc.; (2) The synthesized bio-based photocurable resin has strong mechanical properties and good heat resistance; (3) The synthesis method used by the present invention is simple in process and easy to operate, and is suitable for large-scale industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is the synthetic route of eugenol-based dynamic phenol amino ester photosensitive prepolymer.

[0019] Figure 2 This is the FT-IR spectrum of eugenol-based dynamic phenol amino ester photosensitive prepolymer. DETAILED DESCRIPTION

[0020] The following examples of the present invention are only intended to further illustrate the present invention and are not intended to limit the present invention or its scope.

[0021] Example 1

[0022] (1) Eugenol, pentaerythritol tetrakis(3-mercaptopropionic acid), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone (photoinitiator) and ethyl acetate (organic solvent) were added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate (dynamic phenol urethane directional bonding catalyst) were added. The reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol urethane photosensitive prepolymer, wherein the molar ratio of eugenol: pentaerythritol tetrakis(3-mercaptopropionic acid): ethyl isocyanate methacrylate was 4:1:4, the amount of the catalyst was 1% of the total weight of the raw materials, the amount of the organic solvent was 100% of the total weight of the raw materials; and the amount of the photoinitiator was 2% of the total weight of the raw materials.

[0023] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 20% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total weight of the obtained resin. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0024] Example 2

[0025] (1) Eugenol, pentaerythritol tetrakis(3-mercaptopropionate), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate were added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate were added. The reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol amino ester photosensitive prepolymer, wherein the molar ratio of eugenol: pentaerythritol tetrakis(3-mercaptopropionate): ethyl isocyanate methacrylate was 4:1:4, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0026] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 30% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0027] Example 3

[0028] (1) Eugenol, pentaerythritol tetrakis(3-mercaptopropionate), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate were added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate were added. The reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol amino ester photosensitive prepolymer, wherein the molar ratio of eugenol: pentaerythritol tetrakis(3-mercaptopropionate): ethyl isocyanate methacrylate was 4:1:4, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0029] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 40% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0030] Example 4

[0031] (1) Eugenol, pentaerythritol tetramercaptoacetate, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate are added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate are added. The reaction is continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenolurethane photosensitive prepolymer, wherein the molar ratio of eugenol: pentaerythritol tetramercaptoacetate: ethyl isocyanate methacrylate is 4:1:4, the amount of catalyst is 1% of the total weight of the raw materials, the amount of organic solvent is 100% of the total weight of the raw materials; and the amount of photoinitiator is 2% of the total weight of the raw materials.

[0032] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 20% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total weight of the obtained resin. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0033] Example 5

[0034] (1) Eugenol, pentaerythritol tetramercaptoacetate, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate are added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate are added. The reaction is continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenolurethane photosensitive prepolymer, wherein the molar ratio of eugenol: pentaerythritol tetramercaptoacetate: ethyl isocyanate methacrylate is 4:1:4, the amount of catalyst is 1% of the total weight of the raw materials, the amount of organic solvent is 100% of the total weight of the raw materials; and the amount of photoinitiator is 2% of the total weight of the raw materials.

[0035] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 30% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0036] Example 6

[0037] (1) Eugenol, pentaerythritol tetramercaptoacetate, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate are added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate are added. The reaction is continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenolurethane photosensitive prepolymer, wherein the molar ratio of eugenol: pentaerythritol tetramercaptoacetate: ethyl isocyanate methacrylate is 4:1:4, the amount of catalyst is 1% of the total weight of the raw materials, the amount of organic solvent is 100% of the total weight of the raw materials; and the amount of photoinitiator is 2% of the total weight of the raw materials.

[0038] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 40% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0039] Example 7

[0040] (1) Eugenol, trimethylolpropane tris(3-thiopropionate), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate were added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate were added. The reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol urethane photosensitive prepolymer, wherein the molar ratio of eugenol:trimethylolpropane tris(3-thiopropionate):ethyl isocyanate methacrylate was 3:1:3, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0041] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 20% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total weight of the obtained resin. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0042] Example 8

[0043] (1) Eugenol, trimethylolpropane tris(3-thiopropionate), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate were added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate were added. The reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol urethane photosensitive prepolymer, wherein the molar ratio of eugenol:trimethylolpropane tris(3-thiopropionate):ethyl isocyanate methacrylate was 3:1:3, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0044] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 30% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0045] Example 9

[0046] (1) Eugenol, trimethylolpropane tris(3-thiopropionate), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate were added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate were added. The reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol urethane photosensitive prepolymer, wherein the molar ratio of eugenol:trimethylolpropane tris(3-thiopropionate):ethyl isocyanate methacrylate was 3:1:3, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0047] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 40% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0048] Example 10

[0049] (1) Eugenol, 2,3-dithio(2-mercapto)-1-propanethiol, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate were added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate were added. The reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol amino ester photosensitive prepolymer, wherein the molar ratio of eugenol: 2,3-dithio(2-mercapto)-1-propanethiol: ethyl isocyanate methacrylate was 3:1:3, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0050] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 20% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total weight of the obtained resin. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0051] Example 11

[0052] (1) Add eugenol, 2,3-dithio(2-mercapto)-1-propanethiol, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate into a reactor, stir evenly and irradiate with 36W ultraviolet light for 1 hour, then add ethyl isocyanate methacrylate and dibutyltin dilaurate, and continue to react at a temperature of 60-90°C for 5 hours to obtain eugenol-based dynamic phenol amino ester photosensitive prepolymer, wherein the molar ratio of eugenol: 2,3-dithio(2-mercapto)-1-propanethiol: ethyl isocyanate methacrylate is 3:1:3, the amount of catalyst is 1% of the total weight of the raw materials, the amount of organic solvent is 100% of the total weight of the raw materials; the amount of photoinitiator is 2% of the total weight of the raw materials.

[0053] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 30% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0054] Example 12

[0055] (1) Eugenol, 2,3-dithio(2-mercapto)-1-propanethiol, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate were added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate were added. The reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol amino ester photosensitive prepolymer, wherein the molar ratio of eugenol: 2,3-dithio(2-mercapto)-1-propanethiol: ethyl isocyanate methacrylate was 3:1:3, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0056] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 40% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0057] Example 13

[0058] (1) Eugenol, 2-2'-(1,2-ethylenedioxy)bis(ethylenethiol), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate were added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate were added. The reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol amino ester photosensitive prepolymer, wherein the molar ratio of eugenol: 2-2'-(1,2-ethylenedioxy)bis(ethylenethiol): ethyl isocyanate methacrylate was 2:1:2, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0059] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 20% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total weight of the obtained resin. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0060] Example 14

[0061] (1) Eugenol, 2-2'-(1,2-ethylenedioxy)bis(ethylenethiol), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate were added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate were added. The reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol amino ester photosensitive prepolymer, wherein the molar ratio of eugenol: 2-2'-(1,2-ethylenedioxy)bis(ethylenethiol): ethyl isocyanate methacrylate was 2:1:2, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0062] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 30% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0063] Example 15

[0064] (1) Eugenol, 2-2'-(1,2-ethylenedioxy)bis(ethylenethiol), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate were added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate were added. The reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol amino ester photosensitive prepolymer, wherein the molar ratio of eugenol: 2-2'-(1,2-ethylenedioxy)bis(ethylenethiol): ethyl isocyanate methacrylate was 2:1:2, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0065] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 40% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0066] Example 16

[0067] (1) Eugenol, mercapto-polyethylene glycol-thiol, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate are added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate are added. The reaction is continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol urethane photosensitive prepolymer, wherein the molar ratio of eugenol: mercapto-polyethylene glycol-thiol: ethyl isocyanate methacrylate is 2:1:2, the amount of catalyst is 1% of the total weight of the raw materials, the amount of organic solvent is 100% of the total weight of the raw materials; and the amount of photoinitiator is 2% of the total weight of the raw materials.

[0068] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 20% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total weight of the obtained resin. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0069] Example 17

[0070] (1) Eugenol, mercapto-polyethylene glycol-thiol, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate are added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate are added. The reaction is continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol urethane photosensitive prepolymer, wherein the molar ratio of eugenol: mercapto-polyethylene glycol-thiol: ethyl isocyanate methacrylate is 2:1:2, the amount of catalyst is 1% of the total weight of the raw materials, the amount of organic solvent is 100% of the total weight of the raw materials; and the amount of photoinitiator is 2% of the total weight of the raw materials.

[0071] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 30% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0072] Example 18

[0073] (1) Eugenol, mercapto-polyethylene glycol-thiol, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate are added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate are added. The reaction is continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol urethane photosensitive prepolymer, wherein the molar ratio of eugenol: mercapto-polyethylene glycol-thiol: ethyl isocyanate methacrylate is 2:1:2, the amount of catalyst is 1% of the total weight of the raw materials, the amount of organic solvent is 100% of the total weight of the raw materials; and the amount of photoinitiator is 2% of the total weight of the raw materials.

[0074] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 40% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0075] Example 19

[0076] (1) Eugenol, pentaerythritol tetrakis(3-mercaptopropionate), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate were added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then methyl isocyanate methacrylate and dibutyltin dilaurate were added. The reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol amino ester photosensitive prepolymer, wherein the molar ratio of eugenol: pentaerythritol tetrakis(3-mercaptopropionate): methyl isocyanate methacrylate was 4:1:4, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0077] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 40% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0078] Example 20

[0079] (1) Eugenol, trimethylolpropane tris(3-thiopropionate), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate were added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then methyl isocyanate methacrylate and dibutyltin dilaurate were added. The reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol urethane photosensitive prepolymer, wherein the molar ratio of eugenol:trimethylolpropane tris(3-thiopropionate):methyl isocyanate methacrylate was 3:1:3, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0080] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 40% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0081] Example 21

[0082] (1) Eugenol, 2-2'-(1,2-ethylenedioxy)bis(ethylenethiol), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate were added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then methyl isocyanate methacrylate and dibutyltin dilaurate were added. The reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol amino ester photosensitive prepolymer, wherein the molar ratio of eugenol: 2-2'-(1,2-ethylenedioxy)bis(ethylenethiol): methyl isocyanate methacrylate was 2:1:2, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0083] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 40% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0084] Example 22

[0085] (1) Eugenol, pentaerythritol tetrakis(3-mercaptopropionate), dimethyl benzoin and acetone were added to a reactor, stirred evenly and then irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and 1,4-diazabicyclo[2.2.2]octane were added, and the reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol amino ester photosensitive prepolymer, wherein the molar ratio of eugenol: pentaerythritol tetrakis(3-mercaptopropionate): ethyl isocyanate methacrylate was 4:1:4, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0086] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 50% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0087] Example 23

[0088] (1) Eugenol, pentaerythritol tetrakis(3-mercaptopropionate), benzophenone chloride and tetrahydrofuran were added to a reactor, stirred evenly and then irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and triethylenediamine were added, and the reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenolurethane photosensitive prepolymer, wherein the molar ratio of eugenol: pentaerythritol tetrakis(3-mercaptopropionate): ethyl isocyanate methacrylate was 4:1:4, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0089] (2) Tetrahydrofuran methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, wherein the amount of tetrahydrofuran methacrylate is 50% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0090] Example 24

[0091] (1) Eugenol, pentaerythritol tetrakis(3-mercaptopropionate), dimethyl benzoin and toluene were added to a reactor, stirred evenly and then irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and triethylenediamine were added, and the reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenolurethane photosensitive prepolymer, wherein the molar ratio of eugenol: pentaerythritol tetrakis(3-mercaptopropionate): ethyl isocyanate methacrylate was 4:1:4, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0092] (2) Tetrahydrofuran methacrylate and methyl benzoylformate (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, with the amount of tetrahydrofuran methacrylate being 50% by weight of the obtained resin system and the amount of photoinitiator being 2% by weight of the total resin obtained. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0093] Example 25

[0094] (1) Eugenol, pentaerythritol tetrakis(3-mercaptopropionate), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate were added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate were added. The reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol amino ester photosensitive prepolymer, wherein the molar ratio of eugenol: pentaerythritol tetrakis(3-mercaptopropionate): ethyl isocyanate methacrylate was 4:1:4, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0095] (2) Methyl acrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) are added to the photosensitive prepolymer synthesized in step 1, with the amount of methyl acrylate being 40% by weight of the obtained resin system and the amount of photoinitiator being 2% by weight of the total resin obtained. The mixture is stirred evenly and bubbles are removed to obtain a eugenol-based recyclable photocurable 3D printing material.

[0096] Example 26

[0097] (1) Eugenol, pentaerythritol tetrakis(3-mercaptopropionate), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate were added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate were added. The reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol amino ester photosensitive prepolymer, wherein the molar ratio of eugenol: pentaerythritol tetrakis(3-mercaptopropionate): ethyl isocyanate methacrylate was 4:1:4, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0098] (2) Add vinyl acetate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) to the photosensitive prepolymer synthesized in step 1, with the amount of vinyl acetate being 40% by weight of the obtained resin system and the amount of photoinitiator being 2% by weight of the total resin obtained. Stir evenly and remove bubbles to obtain a eugenol-based recyclable photocurable 3D printing material.

[0099] Example 27

[0100] (1) Eugenol, pentaerythritol tetrakis(3-mercaptopropionate), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate were added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate were added. The reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol amino ester photosensitive prepolymer, wherein the molar ratio of eugenol: pentaerythritol tetrakis(3-mercaptopropionate): ethyl isocyanate methacrylate was 4:1:4, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0101] (2) Add isobornyl acrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) to the photosensitive prepolymer synthesized in step 1, wherein the amount of isobornyl acrylate is 40% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. Stir evenly and remove bubbles to obtain a eugenol-based recyclable photocurable 3D printing material.

[0102] Example 28

[0103] (1) Eugenol, pentaerythritol tetrakis(3-mercaptopropionate), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate were added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate were added. The reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol amino ester photosensitive prepolymer, wherein the molar ratio of eugenol: pentaerythritol tetrakis(3-mercaptopropionate): ethyl isocyanate methacrylate was 4:1:4, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0104] (2) Add isobornyl methacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) to the photosensitive prepolymer synthesized in step 1, wherein the amount of isobornyl methacrylate is 40% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. Stir evenly and remove bubbles to obtain a eugenol-based recyclable photocurable 3D printing material.

[0105] Example 29

[0106] (1) Eugenol, pentaerythritol tetrakis(3-mercaptopropionate), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone and ethyl acetate were added to a reactor, stirred evenly and irradiated with a 36W ultraviolet lamp for 1 hour, and then ethyl isocyanate methacrylate and dibutyltin dilaurate were added. The reaction was continued at a temperature of 60-90°C for 5 hours to obtain a eugenol-based dynamic phenol amino ester photosensitive prepolymer, wherein the molar ratio of eugenol: pentaerythritol tetrakis(3-mercaptopropionate): ethyl isocyanate methacrylate was 4:1:4, the amount of catalyst was 1% of the total weight of the raw materials, the amount of organic solvent was 100% of the total weight of the raw materials; and the amount of photoinitiator was 2% of the total weight of the raw materials.

[0107] (2) Add pentaerythritol tetraacrylate and 2-hydroxy-2-methyl-1-phenyl-1-propanone (photoinitiator) to the photosensitive prepolymer synthesized in step 1, wherein the amount of pentaerythritol tetraacrylate is 40% by weight of the obtained resin system and the amount of photoinitiator is 2% by weight of the total resin obtained. Stir evenly and remove bubbles to obtain a eugenol-based recyclable light-curable 3D printing material.

[0108] Example 30

[0109] 100g of each resin from Examples 1 to 29 was weighed, stirred for 20min, and degassed. Photocuring 3D printing: Form3SLA photocuring 3D printer (Formlabs, USA). Tensile properties: The mechanical properties of the photocuring model were measured using a SANS7CMT-4304 universal testing machine (Shenzhen Xinsansi Instrument Co., Ltd.) in accordance with ASTM D638-2008, with a gauge length of 50mm and a tensile rate of 5.0mm / min. The model size was 80x10x1mm. 2 . Glass transition temperature (T g The dynamic thermomechanical properties were measured using a Q800 solid analyzer (TA, USA). g The recyclability is determined by the peak value of the loss factor (tan δ) versus temperature curve. Recyclability: 3D printed specimens were ground into powder and then chemically degraded in a mixture of ethyl isocyanate methacrylate and diluted monomer at 100-120°C for 1-3 hours. After complete degradation, a certain amount of eugenol-based tetraphenol was added to obtain recycled resin. The resulting resin was re-solidified and its tensile properties and T were measured using the same method as above. g , and calculate the recycling efficiency (ratio of recycled resin to original resin performance). 3D printing penetration depth (Z d ): Calculate the following equation derived from the Beer-Lambert law: Z d =D p ln t d / t0, where Z d , t0, td and I0 are respectively the curing depth, critical exposure time, exposure time (resin surface) and Z d = 0; by plotting 1n(t d ) and Z d The working curve between D p .

[0110] Table 1 Properties and 3D printing parameters of resin samples of Examples 1 to 29

[0111]

[0112]

[0113] Inventions CN117624489A, CN117645690A and CN112029043A are control examples 1, 2 and 3 respectively. As can be seen from the data in the table, the eugenol-based recyclable photocurable 3D printing material prepared by the present invention has good thermal / mechanical properties, excellent chemical recycling recyclability, and a moderate resin transmission depth coefficient, and is expected to be used for printing handicrafts, sacrificial molds, biological scaffold materials, etc.

[0114] The above examples are intended only to illustrate the technical concepts and features of the present invention. Their purpose is to enable those skilled in the art to understand the contents of the present invention and implement them accordingly. They are not intended to limit the scope of protection of the present invention. Any equivalent changes or modifications made in accordance with the spirit of the present invention are intended to be covered by the scope of protection of the present invention.

Claims

1. A method for preparing a eugenol-based recyclable light-curable 3D printing material, characterized in that: The preparation steps are as follows: (1) adding eugenol, polythiol compound, photoinitiator and organic solvent into a reactor, stirring evenly and irradiating with ultraviolet light for 1-4 hours, then adding methacrylic acid isocyanate monomer and dynamic phenol urethane directional bonding catalyst, and continuing the reaction at 50-100°C for 3-9 hours to obtain eugenol-based dynamic phenol urethane photosensitive prepolymer, wherein the molar ratio of eugenol: polythiol compound: methacrylic acid isocyanate monomer is (2-4):1:(2 ~4), the amount of catalyst is 0.5%~2% of the total weight of the raw materials, the amount of photoinitiator is 1~5% of the total weight of the raw materials, and the amount of organic solvent is 100%~200% of the total weight of the raw materials; (2) adding the diluent monomer and photoinitiator to the photosensitive prepolymer obtained in step 1, the amount of diluent monomer is 20%~50% of the total resin system, the amount of photoinitiator is 1~5% of the total weight of the obtained resin, stirring evenly, removing bubbles, and obtaining eugenol-based recyclable light-curable 3D printing material.

2. The method for preparing the eugenol-based recyclable light-curable 3D printing material according to claim 1, characterized in that: The polythiol compound in step (1) is at least one of tetrakis(3-mercaptopropionic acid)pentaerythritol ester, tetrakismercaptoacetic acid pentaerythritol ester, 2,3-dithio(2-mercapto)-1-propanethiol, trimethylolpropane tris(3-mercaptopropionate), 2-2'-(1,2-ethylenedioxy)bis(ethylenethiol), and mercapto-polyethylene glycol-thiol.

3. The method for preparing the eugenol-based recyclable light-curable 3D printing material according to claim 1, characterized in that: The organic solvent in step (1) is at least one of acetone, tetrahydrofuran, ethyl acetate, and toluene, and the amount used is 100% of the total weight of the raw materials.

4. The method for preparing the eugenol-based recyclable light-curable 3D printing material according to claim 1, characterized in that: The methacrylate isocyanate monomer in step (1) is at least one of methyl methacrylate isocyanate and ethyl methacrylate isocyanate.

5. The method for preparing the eugenol-based recyclable light-curable 3D printing material according to claim 1, characterized in that: The dynamic phenolurethane directional bonding catalyst in step (1) is at least one of dibutyltin dilaurate, 1,4-diazabicyclo[2.2.2]octane, and triethylenediamine, and the amount used is 1.0% of the total weight of the raw materials; the molar ratio of the raw materials of eugenol: polythiol compound: methacrylic acid isocyanate is 4:1:

4.

6. The method for preparing the eugenol-based recyclable light-curable 3D printing material according to any one of claims 1 to 5, characterized in that: The diluting monomer in step (2) is at least one of methyl acrylate, vinyl acetate, isobornyl acrylate, tetrahydrofuran methacrylate, isobornyl methacrylate, and pentaerythritol tetraacrylate, and the amount used is 40% of the total resin system.

7. The method for preparing the eugenol-based recyclable light-curable 3D printing material according to claim 6, characterized in that: In step (1) and step (2), the photoinitiator is at least one of benzoin dimethyl ether, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, chlorobenzophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone and methyl benzoylformate, and the amount used is 2% of the total weight of the obtained photocurable resin.

8. The eugenol-based recyclable light-curable 3D printing material prepared by the method of claim 7.

9. Use of the eugenol-based recyclable light-curable 3D printing material according to claim 8 in the preparation of handicrafts, sacrificial molds, dental materials and biological scaffold materials.

10. The use according to claim 9, characterized in that During the printing process, the light-curing 3D printing resin transmission depth coefficient is 0.11-0.29mn.

Images