A kind of soybean oil-based hybrid material for enhanced 3D printing and its preparation method and application

Abstract

The present application belongs to the field of 3D printing technology, and in particular, relates to an enhanced 3D printed soybean oil-based hybrid material, a preparation method and an application thereof; the preparation method of the enhanced 3D printed soybean oil-based hybrid material provided by the present application comprises first preparing a 3D slurry containing raw materials such as epoxy soybean oil acrylate, a diluent, a photoinitiator, n-butyl zirconate, a photoacid generator, a silane coupling agent and a leveling agent, and then sequentially performing 3D printing and baking to obtain a nano-dioxide enhanced 3D printed soybean oil-based hybrid material; and the mechanical properties of the nano-dioxide enhanced 3D printed soybean oil-based hybrid material are further improved by the selection of the photoacid generator, which can solve the technical problem that the existing preparation method cannot prepare a 3D printed soybean oil resin material with high mechanical strength.

Description

Technical Field

[0001] The present application belongs to the field of 3D printing technology, and in particular, relates to an enhanced 3D printing soybean oil-based hybrid material and a preparation method and application thereof. Background Art

[0002] Soybean oil comes from the renewable plant soybean and has the advantages of low price, biocompatibility, degradability, and easy modification. There are many double bonds in the triglyceride chains in soybean oil, but the reactivity of these double bonds is very low and they cannot directly undergo polymerization reactions. Before soybean oil is currently used in the industrial field, the double bonds on soybean oil are generally modified and derivatized to obtain valuable soybean oil derivatives.

[0003] For example, soybean oil can be modified and derivatized to prepare various types of soybean oil polyols, which can be directly used as raw materials for synthesizing different polyurethanes. For example, soybean oil is first epoxidized under the action of hydrogen peroxide and organic acid to obtain epoxidized soybean oil, and then the epoxidized soybean oil is reacted with acrylic acid to generate epoxidized soybean oil acrylate, which can be used to prepare 3D printing soybean oil resin materials; however, due to the limitation of the long-chain fat structure of soybean oil, the soybean oil resin material obtained by 3D printing using epoxidized soybean oil acrylate has low mechanical properties such as tensile strength and elongation at break. Therefore, 3D printing soybean oil resin materials prepared with soybean oil are currently mainly used in the field of coatings with low strength requirements. In the fields with high strength requirements such as automobile bodies, building walls, plastic containers, packaging materials, and plastic parts, petroleum-based resin materials are currently mainly used.

[0004] Soybean oil comes from the renewable plant soybean and is a green and degradable biomass resource. By improving the mechanical properties of 3D printed soybean oil-based materials, it is expected to replace traditional petroleum-based materials with green and degradable biomass resources and achieve sustainable development. Summary of the invention

[0005] In view of this, the present application provides an enhanced 3D printing soybean oil-based hybrid material and a preparation method and application, which are used to solve the technical problem that the existing preparation method cannot prepare 3D printing soybean oil resin materials with high mechanical strength.

[0006] The first aspect of the present application provides a method for preparing a soybean oil-based hybrid material for enhanced 3D printing, the preparation method comprising the steps of:

[0007] Step S1, mixing epoxy soybean oil acrylate, diluent, photoinitiator, n-butyl zirconate, photoacid generator, silane coupling agent and leveling agent uniformly to obtain soybean oil-based hybrid slurry;

[0008] Step S2, using a light-curing 3D printer to 3D print the soybean oil-based hybrid slurry to obtain a 3D printed soybean oil-based hybrid material;

[0009] Step S3, baking the 3D printed soybean oil-based hybrid material to obtain a reinforced 3D printed soybean oil-based hybrid material;

[0010] In step S1, the mass ratio of the epoxy soybean oil acrylate to the diluent is 40-55:22.5-35.

[0011] Preferably, in step S1, the photoacid generator is selected from a mixture of diphenyl-(4-phenylsulfonium)phenylsulfonium hexafluorophosphate and 2-isopropylthioxanthone, a mixture of diphenyl[4-(phenylthio)phenyl]-sulfonium hexafluoroantimonate and 2-isopropylthioxanthone, or a mixture of bis(4-(diphenylsulfonium)phenyl)sulfide-bishexafluorophosphate and 2-isopropylthioxanthone.

[0012] Preferably, in the mixture of diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate and 2-isopropylthioxanthone, the mass ratio of diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate to 2-isopropylthioxanthone is 1:0.05-0.15.

[0013] Preferably, in the mixture of diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate and 2-isopropylthioxanthone, the mass ratio of diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate to 2-isopropylthioxanthone is 1: 0.08-0.12.

[0014] In the mixture of diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate and 2-isopropylthioxanthone, the mass ratio of diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate to 2-isopropylthioxanthone is 4-5:0.2-0.5.

[0015] Preferably, in step S1, calculated in parts by mass, the mass ratio of the epoxy soybean oil acrylate, diluent, photoinitiator, n-butyl zirconate, photoacid generator, silane coupling agent and leveling agent is 40~55:22.5~35:1~3:10~20:2~4:2~4:0.1~0.3.

[0016] Preferably, in step S1, the diluent is selected from at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate;

[0017] The photoinitiator is selected from at least one of TPO-L, 819, 1173, and TMO;

[0018] The silane coupling agent is selected from at least one of KH550, KH560 and KH570;

[0019] The leveling agent is selected from BYK-371.

[0020] Preferably, in step S2, the light-curing 3D printer is selected from an LCD light-curing 3D printer, and the ultraviolet light curing wavelength in the 3D printing process is 250-405 nm.

[0021] Preferably, in step S2, the 3D printed soybean oil-based hybrid material is selected from a 3D printed soybean oil-based hybrid material in the shape of a hollow sphere, a 3D printed soybean oil-based hybrid material in the shape of a hollow cube, a 3D printed soybean oil-based hybrid material in the shape of a hollow cuboid, or a 3D printed soybean oil-based hybrid material in the shape of a hollow cylinder.

[0022] Preferably, in step S3, the baking temperature is 70-90° C. and the baking time is 24-72 hours.

[0023] The second aspect of the present application provides an enhanced 3D printing soybean oil-based hybrid material, which is prepared by the preparation method described in the first aspect.

[0024] The third aspect of the present application provides an application of the enhanced 3D printing soybean oil-based hybrid material described in the second aspect in the preparation of plastic containers, packaging materials, and plastic parts.

[0025] In summary, the present application provides an enhanced 3D printed soybean oil-based hybrid material, a preparation method and an application thereof. The preparation method of the enhanced 3D printed soybean oil-based hybrid material provided by the present application includes: firstly 3D printing a 3D slurry containing raw materials such as epoxy soybean oil acrylate, a diluent, a photoinitiator, n-butyl zirconate, a photoacid generator, a silane coupling agent and a leveling agent to obtain a 3D printed soybean oil-based hybrid material, and then baking the 3D printed soybean oil-based hybrid material to cause the acid-catalyzed n-butyl zirconate in the 3D printed soybean oil-based hybrid material to undergo a sol-gel reaction to in situ synthesize nano zirconium dioxide with a small particle size and uniform dispersion, so that the performance of the nano zirconium dioxide is fully exerted, thereby obtaining a nano-zirconium dioxide enhanced 3D printed soybean oil-based hybrid material, which solves the technical problem that the existing preparation method cannot prepare a 3D printed soybean oil resin material with high mechanical strength. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the specific implementation methods of the present application or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0027] Figure 1A schematic diagram of the acid generation principle of the photoacid generator provided in the examples of this application;

[0028] Figure 2 A schematic diagram of a method for preparing an enhanced 3D printing soybean oil-based hybrid material provided in an embodiment of the present application;

[0029] Figure 3 A total reflection infrared spectrum of an enhanced 3D printed soybean oil-based hybrid material prepared by a preparation method of an enhanced 3D printed soybean oil-based hybrid material provided in Example 1 of the present application;

[0030] Figure 4 An electron microscope schematic diagram of zirconium dioxide for an enhanced 3D printed soybean oil-based hybrid material prepared by a method for preparing an enhanced 3D printed soybean oil-based hybrid material provided in Example 1 of the present application;

[0031] Figure 5 An electron microscope schematic diagram of zirconium dioxide of a 3D printed soybean oil-based hybrid material prepared by a method for preparing a 3D printed soybean oil-based hybrid material provided in Example 17 of the present application;

[0032] Figure 6 A physical picture of the enhanced 3D printed soybean oil-based hybrid material prepared by the method for preparing an enhanced 3D printed soybean oil-based hybrid material provided in Examples 1 and 18 of the present application. DETAILED DESCRIPTION

[0033] The present application provides an enhanced 3D printed soybean oil-based hybrid material and a preparation method and application thereof, which are used to solve the technical problem that the existing preparation method cannot prepare a 3D printed soybean oil resin material with high mechanical strength.

[0034] The technical solution of the present application will be described clearly and completely below in conjunction with the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.

[0035] In view of the low mechanical strength of the current 3D printed soybean oil-based materials, such as tensile strength and elongation at break, it is difficult to apply them to fields with higher strength, which limits the further application and expansion of 3D printed soybean oil-based materials; the present application provides a method for preparing an enhanced 3D printed soybean oil-based hybrid material, and the schematic diagram of the preparation method is as follows Figure 2As shown, the preparation method includes the steps of: firstly, mixing epoxy soybean oil acrylate, diluent, photoinitiator, n-butyl zirconate, photoacid generator, silane coupling agent and leveling agent uniformly to obtain soybean oil-based hybrid slurry; then using a light-curing 3D printer to 3D print the soybean oil-based hybrid slurry to obtain a 3D printed soybean oil-based hybrid material; and then baking the 3D printed soybean oil-based hybrid material to obtain a reinforced 3D printed soybean oil-based hybrid material.

[0036] In the preparation method of the enhanced 3D printing soybean oil-based hybrid material provided in the present application, the epoxy soybean oil acrylate, diluent, photoinitiator and leveling agent in the 3D printing slurry are used to form a matrix of the 3D printing soybean oil-based hybrid material under ultraviolet light irradiation, and the photoacid generator in n-butyl zirconate, photoacid generator and silane coupling agent can be photolyzed and acidified under ultraviolet light irradiation. The schematic diagram of photolysis and acidification is shown in FIG. Figure 1 As shown, the generated acid is evenly dispersed in the matrix of the 3D printed soybean oil-based hybrid material, so that in the subsequent baking process, it can catalyze the zirconium dioxide precursor (n-butyl zirconate) to undergo a sol-gel reaction to in-situ synthesize nano zirconium dioxide. The in-situ synthesized nano zirconium dioxide has a small particle size and is evenly distributed inside and outside. The silane coupling agent also further improves the dispersibility of inorganic nano zirconium dioxide with small particle size and high surface energy in the organic soybean oil-based hybrid material, reducing the agglomeration of nano zirconium dioxide. At the same time, compared with ethyl orthosilicate, n-butyl zirconate is extremely sensitive to moisture, and only a little moisture in the air is enough to cause it to undergo a sol-gel reaction. -The nano zirconium dioxide is synthesized in situ by the gel reaction, thereby reducing the introduction of deionized water, which leads to the deterioration of the compatibility between the original oil phase and the introduced water phase of the system, the difficulty in controlling the sol-gel process, and the easy agglomeration of nano zirconium dioxide. The present application is beneficial to enhancing the mechanical properties of soybean oil-based hybrid materials by in situ synthesizing nano zirconium dioxide with small particle size and good dispersibility. At the same time, in order to enable the soybean oil-based hybrid materials to be better formed into shapes such as spheres and cuboids, it is necessary to control the mass ratio of epoxy soybean oil acrylate and diluent. In the present application, the mass ratio of epoxy soybean oil acrylate and diluent is 40~55:22.5~35.

[0037] Preferably, in the preparation method of the enhanced 3D printing soybean oil-based hybrid material provided in the present application, for the selection of the photoacid generator, a mixture of diphenyl-(4-phenylsulfonium)phenylsulfonium hexafluorophosphate and 2-isopropylthioxanthone, a mixture of diphenyl [4-(phenylthio)phenyl]-sulfonium hexafluoroantimonate and 2-isopropylthioxanthone, and a mixture of bis(4-(diphenylsulfonium)phenyl)sulfide-bishexafluorophosphate and 2-isopropylthioxanthone can be selected. These photoacid generators can catalyze the zirconium dioxide precursor (n-butyl zirconate) to undergo a sol-gel reaction to in-situ synthesize nano zirconium dioxide;

[0038] At the same time, there are differences in the performance of different photoacid generators. The solubility of the mixture of diphenyl [4- (phenylthio) phenyl] - hexafluoroantimonate sulfonium and 2-isopropylthioxanthone is poor, while the mixture of bis (4- (diphenylsulfonium) phenyl) sulfide-bis hexafluorophosphate and 2-isopropylthioxanthone absorbs ultraviolet light and releases it in the form of light; the acid generation efficiency of these two photoacid generators is low. Therefore, in order to improve the effect of catalyzing the zirconium dioxide precursor (n-butyl zirconate) to undergo a sol-gel reaction to in situ synthesize nano zirconium dioxide, the mixture of diphenyl- (4-phenylthio) phenyl sulfonium hexafluorophosphate and 2-isopropylthioxanthone should be further preferred.

[0039] Preferably, in the preparation method of the enhanced 3D printed soybean oil-based hybrid material provided by the present application, in order to better promote the contact between moisture in the air and the enhanced 3D printed soybean oil-based hybrid material, the shape of the 3D printed soybean oil-based hybrid material obtained by printing with a 3D printer in the present application should select a 3D printed hollow shape, such as a hollow spherical 3D printed soybean oil-based hybrid material, a hollow cube 3D printed soybean oil-based hybrid material, a hollow rectangular 3D printed soybean oil-based hybrid material or a hollow cylindrical 3D printed soybean oil-based hybrid material.

[0040] The following is a detailed description of the preparation method of an enhanced 3D printing soybean oil-based hybrid material provided by the present application in combination with embodiments and experimental examples.

[0041] Example 1

[0042] Embodiment 1 of the present application provides a method for preparing a soybean oil-based hybrid material for enhanced 3D printing, the preparation method comprising: a step of configuring a photoacid generator, a step of configuring a 3D printing slurry, a step of performing 3D printing, and a step of baking.

[0043] The step of preparing the photoacid generator includes: mixing 5 grams of diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate and 0.5 grams of 2-isopropylthioxanthone to obtain the photoacid generator;

[0044] The step of preparing the 3D printing slurry includes: uniformly mixing 55g of epoxy soybean oil acrylate, 27.5g of hydroxyethyl methacrylate, 4g of silane coupling agent KH-570, 4g of photoacid generator, 1.8g of photoinitiator TPO-L, 0.2g BYK-371, and 7.5g of zirconium dioxide precursor n-butyl zirconate to obtain 3D printing slurry.

[0045] The steps of 3D printing include: using the LCD 3D printer model W5501 of Shenzhen Weishitech Technology Co., Ltd. to print 3D printing slurry with a wavelength of 405nm, printing 10 3D printed soybean oil-based hybrid material splines, the spline size is the spline size specified in the national standard GB1040-79, the actual picture is as follows Figure 6 As shown in Figure (a).

[0046] The baking step includes: placing 5 of the 10 3D printed soybean oil-based hybrid material sample strips in an 80°C oven for 48 hours to obtain an enhanced 3D printed soybean oil-based hybrid material. The total reflection infrared spectrum of the enhanced 3D printed soybean oil-based hybrid material sample strips is shown in FIG. Figure 3 As shown in the electron microscope image Figure 4 shown.

[0047] Example 2

[0048] Example 2 of the present application provides a method for preparing a soybean oil-based hybrid material for enhanced 3D printing. The difference between the preparation method and Example 1 is that the amount of raw materials is adjusted. The preparation method includes: a step of configuring a photoacid generator, a step of configuring a 3D printing slurry, a step of performing 3D printing, and a step of baking.

[0049] The step of preparing the photoacid generator includes: mixing 5 grams of diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate and 0.5 grams of 2-isopropylthioxanthone to obtain the photoacid generator;

[0050] The step of preparing the 3D printing slurry includes: uniformly mixing 50g of epoxy soybean oil acrylate, 25g of hydroxyethyl methacrylate, 4g of silane coupling agent KH-570, 4g of photoacid generator, 1.8g of photoinitiator TPO-L, 0.2g BYK-371, and 15g of zirconium dioxide precursor n-butyl zirconate to obtain 3D printing slurry.

[0051] The steps of 3D printing include: using a LCD 3D printer model W5501 of Shenzhen Weishitech Technology Co., Ltd. to print 3D printing slurry with a wavelength of 405nm, printing 10 3D printed soybean oil-based hybrid material splines, and the spline size is the spline size specified in the national standard GB1040-79.

[0052] The baking step includes: placing 5 of the 10 3D printed soybean oil-based hybrid material sample strips in an 80° C. oven and baking for 48 hours to obtain enhanced 3D printed soybean oil-based hybrid materials.

[0053] Example 3

[0054] Example 3 of the present application provides a method for preparing a soybean oil-based hybrid material for enhanced 3D printing. The difference between the preparation method and Example 1 is that the amount of raw materials is adjusted. The preparation method includes: a step of configuring a photoacid generator, a step of configuring a 3D printing slurry, a step of performing 3D printing, and a step of baking.

[0055] The step of preparing the photoacid generator includes: mixing 5 grams of diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate and 0.5 grams of 2-isopropylthioxanthone to obtain the photoacid generator;

[0056] The step of preparing the 3D printing slurry includes: uniformly mixing 40g of epoxy soybean oil acrylate, 35g of hydroxyethyl methacrylate, 4g of silane coupling agent KH-570, 4g of photoacid generator, 1.8g of photoinitiator TPO-L, 0.2g BYK-371, and 15g of zirconium dioxide precursor n-butyl zirconate to obtain 3D printing slurry.

[0057] The steps of 3D printing include: using a LCD 3D printer model W5501 of Shenzhen Weishitech Technology Co., Ltd. to print 3D printing slurry with a wavelength of 405nm, printing 10 3D printed soybean oil-based hybrid material splines, and the spline size is the spline size specified in the national standard GB1040-79.

[0058] The baking step includes: placing 5 of the 10 3D printed soybean oil-based hybrid material sample strips in an 80° C. oven and baking for 48 hours to obtain enhanced 3D printed soybean oil-based hybrid materials.

[0059] Example 4

[0060] Example 4 of the present application provides a method for preparing a soybean oil-based hybrid material for enhanced 3D printing. The difference between the preparation method and Example 1 is that the amount of raw materials is adjusted. The preparation method includes: a step of configuring a photoacid generator, a step of configuring a 3D printing slurry, a step of performing 3D printing, and a step of baking.

[0061] The step of preparing the photoacid generator includes: mixing 5 grams of diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate and 0.5 grams of 2-isopropylthioxanthone to obtain the photoacid generator;

[0062] The step of preparing the 3D printing slurry includes: uniformly mixing 45g of epoxy soybean oil acrylate, 22.5g of hydroxyethyl methacrylate, 4g of silane coupling agent KH-570, 4g of photoacid generator, 1.8g of photoinitiator TPO-L, 0.2g BYK-371, and 22.5g of zirconium dioxide precursor n-butyl zirconate to obtain 3D printing slurry.

[0063] The steps of 3D printing include: using a LCD 3D printer model W5501 of Shenzhen Weishitech Technology Co., Ltd. to print 3D printing slurry with a wavelength of 405nm, printing 10 3D printed soybean oil-based hybrid material splines, and the spline size is the spline size specified in the national standard GB1040-79.

[0064] The baking step includes: placing 5 of the 10 3D printed soybean oil-based hybrid material sample strips in an 80° C. oven and baking for 48 hours to obtain enhanced 3D printed soybean oil-based hybrid materials.

[0065] Example 5

[0066] Example 5 of the present application provides a method for preparing a soybean oil-based hybrid material for enhanced 3D printing. The difference between the preparation method and Example 1 is that the amount of raw materials is adjusted. The preparation method includes: a step of configuring a photoacid generator, a step of configuring a 3D printing slurry, a step of performing 3D printing, and a step of baking.

[0067] The step of preparing the photoacid generator includes: mixing 5 grams of diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate and 0.5 grams of 2-isopropylthioxanthone to obtain the photoacid generator;

[0068] The step of preparing the 3D printing slurry includes: uniformly mixing 52g of epoxy soybean oil acrylate, 26g of hydroxyethyl methacrylate, 1g of silane coupling agent KH-570, 4g of photoacid generator, 1.8g of photoinitiator TPO-L, 0.2g of BYK-371, and 15g of zirconium dioxide precursor n-butyl zirconate to obtain the 3D printing slurry.

[0069] The steps of 3D printing include: using a LCD 3D printer model W5501 of Shenzhen Weishitech Technology Co., Ltd. to print 3D printing slurry with a wavelength of 405nm, printing 10 3D printed soybean oil-based hybrid material splines, and the spline size is the spline size specified in the national standard GB1040-79.

[0070] The baking step includes: placing 5 of the 10 3D printed soybean oil-based hybrid material sample strips in an 80° C. oven and baking for 48 hours to obtain enhanced 3D printed soybean oil-based hybrid materials.

[0071] Example 6

[0072] Example 6 of the present application provides a method for preparing an enhanced 3D printing soybean oil-based hybrid material. The difference between the preparation method and Example 1 is that the amount of raw materials is adjusted. The preparation method includes: a step of configuring a photoacid generator, a step of configuring a 3D printing slurry, a step of performing 3D printing, and a step of baking.

[0073] The step of preparing the photoacid generator includes: mixing 5 grams of diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate and 0.5 grams of 2-isopropylthioxanthone to obtain the photoacid generator;

[0074] The step of preparing the 3D printing slurry includes: uniformly mixing 48g of epoxy soybean oil acrylate, 24g of hydroxyethyl methacrylate, 7g of silane coupling agent KH-570, 4g of photoacid generator, 1.8g of photoinitiator TPO-L, 0.2g BYK-371, and 15g of zirconium dioxide precursor n-butyl zirconate to obtain 3D printing slurry.

[0075] The steps of 3D printing include: using a LCD 3D printer model W5501 of Shenzhen Weishitech Technology Co., Ltd. to print 3D printing slurry with a wavelength of 405nm, printing 10 3D printed soybean oil-based hybrid material splines, and the spline size is the spline size specified in the national standard GB1040-79.

[0076] The baking step includes: placing 5 of the 10 3D printed soybean oil-based hybrid material sample strips in an 80° C. oven and baking for 48 hours to obtain enhanced 3D printed soybean oil-based hybrid materials.

[0077] Example 7

[0078] Example 7 of the present application provides a method for preparing an enhanced 3D printing soybean oil-based hybrid material. The difference between the preparation method and Example 1 is that the amount of raw materials is adjusted. The preparation method includes: a step of configuring a photoacid generator, a step of configuring a 3D printing slurry, a step of performing 3D printing, and a step of baking.

[0079] The step of preparing the photoacid generator includes: mixing 5 grams of diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate and 0.5 grams of 2-isopropylthioxanthone to obtain the photoacid generator;

[0080] The step of preparing the 3D printing slurry includes: uniformly mixing 52g of epoxy soybean oil acrylate, 26g of hydroxyethyl methacrylate, 4g of silane coupling agent KH-570, 4g of photoacid generator, 1.8g of photoinitiator TPO-L, 0.2g BYK-371, and 15g of zirconium dioxide precursor n-butyl zirconate to obtain 3D printing slurry.

[0081] The steps of 3D printing include: using a LCD 3D printer model W5501 of Shenzhen Weishitech Technology Co., Ltd. to print 3D printing slurry with a wavelength of 405nm, printing 10 3D printed soybean oil-based hybrid material splines, and the spline size is the spline size specified in the national standard GB1040-79.

[0082] The baking step includes: placing 5 of the 10 3D printed soybean oil-based hybrid material sample strips in an 80° C. oven and baking for 48 hours to obtain enhanced 3D printed soybean oil-based hybrid materials.

[0083] Example 8

[0084] Example 8 of the present application provides a method for preparing an enhanced 3D printing soybean oil-based hybrid material. The difference between the preparation method and Example 1 is that the photoacid generator is adjusted. The preparation method includes: a step of configuring the photoacid generator, a step of configuring a 3D printing slurry, a step of performing 3D printing, and a step of baking.

[0085] The step of preparing the photoacid generator includes: mixing 4 grams of diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate and 0.5 grams of 2-isopropylthioxanthone to obtain the photoacid generator;

[0086] The step of preparing the 3D printing slurry includes: uniformly mixing 55g of epoxy soybean oil acrylate, 27.5g of hydroxyethyl methacrylate, 4g of silane coupling agent KH-570, 4g of photoacid generator, 1.8g of photoinitiator TPO-L, 0.2g BYK-371, and 7.5g of zirconium dioxide precursor n-butyl zirconate to obtain 3D printing slurry.

[0087] The steps of 3D printing include: using a LCD 3D printer model W5501 of Shenzhen Weishitech Technology Co., Ltd. to print 3D printing slurry with a wavelength of 405nm, printing 10 3D printed soybean oil-based hybrid material splines, and the spline size is the spline size specified in the national standard GB1040-79.

[0088] The baking step includes: placing 5 of the 10 3D printed soybean oil-based hybrid material sample strips in an 80° C. oven and baking for 48 hours to obtain enhanced 3D printed soybean oil-based hybrid materials.

[0089] Example 9

[0090] Example 9 of the present application provides a method for preparing a 3D printed soybean oil-based hybrid material. As the first comparative example of the embodiment, the preparation method includes: a step of configuring a 3D printing slurry, a step of performing 3D printing, and a step of baking.

[0091] Among them, the step of preparing the 3D printing slurry includes: uniformly mixing 65g of epoxy soybean oil acrylate, 33g of hydroxyethyl methacrylate, 1.8g of photoinitiator TPO-L, and 0.2g of BYK-371 to obtain the 3D printing slurry.

[0092] The steps of 3D printing include: using a LCD 3D printer model W5501 of Shenzhen Weishitech Technology Co., Ltd. to print 3D printing slurry with a wavelength of 405nm, printing 10 3D printed soybean oil-based hybrid material splines, and the spline size is the spline size specified in the national standard GB1040-79.

[0093] The baking step includes: placing 5 of the 10 3D printed soybean oil-based hybrid material sample strips in an 80° C. oven for baking for 48 hours to obtain the baked 3D printed soybean oil-based hybrid material.

[0094] Example 10

[0095] Example 10 of the present application provides a method for preparing a 3D printed soybean oil-based hybrid material. As a second comparative example of the embodiment, the photoacid generator used is the same as the photoacid generator in Example 1; the preparation method includes: a step of configuring a 3D printing slurry, a step of performing 3D printing, and a step of baking.

[0096] Among them, the step of preparing the 3D printing slurry includes: uniformly mixing 60g of epoxy soybean oil acrylate, 30g of hydroxyethyl methacrylate, 4g of silane coupling agent KH-570, 4g of photoacid generator, 1.8g of photoinitiator TPO-L, and 0.2g BYK-371 to obtain 3D printing slurry.

[0097] The steps of 3D printing include: using a LCD 3D printer model W5501 of Shenzhen Weishitech Technology Co., Ltd. to print 3D printing slurry with a wavelength of 405nm, printing 10 3D printed soybean oil-based hybrid material splines, and the spline size is the spline size specified in the national standard GB1040-79.

[0098] The baking step includes: placing 5 of the 10 3D printed soybean oil-based hybrid material sample strips in an 80° C. oven for baking for 48 hours to obtain the baked 3D printed soybean oil-based hybrid material.

[0099] Embodiment 11

[0100] Example 11 of the present application provides a method for preparing a 3D printed soybean oil-based hybrid material. As a third comparative example of the embodiment, the preparation method includes: a step of configuring a 3D printing slurry, a step of performing 3D printing, and a step of baking.

[0101] Among them, the step of preparing the 3D printing slurry includes: uniformly mixing 58g of epoxy soybean oil acrylate, 28.5g of hydroxyethyl methacrylate, 4g of silane coupling agent KH-570, 1.8g of photoinitiator TPO-L, 0.2g BYK-371, and 7.5g of zirconium dioxide precursor n-butyl zirconate to obtain 3D printing slurry.

[0102] The steps of 3D printing include: using a LCD 3D printer model W5501 of Shenzhen Weishitech Technology Co., Ltd. to print 3D printing slurry with a wavelength of 405nm, printing 10 3D printed soybean oil-based hybrid material splines, and the spline size is the spline size specified in the national standard GB1040-79.

[0103] The baking step includes: placing 5 of the 10 3D printed soybean oil-based hybrid material sample strips in an 80° C. oven for baking for 48 hours to obtain the baked 3D printed soybean oil-based hybrid material.

[0104] Example 12

[0105] Example 12 of the present application provides a method for preparing a 3D printed soybean oil-based hybrid material. As the fourth comparative example of the embodiment, the photoacid generator used is the same as the photoacid generator in Example 1; the preparation method includes: a step of configuring a 3D printing slurry, a step of performing 3D printing, and a step of baking.

[0106] Among them, the step of preparing the 3D printing slurry includes: uniformly mixing 30g of epoxy soybean oil acrylate, 45g of hydroxyethyl methacrylate, 4g of silane coupling agent KH-570, 4g of photoacid generator, 1.8g of photoinitiator TPO-L, 0.2g BYK-371, and 15g of zirconium dioxide precursor n-butyl zirconate to obtain 3D printing slurry.

[0107] The steps of 3D printing include: using a LCD 3D printer model W5501 of Shenzhen Weishitech Technology Co., Ltd. to print 3D printing slurry with a wavelength of 405nm, printing 10 3D printed soybean oil-based hybrid material splines, and the spline size is the spline size specified in the national standard GB1040-79.

[0108] The baking step includes: placing 5 of the 10 3D printed soybean oil-based hybrid material sample strips in an 80° C. oven for baking for 48 hours to obtain the baked 3D printed soybean oil-based hybrid material.

[0109] Embodiment 13

[0110] Example 13 of the present application provides a method for preparing a 3D printed soybean oil-based hybrid material. As the fifth comparative example of the embodiment, the photoacid generator used is the same as the photoacid generator in Example 1; the preparation method includes: a step of configuring a 3D printing slurry, a step of performing 3D printing, and a step of baking.

[0111] Among them, the step of preparing the 3D printing slurry includes: uniformly mixing 20g of epoxy soybean oil acrylate, 55g of hydroxyethyl methacrylate, 4g of silane coupling agent KH-570, 4g of photoacid generator, 1.8g of photoinitiator TPO-L, 0.2g BYK-371, and 15g of zirconium dioxide precursor n-butyl zirconate to obtain 3D printing slurry.

[0112] The steps of 3D printing include: using a LCD 3D printer model W5501 of Shenzhen Weishitech Technology Co., Ltd. to print 3D printing slurry with a wavelength of 405nm, printing 10 3D printed soybean oil-based hybrid material splines, and the spline size is the spline size specified in the national standard GB1040-79.

[0113] The baking step includes: placing 5 of the 10 3D printed soybean oil-based hybrid material sample strips in an 80° C. oven for baking for 48 hours to obtain the baked 3D printed soybean oil-based hybrid material.

[0114] Embodiment 14

[0115] Example 14 of the present application provides a method for preparing a 3D printed soybean oil-based hybrid material. As the sixth comparative example of the embodiment, the photoacid generator used is different from the photoacid generator in Example 1; the preparation method includes: a step of configuring the photoacid generator, a step of configuring a 3D printing slurry, a step of performing 3D printing, and a step of baking.

[0116] The step of preparing the photoacid generator includes: mixing 5 grams of diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate and 0.2 grams of 2-isopropylthioxanthone to obtain the photoacid generator;

[0117] The step of preparing the 3D printing slurry includes: uniformly mixing 55g of epoxy soybean oil acrylate, 27.5g of hydroxyethyl methacrylate, 4g of silane coupling agent KH-570, 4g of photoacid generator, 1.8g of photoinitiator TPO-L, 0.2g BYK-371, and 7.5g of zirconium dioxide precursor n-butyl zirconate to obtain 3D printing slurry.

[0118] The steps of 3D printing include: using a LCD 3D printer model W5501 of Shenzhen Weishitech Technology Co., Ltd. to print 3D printing slurry with a wavelength of 405nm, printing 10 3D printed soybean oil-based hybrid material splines, and the spline size is the spline size specified in the national standard GB1040-79.

[0119] The baking step includes: placing 5 of the 10 3D printed soybean oil-based hybrid material sample strips in an 80° C. oven for baking for 48 hours to obtain the baked 3D printed soybean oil-based hybrid material.

[0120] Embodiment 15

[0121] Example 15 of the present application provides a method for preparing a 3D printed soybean oil-based hybrid material. As the seventh comparative example of the embodiment, the photoacid generator used is different from the photoacid generator in Example 1; the preparation method includes: a step of configuring the photoacid generator, a step of configuring the 3D printing slurry, a step of performing 3D printing, and a step of baking.

[0122] The step of preparing the photoacid generator includes: mixing 5 grams of diphenyl[4-(phenylthio)phenyl]-sulfonium hexafluoroantimonate and 0.5 grams of 2-isopropylthioxanthenone to obtain the photoacid generator;

[0123] The step of preparing the 3D printing slurry includes: uniformly mixing 55g of epoxy soybean oil acrylate, 27.5g of hydroxyethyl methacrylate, 4g of silane coupling agent KH-570, 4g of photoacid generator, 1.8g of photoinitiator TPO-L, 0.2g BYK-371, and 7.5g of zirconium dioxide precursor n-butyl zirconate to obtain 3D printing slurry.

[0124] The steps of 3D printing include: using a LCD 3D printer model W5501 of Shenzhen Weishitech Technology Co., Ltd. to print 3D printing slurry with a wavelength of 405nm, printing 10 3D printed soybean oil-based hybrid material splines, and the spline size is the spline size specified in the national standard GB1040-79.

[0125] The baking step includes: placing 5 of the 10 3D printed soybean oil-based hybrid material sample strips in an 80° C. oven for baking for 48 hours to obtain the baked 3D printed soybean oil-based hybrid material.

[0126] Example 16

[0127] Example 16 of the present application provides a method for preparing a 3D printed soybean oil-based hybrid material. As the eighth comparative example of the embodiment, the photoacid generator used is different from the photoacid generator in Example 1; the preparation method includes: a step of configuring the photoacid generator, a step of configuring the 3D printing slurry, a step of performing 3D printing, and a step of baking.

[0128] The step of preparing the photoacid generator includes: mixing 5 grams of bis(4-(diphenylsulfonium)phenyl)sulfide-bis(hexafluorophosphate) and 0.5 grams of 2-isopropylthioxanthenone to obtain the photoacid generator;

[0129] The step of preparing the 3D printing slurry includes: uniformly mixing 55g of epoxy soybean oil acrylate, 27.5g of hydroxyethyl methacrylate, 4g of silane coupling agent KH-570, 4g of photoacid generator, 1.8g of photoinitiator TPO-L, 0.2g BYK-371, and 7.5g of zirconium dioxide precursor n-butyl zirconate to obtain 3D printing slurry.

[0130] The steps of 3D printing include: using a LCD 3D printer model W5501 of Shenzhen Weishitech Technology Co., Ltd. to print 3D printing slurry with a wavelength of 405nm, printing 10 3D printed soybean oil-based hybrid material splines, and the spline size is the spline size specified in the national standard GB1040-79.

[0131] The baking step includes: placing 5 of the 10 3D printed soybean oil-based hybrid material sample strips in an 80° C. oven for baking for 48 hours to obtain the baked 3D printed soybean oil-based hybrid material.

[0132] Embodiment 17

[0133] Example 17 of the present application provides a method for preparing a 3D printed soybean oil-based hybrid material, as the ninth comparative example of the embodiment; the preparation method includes: the steps of configuring a 3D printing slurry, performing 3D printing, and baking.

[0134] Among them, the step of preparing the 3D printing slurry includes: evenly mixing 55g of epoxy soybean oil acrylate, 27.5g of hydroxyethyl methacrylate, 4g of silane coupling agent KH-570, 4g of hydrochloric acid, 1.8g of photoinitiator TPO-L, 0.2g BYK-371, and 7.5g of zirconium dioxide precursor n-butyl zirconate to obtain 3D printing slurry.

[0135] The steps of 3D printing include: using a LCD 3D printer model W5501 of Shenzhen Weishitech Technology Co., Ltd. to print 3D printing slurry with a wavelength of 405nm, printing 10 3D printed soybean oil-based hybrid material splines, and the spline size is the spline size specified in the national standard GB1040-79.

[0136] The baking step includes: placing 5 of the 10 3D printed soybean oil-based hybrid material specimens in an 80°C oven for 48 hours to obtain the baked 3D printed soybean oil-based hybrid material, as shown in the electron microscope image. Figure 5 shown.

[0137] Embodiment 18

[0138] Example 18 of the present application provides a method for preparing an enhanced 3D printing soybean oil-based hybrid material, the preparation method comprising: a step of configuring a photoacid generator, a step of configuring a 3D printing slurry, a step of performing 3D printing, and a step of baking.

[0139] The step of preparing the photoacid generator includes: mixing 5 grams of diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate and 0.5 grams of 2-isopropylthioxanthone to obtain the photoacid generator;

[0140] The step of preparing the 3D printing slurry includes: uniformly mixing 55g of epoxy soybean oil acrylate, 27.5g of hydroxyethyl methacrylate, 4g of silane coupling agent KH-570, 4g of photoacid generator, 1.8g of photoinitiator TPO-L, 0.2g BYK-371, and 7.5g of zirconium dioxide precursor n-butyl zirconate to obtain 3D printing slurry.

[0141] The steps of 3D printing include: using the LCD 3D printer model W5501 of Shenzhen Weishitech Technology Co., Ltd. to print 3D printing slurry with a wavelength of 405nm, printing two 3D printed soybean oil-based hybrid materials, one is a 3D printed soybean oil-based hybrid material in the shape of a hollow sphere, and the other is a 3D printed soybean oil-based hybrid material in the shape of a hollow cube. The actual picture of the 3D printed soybean oil-based hybrid material in the shape of a hollow sphere is as follows: Figure 6 As shown in Figure (b), the actual image of the 3D printed soybean oil-based hybrid material in the shape of a hollow cube is shown in Figure 6 As shown in Figure (c).

[0142] The baking step includes: placing two 3D printed soybean oil-based hybrid materials in an oven at 80° C. and baking for 48 hours to obtain a reinforced 3D printed soybean oil-based hybrid material.

[0143] Experimental Example 1

[0144] Experimental Example 1 of the present application performs performance tests on the 3D printing slurry, enhanced 3D printing soybean oil-based hybrid material or 3D printing soybean oil-based hybrid material provided in Examples 1-17, and the performance tests include storage stability tests, mechanical property tests and microstructure characterization.

[0145] Among them, the object of the storage stability test is the 3D printing slurry provided in Examples 1-17, and the test instrument and process are to use the HAAKE MARS rotational rheometer of Thermo Fisher Scientific, USA for testing. The test temperature during the test is 25°C, the test speed range is 0.1~1000 1 / s, the rotor is a flat rotor with a diameter of 20mm, and the steady-state mode is selected to test the viscosity. The normal force Fn during the test is kept below 0.1N. The test results are shown in Tables 1 and 2;

[0146] The objects of the mechanical property test are the specimens of the enhanced 3D printed soybean oil-based hybrid materials or 3D printed soybean oil-based hybrid materials provided in Examples 1-17. The test instrument and process are to use the CMT 4204 electronic universal testing machine of MTS Systems, USA, to perform the test in accordance with the national standard GB1040-79. Five specimens are tested before and after being baked in an oven at 80°C for 48 hours. The test results are averaged. The test results are shown in Tables 1 and 2.

[0147] The object of microstructure characterization is the sample strips in test examples 1-17 after being baked in an oven at 80°C for 48 hours. The test instrument and process are carried out using total reflection infrared spectroscopy (ATR) and SEM according to the instrument operation flow; the test results are shown in Tables 3 and 4.

[0148] Table 1: Storage stability test and mechanical properties test results

[0149]

[0150] Table 2: Storage stability test and mechanical properties test results

[0151]

[0152] Table 3: Microscopic characterization test results of nano zirconium dioxide

[0153]

[0154] Table 4: Microscopic characterization test results of nano zirconium dioxide

[0155]

[0156] It can be seen from Table 1, Table 2, Table 3 and Table 4 that the preparation methods of enhanced 3D printing soybean oil-based hybrid materials provided in Examples 1-8 of the present application can all realize 3D printing, and the materials prepared by the preparation methods have good mechanical properties such as tensile strength and elongation at break, overcoming the defect that the current preparation methods cannot prepare 3D printing soybean oil resin materials with high mechanical strength; however, in Examples 12-13, due to excessive diluent dosage, printing and curing could not be performed and the test could not be completed.

[0157] Compared with the enhanced 3D printing soybean oil-based hybrid materials provided in Examples 1-8 of the present application, the preparation methods of the enhanced 3D printing soybean oil-based hybrid materials provided in Examples 9-11 and 14-13 can also realize 3D printing, but Example 9 does not include a silane coupling agent, a photoacid generator, and n-butyl zirconate, and there is no significant change in the mechanical properties before and after the sol-gel reaction; Example 10 does not include n-butyl zirconate, and the sol-gel reaction cannot be carried out without n-butyl zirconate, and there is no significant change in the mechanical properties before and after the sol-gel reaction; Example 11 does not include a photoacid generator, and the catalytic effect on the sol-gel is poor, and the mechanical properties before and after the sol-gel reaction are The mechanical properties are almost the same; the amount of 2-isopropylthioxanthone added in the photoacid generator used in Example 14 is small, and the photoacid generator used in Example 15 has poor solubility. The photoacid generator used in Example 16 absorbs purple light and releases it in the form of light, and its acid generation efficiency is low. The amount and particle size of nano zirconium dioxide generated are worse than those in Example 1, and the mechanical properties are also weaker than those in Example 1. Example 17 uses hydrochloric acid vapor to catalyze the sol-gel reaction process. The pH on the sample surface is lower than that on the inside, which makes the zirconium dioxide particles unevenly distributed inside and outside, and the particle size is large, resulting in poor effect of zirconium dioxide in enhancing mechanical properties such as tensile strength and elongation at break.

[0158] The above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, a person skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some or all of the technical features thereof may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A method for preparing a soybean oil-based hybrid material for enhanced 3D printing, characterized in that: Includes steps: Step S1, mixing epoxy soybean oil acrylate, diluent, photoinitiator, n-butyl zirconate, photoacid generator, silane coupling agent and leveling agent uniformly to obtain soybean oil-based hybrid slurry; Step S2, using a light-curing 3D printer to 3D print the soybean oil-based hybrid slurry to obtain a 3D printed soybean oil-based hybrid material; Step S3, baking the 3D printed soybean oil-based hybrid material to obtain a reinforced 3D printed soybean oil-based hybrid material; In step S1, the mass ratio of the epoxy soybean oil acrylate, the diluent, the photoinitiator, the n-butyl zirconate, the photoacid generator, the silane coupling agent and the leveling agent is 40-55: 22.5-35: 1-3: 10-20: 2-4: 2-4: 0.1-0.3 in parts by mass; In step S1, the photoacid generator is selected from a mixture of diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate and 2-isopropylthioxanthone; the mass ratio of diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate to 2-isopropylthioxanthone is 1:0.05-0.

15.

2. The method for preparing an enhanced 3D printing soybean oil-based hybrid material according to claim 1, characterized in that: In step S1, the diluent is selected from at least one of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate; The photoinitiator is selected from at least one of TPO-L, 819, 1173, and TMO; The silane coupling agent is selected from at least one of KH550, KH560 and KH570; The leveling agent is selected from BYK-371.

3. The method for preparing an enhanced 3D printing soybean oil-based hybrid material according to claim 1, characterized in that: In step S2, the light-curing 3D printer is selected from an LCD light-curing 3D printer, and the ultraviolet light curing wavelength in the 3D printing process is 250-405nm.

4. The method for preparing an enhanced 3D printing soybean oil-based hybrid material according to claim 1, characterized in that: In step S2, the 3D printed soybean oil-based hybrid material is selected from a 3D printed soybean oil-based hybrid material in the shape of a hollow sphere, a 3D printed soybean oil-based hybrid material in the shape of a hollow cube, a 3D printed soybean oil-based hybrid material in the shape of a hollow cuboid, or a 3D printed soybean oil-based hybrid material in the shape of a hollow cylinder.

5. The method for preparing an enhanced 3D printing soybean oil-based hybrid material according to claim 1, characterized in that: In step S3, the baking temperature is 70-90° C. and the baking time is 24-72 hours.

6. An enhanced 3D printing soybean oil-based hybrid material, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 5.

7. Use of the enhanced 3D printing soybean oil-based hybrid material according to claim 6 in the preparation of plastic containers, plastic packaging materials or plastic parts.

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