Photocurable 3D printable material, photocured 3D printed gel product and method for preparing the same

Abstract

The application provides a photocurable 3D printing material, a photocured 3D printing gel product and a preparation method thereof, the photocurable 3D printing material comprises a polymerizable monomer, a UV initiator and an imidazole ionic liquid without carbon-carbon double bond, wherein, no polymerization inhibitor or UV absorber is added. The application firstly finds that the ionic liquid has a polymerization inhibition function, the photocurable 3D printing material can not add the polymerization inhibitor or the UV absorber, the ionic liquid replaces the polymerization inhibitor, and polymerization can also be prevented. In addition, the photocured 3D printing gel product has good transparency and can be applied to various occasions, and has excellent electric conductivity, which provides a research idea for manufacturing high-precision conductive sensors.

Description

Technical Field

[0001] This invention relates to the field of intelligent polymer materials technology, and more specifically to photocurable 3D printable materials, photocurable 3D printing gel products and their preparation methods. Background Technology

[0002] In 3D printing technology, the most important photopolymer 3D printing technologies are SLA (StereoLithography Apparatus), DLP (Digital Light Processing), and the CLIP (Continuous Liquid Interface Production) technology developed from them. Photopolymer 3D printing is suitable for printing models or products with high precision requirements, good surface quality, and fine details. It is currently the most widely used 3D printing technology in the industrial field. Currently, the materials used in photopolymer 3D printing are photosensitive resins, including epoxy resins, phenolic resins, acrylic resins, amino resins, polyethersulfone resins, fluorocarbon resins, and bio-based resins.

[0003] In existing technologies, to prevent excessive polymerization during the photopolymerization 3D printing process from affecting printing accuracy, a certain amount of polymerization inhibitor is often added to the system to prevent excessive polymerization and improve printing accuracy. However, polymerization inhibitors are generally colored dyes, and the printed samples will have different colors (for example, currently, oxysulfuron is a relatively effective polymerization inhibitor, making the sample appear yellow), which limits its application in some situations where good sample transparency is required.

[0004] Given the problems and shortcomings of existing technologies, the preparation of tribologically tunable gradient materials still requires further improvement and development. Summary of the Invention

[0005] This invention provides a photocurable 3D printing material, a photocurable 3D printing gel product, and a method for preparing the same. The specific technical solution is as follows:

[0006] A photopolymerizable 3D printable material includes a polymerizable monomer, a UV initiator, and an imidazole ionic liquid without carbon-carbon double bonds, wherein no polymerization inhibitor or UV absorber is added, and the imidazole ionic liquid is used as a polymerization inhibitor.

[0007] Furthermore, the imidazole ionic liquids that do not contain carbon-carbon double bonds are 1-butyl-3-methylimidazolium tetrafluoroborate, 1,3-dimethylimidazolium nitrate, or 1-ethyl-3-methylimidazolium ethyl sulfate.

[0008] Furthermore, the polymerizable monomers are acrylamide and / or acrylic acid;

[0009] Furthermore, the polymerizable monomers are acrylamide and acrylic acid;

[0010] Furthermore, it also includes polyethylene glycol diacrylate;

[0011] Further, the polymerizable monomer is 50-80 parts, the ultraviolet photoinitiator is 0.1-0.3 parts, the imidazole ionic liquid without carbon-carbon double bonds is 0.5-2 parts, and the polyethylene glycol diacrylate is 3-6 parts.

[0012] In addition, the present invention also provides a photocurable 3D printing gel product, which is obtained by printing the above-mentioned photocurable 3D printing material using a photocurable 3D printing method.

[0013] This invention also provides a method for preparing a photopolymerizable 3D printed gel product, comprising the following steps: mixing and dissolving various raw materials in water according to a certain ratio to obtain a mixture, introducing the mixture into the resin tank of a 3D printing device, performing 3D modeling using the software of the photopolymerizable 3D printer, and then performing 3D printing to obtain the gel product.

[0014] Furthermore, for each printed layer of product, the UV irradiation time is 6-10 seconds.

[0015] Furthermore, the power of the ultraviolet light is 100-200mW.

[0016] Due to the adoption of the above technical solutions, the beneficial technical effects of the present invention are as follows:

[0017] 1. This invention is the first to discover that ionic liquids have polymerization inhibition function. Materials that can be photocured for 3D printing do not need to be added with polymerization inhibitors or ultraviolet light absorbers. Ionic liquids can replace polymerization inhibitors and can also prevent rapid polymerization.

[0018] 2. The photopolymer 3D printing gel product of this invention has good transparency and can be used in various occasions;

[0019] 3. The photopolymer 3D printing gel product of this invention has excellent electrical conductivity, which provides a research approach for manufacturing high-precision conductive sensors. Attached Figure Description

[0020] Figure 1 Image of the gel product prepared in Example 1;

[0021] Figure 2 Image of the gel product prepared for Comparative Example 1.

[0022] Figure 3 Image of the gel product prepared for Comparative Example 2. Detailed Implementation

[0023] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0024] A photopolymerizable 3D printing material comprises a polymerizable monomer, a UV photoinitiator, and an imidazole-based ionic liquid without carbon-carbon double bonds. No polymerization inhibitor or UV absorber is added; the imidazole-based ionic liquid acts as the polymerization inhibitor. This invention, by using an ionic liquid instead of a polymerization inhibitor without adding one, effectively prevents rapid polymerization and results in a product with good transparency. Furthermore, the addition of the ionic liquid imparts beneficial electrical conductivity to the product. This invention solves the problem in existing technologies where the addition of polymerization inhibitors leads to products with varying colors.

[0025] Imidazole ionic liquids that do not contain carbon-carbon double bonds are 1-butyl-3-methylimidazolium tetrafluoroborate, 1,3-dimethylimidazolium nitrate, or 1-ethyl-3-methylimidazolium ethyl sulfate. If imidazolium ionic liquids contain carbon-carbon double bonds, these double bonds will react with the double bonds of polymerizable monomers, participating in polymerization and affecting the properties of the finished product.

[0026] The polymerizable monomers are acrylamide and / or acrylic acid. More preferably, the polymerizable monomers are acrylamide and acrylic acid.

[0027] In addition, materials that can be photopolymerized for 3D printing include polyethylene glycol diacrylate, which is used as a chain extender for chain growth in 3D printing.

[0028] By weight, the polymerizable monomer is 50-80 parts, the ultraviolet photoinitiator is 0.1-0.3 parts, the imidazole ionic liquid without carbon-carbon double bonds is 0.5-2 parts, and the polyethylene glycol diacrylate is 3-6 parts.

[0029] The preparation method of photopolymerizable 3D printing gel products includes the following steps: mixing polymerizable monomers, ultraviolet photoinitiators and imidazole ionic liquids without carbon-carbon double bonds in water according to a certain ratio to obtain a mixture, introducing the mixture into the resin tank of a 3D printing device, performing 3D modeling using the software of the photopolymerizable 3D printer, and then performing 3D printing to obtain the gel product.

[0030] Furthermore, for each printed layer of product, the UV irradiation time is 6-10 seconds.

[0031] Furthermore, the power of the ultraviolet light is 100-200mW. Compared with the existing photopolymerization 3D printing technology, this invention adjusts the ultraviolet light irradiation time and ultraviolet light power according to the actual preparation method of photopolymerization 3D printing gel products. The ultraviolet light irradiation time and ultraviolet light power are matched with the paper cup method, so that the curing effect of the gel product is optimal.

[0032] Example 1

[0033] Preparation method of photopolymer 3D printing gel products

[0034] A mixture of 35 parts acrylamide, 30 parts acrylic acid, 0.2 parts UV photoinitiator, 1 part 1-butyl-3-methylimidazolium tetrafluoroborate, and 4 parts polyethylene glycol diacrylate was dissolved in 100 parts water to obtain a mixture. The mixture was then introduced into the resin tank of a 3D printing device. 3D modeling was performed using the software of the photopolymer 3D printer. After modeling, 3D printing was performed, controlling the UV irradiation time for each printed layer to be 8 seconds and the UV power to be 150mW, to obtain a gel product.

[0035] Example 2

[0036] Preparation method of photopolymer 3D printing gel products

[0037] A mixture of 50 parts acrylamide, 0.1 parts UV photoinitiator, 0.5 parts 1,3-dimethylimidazolium nitrate, and 3 parts polyethylene glycol diacrylate was dissolved in 100 parts water to obtain a mixture. The mixture was then introduced into the resin tank of a 3D printing device. 3D modeling was performed using the software of the photopolymer 3D printer. After modeling, 3D printing was performed, controlling the UV irradiation time for each printed layer to be 6 seconds and the UV power to be 200mW, to obtain a gel product.

[0038] Example 3

[0039] Preparation method of photopolymer 3D printing gel products

[0040] A mixture of 80 parts acrylic acid, 0.3 parts UV photoinitiator, 2 parts 1,3-dimethylimidazolium nitrate, and 6 parts polyethylene glycol diacrylate was dissolved in 100 parts water to obtain a mixture. The mixture was then introduced into the resin tank of a 3D printing equipment. 3D modeling was performed using the software of the photopolymer 3D printer. After modeling, 3D printing was performed, controlling the UV irradiation time for each printed layer to be 10 seconds and the UV power to be 100mW, to obtain a gel product.

[0041] Comparative Example 1

[0042] Compared to Example 1, 1-butyl-3-methylimidazolium tetrafluoroborate was not added, but the other steps were the same as in Example 1.

[0043] Comparative Example 2

[0044] Compared with Example 1, 1-butyl-3-methylimidazolium tetrafluoroborate was not added, but 0.1 parts of Olisin polymerization inhibitor were added, and the other steps were the same as in Example 1.

[0045] The products obtained in Example 1 and Comparative Examples 1-2 were visually observed, and the results are as follows: Figure 1-3 As shown. Figure 1 The product contains no other colors mixed in. Figure 2 The product produced explosive polymerization and Figure 2 Part A in the middle is yellow, while Figure 3 Product B is yellow in color due to the addition of a polymerization inhibitor. In Comparative Example 1, the reaction underwent explosive polymerization, resulting in a product that cannot be used normally.

[0046] The conductivity of the products obtained in Examples 1-3 and Comparative Examples 1-2 was tested, and the test results are shown in Table 1 below.

[0047] Table 1. Results of conductivity tests on the products obtained in Examples 1-3 and Comparative Examples 1-2.

[0048] Example 1 180kΩ Example 2 212kΩ Example 3 120kΩ Comparative Example 1 5MΩ Comparative Example 2 3MΩ

[0049] As clearly shown in Table 1 above, the resistance values ​​of the products obtained in Examples 1-3 and Comparative Examples 1-2 are not on the same order of magnitude. The resistance value of the products in Examples 1-3 is much smaller than that of the products obtained in Comparative Examples 1-2. In other words, the conductivity of the products in Examples 1-3 is better than that of the products obtained in Comparative Examples 1-2. This provides a research approach for manufacturing high-precision conductive sensors. In addition, the conductivity of the product is also related to the amount of example liquid added. The more example liquid added, the better the conductivity of the product.

[0050] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A photopolymerizable 3D printable material, characterized in that, Its formulation consists of polymerizable monomers, ultraviolet photoinitiators, and imidazole ionic liquids without carbon-carbon double bonds. No polymerization inhibitors or ultraviolet absorbers are added, and imidazole ionic liquids without carbon-carbon double bonds replace polymerization inhibitors. Its raw materials also include polyethylene glycol diacrylate; By mass, the polymerizable monomer is 50-80 parts, the ultraviolet photoinitiator is 0.1-0.3 parts, the imidazole ionic liquid without carbon-carbon double bonds is 0.5-2 parts, and the polyethylene glycol diacrylate is 3-6 parts. Imidazole ionic liquids that do not contain carbon-carbon double bonds are 1-butyl-3-methylimidazolium tetrafluoroborate, 1,3-dimethylimidazolium nitrate, or 1-ethyl-3-methylimidazolium ethyl sulfate. The polymerizable monomers are acrylamide and / or acrylic acid.

2. A photocurable 3D printing gel product, obtained by printing the photocurable 3D printing material as described in claim 1 using a photocurable 3D printing method.

3. A method for preparing the photocurable 3D printing gel product as described in claim 2, characterized in that, Includes the following steps: The raw materials are mixed and dissolved in water according to the proportion to obtain a mixture. The mixture is then introduced into the resin tank of the 3D printing equipment. The software of the photopolymer 3D printer is used to create a 3D model. After modeling, the product is 3D printed to obtain a gel product. During 3D printing, the UV irradiation time is 6-10 seconds for each layer of the product being printed; In 3D printing, the power of ultraviolet light is 100-200 mW.

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