Water-based hyperbranched uv resin for 3D printing as well as preparation method and application of water-based hyperbranched uv resin

Abstract

The invention provides water-based hyperbranched uv resin for 3D printing as well as a preparation method and application of the water-based hyperbranched uv resin. The resin is prepared from 0-55% of a polyurethane acrylate prepolymer and 0-65% of an epoxy acrylate prepolymer, the polyurethane acrylate prepolymer comprises the following components: a UV curing diluting monomer, a hydroxy acid monomer, acid anhydride, isocyanate, polyol, a catalyst, a polymerization inhibitor, hydroxy acrylate and a neutralizer; the epoxy acrylate prepolymer comprises the following components: dibasic acid, dihydric alcohol, amino acid, an epoxy acrylic monomer, a neutralizer, a catalyst, a polymerization inhibitor and a UV curing diluting monomer. The prepared uv resin has low viscosity, can be washed with water, has low shrinkage, and can be widely applied to the fields of spaceflight, medical treatment, artwork design, shoemaking and the like.

Description

Technical Field

[0001] The present invention relates to the fields of aerospace, medical treatment, artwork, clothing, shoemaking, and more specifically to a water-based hyperbranched UV resin for 3D printing and a preparation method and application thereof. Background Art

[0002] In today's ever-changing technological era, people have higher and higher demands for the quality of life, whether it is the material needs of food, clothing, housing and transportation, or the spiritual needs of art, and the requirements for environmental protection, health, differentiation, precision, etc. are getting higher and higher. Traditional manufacturing and processing technology can no longer meet these requirements of people. Therefore, 3D printing technology, as a cutting-edge manufacturing technology, is leading the profound transformation of the manufacturing industry with its unique charm and unlimited potential.

[0003] In the traditional manufacturing model, mass production often means standardization and homogenization of products. At the same time, in the traditional manufacturing process, mold making, prototype development and other links are often time-consuming, labor-intensive and costly, resulting in low manufacturing efficiency. 3D printing technology, with its ability to directly convert from digital models to physical objects, provides unprecedented convenience for personalized customization. At the same time, by reducing the intermediate steps and directly going from digital design to physical manufacturing, the cost of the initial product development is significantly reduced, and the time cycle from product design to market is greatly shortened. This is of great significance for quickly responding to market changes and accelerating product iteration. In addition, facing the dual pressures of global resource tension and environmental protection, 3D printing technology has become an important force in promoting sustainable production with its high material utilization rate and low waste generation. By precisely controlling the amount of materials used and reducing the waste of raw materials, and at the same time, using recyclable or biodegradable materials for printing, it helps to reduce environmental pollution and promote the development of a circular economy.

[0004] 3D printing technology has unparalleled advantages, but UV resin, one of the main raw materials for 3D printing, has brought some problems due to its own characteristics. For example, the resin has high viscosity, and a large amount of dilution monomer is needed to reduce the viscosity, resulting in a decline in the performance of the final product; the monomer is corrosive and volatile, which brings some risks during use; after printing, a large amount of solvent is needed to clean the material tank, causing environmental pollution; UV resin has a certain degree of shrinkage during the curing process, causing the size of the final product to change, making it impossible to use in some high-precision fields. Summary of the invention

[0005] In view of the above-mentioned deficiencies in the prior art, the purpose of the present invention is to provide a 3D printing water-based hyperbranched UV resin and its preparation method and application. The product can be washed with water, avoiding the use of solvents and greatly reducing environmental pollution. It has a hyperbranched structure, which greatly reduces the viscosity of the resin and greatly reduces the use of diluent monomers.

[0006] In order to achieve the above-mentioned object, the present invention provides a water-based hyperbranched UV resin for 3D printing, wherein the resin is composed of 0-55% polyurethane acrylate prepolymer and 0-65% epoxy acrylate prepolymer; the polyurethane acrylate prepolymer comprises the following components in parts by weight: 20-50 parts of UV curing dilution monomer, 0-15 parts of hydroxy acid monomer, 0-10 parts of acid anhydride, 30-70 parts of isocyanate, 5-20 parts of polyol, 0.06-0.16 parts of catalyst, The epoxy acrylate prepolymer comprises the following components in parts by weight: 78-107 parts of dibasic acid, 70-95 parts of diol, 175-240 parts of amino acid, 110-195 parts of epoxy acrylic monomer, 50-100 parts of neutralizer, 1.4-2.4 parts of catalyst, 0.01-0.05 parts of inhibitor and 15-25 parts of UV curing diluent monomer.

[0007] In one embodiment, the water content of the UV curable diluent monomer, hydroxy acid monomer, isocyanate, polyol, catalyst, inhibitor, solvent, and hydroxy acrylate is less than 500 ppm.

[0008] In one embodiment, the UV curable diluent monomer is at least one of acryloyl morpholine (ACMO), o-phenylphenoxyethyl acrylate (0PPEA), tetrahydrofuran acrylate (THFA), ethoxylated trimethylolpropane triacrylate (3EOTMPTA), and trimethylolpropane triacrylate (TMPTA).

[0009] In one embodiment, the polyol is at least one of an intermediate polyol in the synthesis process of epoxy acrylate prepolymer, Dow SD301, boltorn dendritic polyol, and pentaerythritol.

[0010] In one embodiment, the isocyanate is at least one of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), and 4,4'-dicyclohexylmethane diisocyanate (HMDI); the hydroxy acid monomer is at least one of 2,2-dimethylolpropionic acid (DMPA), dimethylolbutyric acid (DMBA), and isethionic acid; the acid anhydride is at least one of succinic anhydride, phthalic anhydride, acetic anhydride, and maleic anhydride; the hydroxy acrylate is at least one of dipentaerythritol pentaacrylate, pentaerythritol triacrylate, hydroxy butyl acrylate, and hydroxy ethyl acrylate.

[0011] In one embodiment, the polyurethane acrylate prepolymer catalyst is at least one of organic bismuth, solid amine, N-methylmorpholine, and N,N'-diethylpiperazine; the epoxy acrylate prepolymer catalyst is at least one of p-toluenesulfonic acid monohydrate (P-TSA), concentrated hydrochloric acid, concentrated sulfuric acid, thionyl chloride, and trifluoromethanesulfonic acid.

[0012] In one embodiment, the dibasic acid is at least one of oxalic acid, malonic acid, succinic acid, and fumaric acid; the diol is at least one of butanediol, hexanediol, and neopentyl glycol; the amino acid is at least one of glutamic acid, aspartic acid, and acetylglutamic acid; and the epoxy acrylic monomer is at least one of glycidyl methacrylate (GMA) and versatate glycidyl ester.

[0013] In one embodiment, the inhibitor is at least one of p-hydroxyanisole, hydroquinone, and 2,5-dimethylhydroquinone; the neutralizer is at least one of triethylamine, N,N-dimethylethanolamine, ammonia water, sodium hydroxide, and potassium hydroxide.

[0014] The present invention also provides a method for preparing the above-mentioned water-based hyperbranched UV resin for 3D printing, comprising the following steps: the first step is to synthesize an epoxy acrylic prepolymer, comprising the following steps: S1: 15-25 parts of UV curing dilution monomer, 8-12 parts of dibasic acid, 25-35 parts of amino acid, and 0.1-0.3 parts of catalyst are mixed evenly, and stirred for reaction at 130-160°C for 4 hours until no water is discharged, and condensation and water are removed during the reaction to obtain a first reaction liquid; S2: 50-70 parts of amino acid and 0.2-0.4 parts of catalyst are added to the first reaction liquid, and the reaction is stirred for reaction at 130-160°C for 4 hours until no water is discharged to obtain a second reaction liquid; S3: Add S4: add 70-95 parts of diol and 0.3-0.5 parts of catalyst to the third reaction liquid, stir and react at 130-160°C for 4h, until no water is discharged, to obtain a third reaction liquid; S5: add 100-135 parts of amino acid and 0.5-0.7 parts of catalyst to the fourth reaction liquid, stir and react at 130-160°C for 4h, until no water is discharged, to obtain a fifth reaction liquid; S6: add 110-195 parts of epoxy acrylic monomer and 0.01-0.05 parts of inhibitor to the fifth reaction liquid, Stirring and reacting at 130-160°C for 3h, cooling to 45°C to obtain a sixth reaction liquid; S7: adding 50-100 parts of a neutralizing agent to the sixth reaction liquid, stirring for 30 minutes, and obtaining an epoxy acrylate prepolymer; the second step, synthesizing a polyurethane acrylate prepolymer, comprising the following steps: S1: uniformly mixing 0-10 parts of anhydride and 5-20 parts of a polyol, reacting at 80-100°C for 3h to obtain a first reaction liquid; S2: adding 30-70 parts of an isocyanate, 0-15 parts of a hydroxy acid monomer, 20-50 parts of a UV curing diluent monomer, 0.01-0.06 parts of a catalyst, and 0.01-0.06 parts of an inhibitor to the first reaction liquid, and reacting at 70-80°C for 2-3h, Until the mass concentration of isocyanate ions reaches 2%-6%, a second reaction solution is obtained; S3: 20-300 parts of hydroxy acrylate, 0.05-0.1 parts of catalyst, and 0.05-0.1 parts of inhibitor are added to the second reaction solution, and the reaction is stirred at 60-80°C until the mass concentration of isocyanate ions is less than 0.6%; S4: when the solution temperature of S3 drops below 40°C, 2-15 parts of neutralizer are added, and the reaction is stirred for 30-45 minutes. When the temperature begins to drop uniformly, the stirring reaction is stopped to obtain a polyurethane acrylate prepolymer; the third step is to mix 0-55 parts of polyurethane acrylate prepolymer and 0-65 parts of epoxy acrylate prepolymer evenly to obtain a water-based hyperbranched UV resin for 3D printing.

[0015] The present invention also provides an application of the above-mentioned water-based hyperbranched UV resin for 3D printing in the fields of aerospace, medical treatment, artwork, shoemaking, automobiles, etc.

[0016] The beneficial effects of the present invention are as follows:

[0017] The present invention introduces hydrophilic groups on the basis of traditional UV resin to make it have good water solubility; at the same time, the resin synthesized by the present invention is 100% solid and does not contain any volatile components. Unlike traditional water-based UV that contains a certain amount of water as a dilution solvent, the present invention can be directly UV-cured during use, eliminating the time for water volatilization, and providing the possibility of use in 3D printing. At the same time, it can avoid the use of a large amount of solvent to clean the material tank, making the resin green, environmentally friendly, safe and healthy during use.

[0018] In addition, the present invention can synthesize polyols with super high functionality and more reactive groups. Compared with polyols on the market, the polyols synthesized by the present invention have controllable structures, more reactive groups and lower viscosity. Therefore, in the final 3D printing formula, the amount of diluent monomer used can be greatly reduced (in conventional 3D printing formulas, the diluent monomer content is 50-80%, and when using the resin of the present invention, at the same viscosity, the diluent monomer content is only 5-15%), so that the performance of the final product is more excellent and can be adjusted according to actual conditions, and is no longer limited by the diluent monomer.

[0019] Due to the epoxy acrylate introduced in the present invention, the shrinkage rate is greatly reduced, the precision of the product is improved, and the possibility of its use in high-precision fields is provided. At the same time, the hyperbranched structure of the present invention greatly increases the double bond content per unit volume, accelerates the curing rate of the product, and at the same time, due to the characteristics of the hyperbranched structure, although the double bond content is high, the shrinkage rate is low, which further improves the precision of the product.

[0020] The product of the invention can be widely used in the fields of artistic creation, aerospace, medical treatment, automobile, shoemaking, clothing, jewelry and personalized gift design. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the technical solution of the present invention, the drawings required to be used in the embodiments are briefly introduced below.

[0022] Figure 1 These are the resin products prepared according to Examples 1 to 4 of the present invention.

[0023] Figure 2 The pictures are the appearance of the products prepared according to Examples 1 to 4 of the present invention in the water addition test before curing.

[0024] Figure 3The pictures are of whether there is residual resin in the container during the water addition test before curing of the products prepared according to Examples 1 to 4 of the present invention. DETAILED DESCRIPTION

[0025] The present invention is further described in detail below in conjunction with specific embodiments. The embodiments of the present invention are provided for the sake of illustration and convenience of description, and are not intended to be exhaustive or to limit the present invention to the disclosed forms. Many modifications and variations are apparent to those of ordinary skill in the art. The embodiments are selected and described to better illustrate the principles and practical applications of the present invention, and to enable those of ordinary skill in the art to understand the present invention and thereby design various embodiments with various modifications suitable for specific uses.

[0026] The water-based hyperbranched UV resin for 3D printing provided by the present invention consists of 0-55% of polyurethane acrylate prepolymer and 0-65% of epoxy acrylate prepolymer. The polyurethane acrylate prepolymer comprises the following components in parts by weight: 20-50 parts of UV curing dilution monomer, 0-15 parts of hydroxy acid monomer, 0-10 parts of acid anhydride, 30-70 parts of isocyanate, 5-20 parts of polyol, 0.06-0.16 parts of catalyst, 0.06-0.16 parts of inhibitor, 20-300 parts of hydroxy acrylate, and 2-15 parts of neutralizer; the epoxy acrylate prepolymer comprises the following components in parts by weight: 78-107 parts of dibasic acid, 70-95 parts of diol, 175-240 parts of amino acid, 110-195 parts of epoxy acrylic monomer, 50-100 parts of neutralizer, 1.4-2.4 parts of catalyst, 0.01-0.05 parts of inhibitor, and 15-25 parts of UV curing dilution monomer.

[0027] In the water-based hyperbranched UV resin for 3D printing provided according to the present invention, the water content of the UV curing dilution monomer, hydroxy acid monomer, isocyanate, polyol, catalyst, inhibitor, solvent, and hydroxy acrylate is less than 500 ppm.

[0028] In the water-based hyperbranched UV resin for 3D printing provided according to the present invention, the UV curing diluent monomer is at least one of acryloylmorpholine (ACMO), o-phenylphenoxyethyl acrylate (0PPEA), tetrahydrofuran acrylate (THFA), ethoxylated trimethylolpropane triacrylate (3EOTMPTA), and trimethylolpropane triacrylate (TMPTA).

[0029] In the polyurethane acrylate prepolymer according to the present invention, the polyol is at least one of an intermediate polyol in the synthesis process of epoxy acrylate prepolymer, Dow SD301, boltorn dendritic polyol, and pentaerythritol.

[0030] In the polyurethane acrylate prepolymer according to the present invention, the isocyanate is at least one of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), and 4,4'-dicyclohexylmethane diisocyanate (HMDI); the hydroxy acid monomer is at least one of 2,2-dimethylolpropionic acid (DMPA), dimethylolbutyric acid (DMBA), and isethionic acid; the acid anhydride is at least one of succinic anhydride, phthalic anhydride, acetic anhydride, and maleic anhydride; and the hydroxy acrylate is at least one of dipentaerythritol pentaacrylate, pentaerythritol triacrylate, butyl hydroxy acrylate, and ethyl hydroxy acrylate.

[0031] In the water-based hyperbranched UV resin for 3D printing provided by the present invention, the polyurethane acrylate prepolymer catalyst is at least one of organic bismuth, solid amine, N-methylmorpholine, and N,N'-diethylpiperazine; the epoxy acrylate prepolymer catalyst is at least one of p-toluenesulfonic acid monohydrate (P-TSA), concentrated hydrochloric acid, concentrated sulfuric acid, thionyl chloride, and trifluoromethanesulfonic acid.

[0032] In the epoxy acrylate prepolymer according to the present invention, the dibasic acid is at least one of oxalic acid, malonic acid, succinic acid, and fumaric acid; the diol is at least one of butanediol, hexanediol, and neopentyl glycol; the amino acid is at least one of glutamic acid, aspartic acid, and acetylglutamic acid; and the epoxy acrylic monomer is at least one of glycidyl methacrylate (GMA) and versatate glycidyl carbonate.

[0033] In the water-based hyperbranched UV resin for 3D printing provided by the present invention, the inhibitor is at least one of p-hydroxyanisole, hydroquinone, and 2,5-dimethylhydroquinone; the neutralizer is at least one of triethylamine, N,N-dimethylethanolamine, ammonia water, sodium hydroxide, and potassium hydroxide.

[0034] The preparation method of the water-based hyperbranched UV resin for 3D printing according to the present invention comprises the following steps: the first step is to synthesize an epoxy acrylic prepolymer, comprising the following steps: S1: 15-25 parts of UV curing dilution monomer, 8-12 parts of dibasic acid, 25-35 parts of amino acid, and 0.1-0.3 parts of catalyst are mixed evenly, stirred and reacted at 130-160°C for 4 hours until no water is discharged (the reaction will generate no, if no water is generated, it proves that the reaction is completed), condense and remove water during the reaction to obtain a first reaction liquid; S2: 50-70 parts of amino acid and 0.2-0.4 parts of catalyst are added to the first reaction liquid, stirred and reacted at 130-160°C for 4 hours until no water is discharged to obtain a second reaction liquid; S3: 70-95 parts of diol and 0.3-0.5 parts of catalyst are added to the second reaction liquid, stirred and reacted at 130-160°C for 4 hours until no water is discharged to obtain a second reaction liquid. The mixture was stirred at 160°C for 4 hours until no water was discharged to obtain a third reaction liquid; S4: 70-95 parts of a dibasic acid and 0.3-0.5 parts of a catalyst were added to the third reaction liquid, and the mixture was stirred at 130-160°C for 4 hours until no water was discharged to obtain a fourth reaction liquid; S5: 100-135 parts of an amino acid and 0.5-0.7 parts of a catalyst were added to the fourth reaction liquid, and the mixture was stirred at 130-160°C for 4 hours until no water was discharged to obtain a fifth reaction liquid; S6: 110-195 parts of an epoxy acrylic monomer and 0.01-0.05 parts of an inhibitor were added to the fifth reaction liquid, and the mixture was stirred at 130-160°C for 3 hours, and the mixture was cooled to 45°C to obtain a sixth reaction liquid; S7: 50-100 parts of a neutralizer were added to the sixth reaction liquid, and the mixture was stirred for 30 minutes to obtain an epoxy acrylate prepolymer. The second step is to synthesize a polyurethane acrylate prepolymer, which includes the following steps: S1: uniformly mix 0-10 parts of anhydride and 5-20 parts of polyol, and react at 80-100° C. for 3 hours to obtain a first reaction liquid; S2: add 30-70 parts of isocyanate, 0-15 parts of hydroxy acid monomer, 20-50 parts of UV curing dilution monomer, 0.01-0.06 parts of catalyst, and 0.01-0.06 parts of polymerization inhibitor to the first reaction liquid, and react at 70-80° C. for 2-3 hours until the mass of the isocyanate ion is reduced. The concentration reaches 2%-6% to obtain a second reaction solution; S3: add 20-300 parts of hydroxy acrylate, 0.05-0.1 parts of catalyst, and 0.05-0.1 parts of inhibitor to the second reaction solution, and stir the reaction at 60-80°C until the mass concentration of isocyanate ion is less than 0.6%; S4: When the solution temperature of S3 drops below 40°C, add 2-15 parts of neutralizer, stir the reaction for 30-45 minutes, and when the temperature begins to drop at a uniform rate, stop stirring the reaction to obtain a polyurethane acrylate prepolymer. The third step is to evenly mix 0-55 parts of polyurethane acrylate prepolymer and 0-65 parts of epoxy acrylate prepolymer to obtain a water-based hyperbranched UV resin for 3D printing.

[0035] The water-based hyperbranched UV resin for 3D printing according to the present invention can be applied in the fields of artistic creation, aerospace, medical treatment, automobiles, artworks, shoemaking, clothing, jewelry, and personalized gift design.

[0036] The uv resin of the present invention introduces a hydrophilic group, which is very water-soluble, so that the material tank for holding the resin can be cleaned with clean water, and no solvent is used, so that environmental protection and pollution-free are achieved. At the same time, the hyperbranched polyol synthesized by oneself is used to make the final resin branching degree higher, and the viscosity is lower, which greatly reduces the use of the diluting monomer, makes the final product performance more excellent, and can be adjusted according to actual conditions, and is no longer restricted by the diluting monomer. At the same time, epoxy acrylate is introduced to greatly reduce its shrinkage rate, improve the precision of the product, and provide possibility for its use in the high-precision end field. At the same time, the hyperbranched structure of the present invention greatly increases the double bond content in the unit volume, accelerates the curing rate of the product, and at the same time, due to the characteristics of the hyperbranched structure, although the double bond content is high, the shrinkage rate is relatively low, which further improves the precision of the product. In addition, the present invention contains two structures of epoxy and polyurethane, and has both the hardness of epoxy and the toughness of polyurethane, so that the final product performance is more perfect and excellent, and can be widely used in the fields of artistic creation, aerospace, medical treatment, automobile, shoemaking, clothing, jewelry and personalized gift design.

[0037] The preparation method of the present invention is divided into three steps for reaction: in the first step, steps S1-S6 are controlled by reaction time and temperature, and the reaction time and reaction end point of the step are determined by whether water is still generated and flowing out. In the second step, step S1 is controlled by reaction time and temperature, steps S2 and S3 are controlled by reaction time and temperature, and the reaction time and reaction end point of the step are determined by detecting the mass concentration of isocyanate ions, and step S4 is controlled by reaction time and temperature, and the reaction end point of the step is when the temperature starts to decrease at a uniform rate. In the third step, the performance of the final product is controlled by adjusting the ratio of the two components, thereby obtaining resins with different performances.

[0038] The invention controls the production process according to the reaction temperature, reaction time, mass concentration of isocyanate ions and whether water is continuously generated, thereby synthesizing a water-based hyperbranched UV resin for 3D printing, which not only has a low viscosity, but can also be washed with water and has a low shrinkage rate.

[0039] The following is a detailed description of the 3D printing water-based hyperbranched UV resin and its preparation method and application in conjunction with specific embodiments of the present invention.

[0040] Main raw materials and equipment used: Unless otherwise specified, the raw materials and equipment of each embodiment and comparative example are the same; materials without specifying the specific model or type are from the same common model purchased on the market, without specific limitation.

[0041] Example 1

[0042] The preparation method of the aqueous hyperbranched UV resin for 3D printing provided in this embodiment comprises the following steps:

[0043] The first step is to synthesize epoxy acrylic prepolymer, comprising the following steps:

[0044] S1: 20 parts of acryloylmorpholine (ACMO), 11.8 parts of succinic acid, 29.4 parts of glutamic acid, and 0.2 parts of p-toluenesulfonic acid monohydrate (P-TSA) were mixed uniformly, and stirred for reaction at 150°C for 4 hours (no more water was discharged), and water was condensed and removed during the reaction to obtain a first reaction liquid; S2: 55.9 parts of glutamic acid and 0.3 parts of p-toluenesulfonic acid monohydrate (P-TSA) were added to the first reaction liquid, and stirred for reaction at 150°C for 4 hours until no more water was discharged to obtain a second reaction liquid; S3: 94.5 parts of hexanediol and 0.4 parts of p-toluenesulfonic acid monohydrate (P-TSA) were added to the second reaction liquid, and stirred for reaction at 150°C for 4 hours until no more water was discharged to obtain a third reaction liquid; S4: 94.5 parts of succinic acid and 0.4 parts of p-toluenesulfonic acid monohydrate (P-TSA) were added to the third reaction liquid, and the mixture was stirred and reacted at 150°C for 4 hours until no more water was discharged to obtain a fourth reaction liquid; S5: 117.7 parts of glutamic acid and 0.6 parts of p-toluenesulfonic acid monohydrate (P-TSA) were added to the fourth reaction liquid, and the mixture was stirred and reacted at 150°C for 4 hours until no more water was discharged to obtain a fifth reaction liquid; S6: 113.7 parts of glycidyl methacrylate (GMA) and 0.03 parts of hydroquinone were added to the fifth reaction liquid, and the mixture was stirred and reacted at 130°C for 3 hours, and the mixture was cooled to 45°C to obtain a sixth reaction liquid; S7: 81 parts of triethylamine were added to the sixth reaction liquid, and the mixture was stirred for 30 minutes to obtain an epoxy acrylate prepolymer.

[0045] The second step is to synthesize the polyurethane acrylate prepolymer, which includes the following steps:

[0046] S1: 2.94 parts of maleic anhydride and 15 parts of the third reaction solution of the third step (S3) in the first step are mixed evenly, and the mixture is reacted at 95°C for 3 hours to obtain a first reaction solution; S2: 44.44 parts of isophorone diisocyanate (IPDI), 12.06 parts of 2,2-dihydroxymethylpropionic acid (DMPA), 30 parts of ethoxylated trimethylolpropane triacrylate (3EOTMPTA), 0.03 parts of organic bismuth, and 0.03 parts of hydroquinone are added to the first reaction solution, and the mixture is reacted at 75°C for 2 hours. .5h, until the mass concentration of isocyanate ions reaches 5%-6%, to obtain a second reaction solution; S3: add 96 parts of pentaerythritol triacrylate, 0.07 parts of organic bismuth, and 0.07 parts of hydroquinone to the second reaction solution, and stir to react at 75°C until the mass concentration of isocyanate ions is less than 0.6%; S4: when the solution temperature of S3 drops below 40°C, add 12.14 parts of triethylamine, stir to react for 30 minutes, and when the temperature begins to drop uniformly, stop stirring the reaction to obtain a polyurethane acrylate prepolymer.

[0047] In the third step, 50 parts of the first step epoxy acrylate prepolymer and 50 parts of the second step polyurethane acrylate prepolymer are evenly mixed to prepare a water-based hyperbranched UV resin for 3D printing.

[0048] Example 2

[0049] The preparation method of the aqueous hyperbranched UV resin for 3D printing provided in this embodiment comprises the following steps:

[0050] The first step is to synthesize epoxy acrylic prepolymer, comprising the following steps:

[0051] S1: 25 parts of trimethylolpropane triacrylate (TMPTA), 9 parts of oxalic acid, 29.4 parts of glutamic acid, and 0.2 parts of p-toluenesulfonic acid monohydrate (P-TSA) were mixed uniformly, and stirred for reaction at 150°C for 4 hours (no more water was discharged), and water was condensed and removed during the reaction to obtain a first reaction liquid; S2: 55.9 parts of glutamic acid and 0.3 parts of p-toluenesulfonic acid monohydrate (P-TSA) were added to the first reaction liquid, and stirred for reaction at 150°C for 4 hours until no more water was discharged to obtain a second reaction liquid; S3: 83.3 parts of neopentyl glycol and 0.4 parts of p-toluenesulfonic acid monohydrate (P-TSA) were added to the second reaction liquid, and stirred for reaction at 150°C for 4 hours until no more water was discharged to obtain a third reaction liquid; S4: Add 72 parts of oxalic acid and 0.4 parts of p-toluenesulfonic acid monohydrate (P-TSA) to the reaction liquid, stir and react at 150°C for 4 hours until no more water is discharged, to obtain a fourth reaction liquid; S5: Add 117.7 parts of glutamic acid and 0.6 parts of p-toluenesulfonic acid monohydrate (P-TSA) to the fourth reaction liquid, stir and react at 150°C for 4 hours until no more water is discharged, to obtain a fifth reaction liquid; S6: Add 113.7 parts of glycidyl methacrylate (GMA) and 0.03 parts of hydroquinone to the fifth reaction liquid, stir and react at 130°C for 3 hours, and cool to 45°C to obtain a sixth reaction liquid; S7: Add 71.23 parts of N,N-dimethylethanolamine to the sixth reaction liquid, stir for 30 minutes, to obtain an epoxy acrylate prepolymer.

[0052] Step 2: Synthesizing polyurethane acrylate prepolymer, including the following steps:

[0053] S1: 4.44 parts of maleic anhydride, 10 parts of the third reaction solution of the third sub-step (S3) in the first step, and 10 parts of Dow SD301 were mixed evenly, and reacted at 95° C. for 3 hours to obtain a first reaction solution;

[0054] S2: add 44.44 parts of isophorone diisocyanate (IPDI), 10.72 parts of 2,2-dihydroxymethyl propionic acid (DMPA), 40 parts of o-phenylphenoxyethyl acrylate (OPPEA), 0.04 parts of organic bismuth, and 0.04 parts of hydroquinone to the first reaction liquid, and react at 75° C. for 2.5 hours until the mass concentration of isocyanate ions is less than 4.6%-5.6%, thereby obtaining a second reaction liquid; S3: add 45 parts of pentaerythritol triacrylate, 108 parts of dipentaerythritol pentaacrylate, 0.08 parts of organic bismuth, and 0.08 parts of hydroquinone to the second reaction liquid, and stir and react at 75° C. until the mass concentration of isocyanate ions is less than 0.6%; S4: when the solution temperature of S3 drops below 40° C., add 11.1 parts of triethylamine, stir and react for 30 minutes, and when the temperature begins to drop at a uniform rate, stop stirring and react to obtain a polyurethane acrylate prepolymer.

[0055] In the third step, 60 parts of the first step epoxy acrylate prepolymer and 40 parts of the second step polyurethane acrylate prepolymer are evenly mixed to prepare a water-based hyperbranched UV resin for 3D printing.

[0056] Example 3

[0057] The preparation method of the aqueous hyperbranched UV resin for 3D printing provided in this embodiment comprises the following steps:

[0058] The first step is to synthesize epoxy acrylic prepolymer, comprising the following steps:

[0059] S1: 25 parts of tetrahydrofuran acrylate (THFA), 9 parts of oxalic acid, 26.6 parts of aspartic acid and 0.2 parts of trifluoromethanesulfonic acid were mixed evenly, and stirred for reaction at 145°C for 4 hours (no more water was discharged), and water was condensed and removed during the reaction to obtain a first reaction liquid; S2: 53.2 parts of aspartic acid and 0.3 parts of trifluoromethanesulfonic acid were added to the first reaction liquid, and stirred for reaction at 145°C for 4 hours until no more water was discharged to obtain a second reaction liquid; S3: 72.08 parts of butanediol and 0.4 parts of trifluoromethanesulfonic acid were added to the second reaction liquid, and stirred for reaction at 145°C for 4 hours until no more water was discharged to obtain a third reaction liquid; S4: Add 72 parts of oxalic acid and 0.4 parts of trifluoromethanesulfonic acid, stir and react at 145°C for 4 hours until no water is discharged to obtain a fourth reaction liquid; S5: add 106.5 parts of aspartic acid and 0.6 parts of trifluoromethanesulfonic acid to the fourth reaction liquid, stir and react at 145°C for 4 hours until no water is discharged to obtain a fifth reaction liquid; S6: add 182.56 parts of tert-butyl glycidyl carbonate and 0.04 parts of hydroquinone to the fifth reaction liquid, stir and react at 135°C for 3 hours, cool to 45°C to obtain a sixth reaction liquid; S7: add 71.23 parts of N,N-dimethylethanolamine to the sixth reaction liquid, stir for 30 minutes to obtain an epoxy acrylate prepolymer.

[0060] The second step is to synthesize the polyurethane acrylate prepolymer, which includes the following steps:

[0061] S1: 3 parts of succinic anhydride, 12 parts of the third reaction solution of the third step (S3) in the first step, and 8 parts of boltorn P1000 were mixed evenly, and the mixture was reacted at 95°C for 3 hours to obtain a first reaction solution; S2: 52.47 parts of 4,4'-dicyclohexylmethane diisocyanate (HMDI), 10.36 parts of dihydroxymethylbutyric acid (DMBA), 20 parts of acryloyl morpholine (ACMO), 0.04 parts of N-methylmorpholine, and 0.04 p-hydroxyanisole were added to the first reaction solution, and the mixture was reacted at 75°C for 2.5 hours until the mass of the isocyanate ion was reduced to 1. The mass concentration is less than 4.78%-5.78% to obtain a second reaction liquid; S3: add 10.2 parts of ethyl hydroxyacrylate, 98.3 parts of dipentaerythritol pentaacrylate, 0.06 parts of N-methylmorpholine, and 0.06 p-hydroxyanisole to the second reaction liquid, and stir to react at 75°C until the mass concentration of isocyanate ion is less than 0.6%; S4: when the solution temperature of S3 drops below 40°C, add 8.9 parts of N,N-dimethylethanolamine, stir to react for 30 minutes, and when the temperature begins to drop at a uniform rate, stop stirring the reaction to obtain a polyurethane acrylate prepolymer.

[0062] In the third step, 55 parts of the first step epoxy acrylate prepolymer and 45 parts of the second step polyurethane acrylate prepolymer are evenly mixed to prepare a water-based hyperbranched UV resin for 3D printing.

[0063] Example 4

[0064] The preparation method of the aqueous hyperbranched UV resin for 3D printing provided in this embodiment comprises the following steps:

[0065] The first step is to synthesize epoxy acrylic prepolymer, comprising the following steps:

[0066] S1: 25 parts of trimethylolpropane triacrylate (TMPTA), 10.4 parts of malonic acid, 33.8 parts of acetylglutamic acid and 0.2 parts of trifluoromethanesulfonic acid were mixed uniformly, and stirred for reaction at 155°C for 4 hours (no more water was discharged), and water was condensed and removed during the reaction to obtain a first reaction liquid; S2: 67.6 parts of acetylglutamic acid and 0.3 parts of trifluoromethanesulfonic acid were added to the first reaction liquid, and stirred for reaction at 155°C for 4 hours until no more water was discharged to obtain a second reaction liquid; S3: 72.08 parts of butanediol and 0.4 parts of trifluoromethanesulfonic acid were added to the second reaction liquid, and stirred for reaction at 155°C for 4 hours until no more water was discharged to obtain a third reaction liquid; S4: Add 83.2 parts of malonic acid and 0.4 parts of trifluoromethanesulfonic acid to the reaction liquid, stir and react at 155°C for 4 hours until no water is discharged, to obtain a fourth reaction liquid; S5: add 135 parts of acetylglutamic acid and 0.6 parts of trifluoromethanesulfonic acid to the fourth reaction liquid, stir and react at 155°C for 4 hours until no water is discharged, to obtain a fifth reaction liquid; S6: add 182.56 parts of tert-butyl glycidyl carbonate and 0.04 parts of hydroquinone to the fifth reaction liquid, stir and react at 145°C for 3 hours, and cool to 45°C to obtain a sixth reaction liquid; S7: add 71.23 parts of N,N-dimethylethanolamine to the sixth reaction liquid, stir for 30 minutes, to obtain an epoxy acrylate prepolymer.

[0067] The second step is to synthesize the polyurethane acrylate prepolymer, which includes the following steps:

[0068] S1: 3.02 parts of acetic anhydride, 15 parts of the third reaction solution of the third step (S3) in the first step, and 5 parts of boltorn P1000 were mixed evenly, and the mixture was reacted at 95°C for 3 hours to obtain a first reaction solution; S2: 52.47 parts of 4,4'-dicyclohexylmethane diisocyanate (HMDI), 11.84 parts of dihydroxymethylbutyric acid (DMBA), 25 parts of acryloyl morpholine (ACMO), 0.04 parts of N-methylmorpholine, and 0.04 p-hydroxyanisole were added to the first reaction solution, and the mixture was reacted at 75°C for 2.5 hours until the isocyanate ion was The mass concentration of is less than 4.6%-5.6% to obtain a second reaction liquid; S3: add 12.78 parts of butyl hydroxyacrylate, 80 parts of pentaerythritol triacrylate, 0.05 parts of N-methylmorpholine, and 0.05 p-hydroxyanisole to the second reaction liquid, and stir to react at 75°C until the mass concentration of isocyanate ion is less than 0.6%; S4: when the solution temperature of S3 drops below 40°C, add 9.79 parts of N,N-dimethylethanolamine, stir to react for 30 minutes, and when the temperature begins to drop at a uniform rate, stop stirring the reaction to obtain a polyurethane acrylate prepolymer.

[0069] In the third step, 50 parts of the first step epoxy acrylate prepolymer and 50 parts of the second step polyurethane acrylate prepolymer are evenly mixed to prepare a water-based hyperbranched UV resin for 3D printing.

[0070] Performance Testing

[0071] 1. Physical property index test

[0072] Viscosity test: using a rotor viscometer, rotor 2, 60 speed. The test results of Examples 1-4 are shown in Table 1.

[0073] Table 1 Viscosity test results

[0074] sample Example 1 Example 2 Example 3 Example 4 Viscosity / mpa.s 500 400 390 450

[0075] It can be seen from the test results in Table 1 that the resin synthesized by the present invention has a viscosity below 500 mPa.s, and can be directly used for 3D printing without dilution. It can ensure that the performance of the final product is basically determined by the resin itself and is no longer affected by the dilution monomer, and can be more widely used in actual life production.

[0076] 2. Resin volume shrinkage test

[0077] Density method: The shrinkage rate is calculated by measuring the density of the resin before and after curing. The formula is (ρafter-ρbefore) / ρafter×100%, where ρafter and ρbefore are the densities after curing and before curing, respectively. The density is determined by using a hydrometer in combination with the buoyancy method. The test results of Examples 1-4 are shown in Table 2.

[0078] Table 2 Volume shrinkage test results

[0079] sample Example 1 Example 2 Example 3 Example 4 Volume shrinkage / % 0.2 0.1 0.15 0.17

[0080] It can be seen from the test results in Table 2 that the volume shrinkage of the resin of the present invention is extremely low and can be basically ignored, which greatly improves the accuracy of 3D printing and provides the possibility for its application in some high-precision fields.

[0081] In addition, the present invention is a mixture of two components, one component is epoxy acrylate, which has extremely low shrinkage and high strength; the other component is polyurethane acrylate, which has excellent wear resistance and weather resistance. Therefore, the two components can be mixed in different proportions to meet specific needs in practical applications.

[0082] 3. Water solubility and water resistance test

[0083] Before curing, add water directly to the resin and stir with a glass rod to see whether it is easy to dissolve in water and the appearance after dissolving in water. At the same time, wash the container containing the resin with running water to see whether the container can be cleaned and whether there is any resin residue on the surface. Put the cured resin in 100℃ boiling water for 1 hour, then put it in water at room temperature (25℃) for 7 days, and observe whether the appearance of the resin changes and turns white. The test results of Examples 1-4 are shown in Table 3. The actual pictures are as follows Figures 1 to 3 shown.

[0084] Table 3 Water solubility and water resistance test results

[0085]

[0086]

[0087] According to the test results in Table 3 and Figures 1 to 3 It can be seen that the resin of the present invention is very water-soluble, and the container containing the resin is clean and has no resin residue after being washed with running water, which can ensure that the material tank can be directly washed with water in actual use without using solvents, which not only reduces the cost of use, but also is environmentally friendly and pollution-free. In addition, although the resin in the present invention is easily water-soluble, since amines are used as neutralizers, the amines can be volatilized, and after curing, there is no free amine residue in the system, which ensures that it has good water resistance. The test results also prove that the resin of the present invention has excellent resistance to both normal temperature water and boiling water.

[0088] Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field and related fields without creative work should fall within the scope of protection of the present invention. The structures, devices and operating methods not specifically described and explained in the present invention are implemented according to the conventional means in the field unless otherwise specified and limited.

Claims

1. A water-based hyperbranched UV resin for 3D printing, characterized in that: The resin is composed of 0-55% polyurethane acrylate prepolymer and 0-65% epoxy acrylate prepolymer; The polyurethane acrylate prepolymer comprises the following components in parts by weight: 20-50 parts of UV curable diluent monomer, 0-15 parts of hydroxy acid monomer, 0-10 parts of acid anhydride, 30-70 parts of isocyanate, 5-20 parts of polyol, 0.06-0.16 parts of catalyst, 0.06-0.16 parts of inhibitor, 20-300 parts of hydroxy acrylate, and 2-15 parts of neutralizer; The epoxy acrylate prepolymer comprises the following components in parts by weight: 78-107 parts of dibasic acid, 70-95 parts of diol, 175-240 parts of amino acid, 110-195 parts of epoxy acrylic monomer, 50-100 parts of neutralizer, 1.4-2.4 parts of catalyst, 0.01-0.05 parts of inhibitor, and 15-25 parts of UV curing dilution monomer.

2. The water-based hyperbranched UV resin for 3D printing according to claim 1, characterized in that The water content of the UV curing diluent monomer, hydroxy acid monomer, isocyanate, polyol, catalyst, inhibitor, solvent and hydroxy acrylate is lower than 500 ppm.

3. The water-based hyperbranched UV resin for 3D printing according to claim 1, characterized in that The UV curable diluent monomer is at least one of acryloyl morpholine (ACMO), o-phenylphenoxyethyl acrylate (0PPEA), tetrahydrofuran acrylate (THFA), ethoxylated trimethylolpropane triacrylate (3EOTMPTA), and trimethylolpropane triacrylate (TMPTA).

4. The water-based hyperbranched UV resin for 3D printing according to claim 1, characterized in that The polyol is at least one of an intermediate polyol in the synthesis process of epoxy acrylate prepolymer, Dow SD301, boltorn dendritic polyol, and pentaerythritol.

5. The water-based hyperbranched UV resin for 3D printing according to claim 1, characterized in that The isocyanate is at least one of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), and 4,4'-dicyclohexylmethane diisocyanate (HMDI); the hydroxy acid monomer is at least one of 2,2-dihydroxymethylpropionic acid (DMPA), dihydroxymethylbutyric acid (DMBA), and isethionic acid; the acid anhydride is at least one of succinic anhydride, phthalic anhydride, acetic anhydride, and maleic anhydride; the hydroxy acrylate is at least one of dipentaerythritol pentaacrylate, pentaerythritol triacrylate, hydroxy butyl acrylate, and hydroxy ethyl acrylate.

6. The water-based hyperbranched UV resin for 3D printing according to claim 1, characterized in that The polyurethane acrylate prepolymer catalyst is at least one of organic bismuth, solid amine, N-methylmorpholine, and N,N'-diethylpiperazine; the epoxy acrylate prepolymer catalyst is at least one of p-toluenesulfonic acid monohydrate (P-TSA), concentrated hydrochloric acid, concentrated sulfuric acid, thionyl chloride, and trifluoromethanesulfonic acid.

7. The water-based hyperbranched UV resin for 3D printing according to claim 1, characterized in that: The dibasic acid is at least one of oxalic acid, malonic acid, succinic acid, and fumaric acid; the diol is at least one of butanediol, hexanediol, and neopentyl glycol; the amino acid is at least one of glutamic acid, aspartic acid, and acetylglutamic acid; and the epoxy acrylic monomer is at least one of glycidyl methacrylate (GMA) and glycidyl versatate.

8. The water-based hyperbranched UV resin for 3D printing according to claim 1, characterized in that: The inhibitor is at least one of p-hydroxyanisole, hydroquinone, and 2,5-dimethylhydroquinone; the neutralizer is at least one of triethylamine, N,N-dimethylethanolamine, ammonia water, sodium hydroxide, and potassium hydroxide.

9. The method for preparing a water-based hyperbranched UV resin for 3D printing according to any one of claims 1 to 8, characterized in that: The steps include: The first step is to synthesize epoxy acrylic prepolymer, comprising the following steps: S1: 15-25 parts of UV curable diluent monomer, 8-12 parts of dibasic acid, 25-35 parts of amino acid and 0.1-0.3 parts of catalyst are mixed evenly, and stirred at 130-160° C. for 4 hours until no water is discharged. During the reaction, water is condensed and removed to obtain a first reaction solution; S2: Add 50-70 parts of amino acid and 0.2-0.4 parts of catalyst to the first reaction solution, stir and react at 130-160° C. for 4 hours until no water is discharged, to obtain a second reaction solution; S3: Add 70-95 parts of diol and 0.3-0.5 parts of catalyst to the second reaction liquid, stir and react at 130-160° C. for 4 hours until no water is discharged, to obtain a third reaction liquid; S4: adding 70-95 parts of dibasic acid and 0.3-0.5 parts of catalyst to the third reaction liquid, stirring and reacting at 130-160° C. for 4 hours until no water is discharged, to obtain a fourth reaction liquid; S5: adding 100-135 parts of amino acid and 0.5-0.7 parts of catalyst to the fourth reaction liquid, stirring and reacting at 130-160° C. for 4 hours until no water is discharged, to obtain a fifth reaction liquid; S6: adding 110-195 parts of epoxy acrylic monomer and 0.01-0.05 parts of polymerization inhibitor to the fifth reaction liquid, stirring and reacting at 130-160° C. for 3 hours, and cooling to 45° C. to obtain a sixth reaction liquid; S7: adding 50-100 parts of a neutralizing agent to the sixth reaction solution and stirring for 30 minutes to obtain an epoxy acrylate prepolymer; The second step is to synthesize the polyurethane acrylate prepolymer, which includes the following steps: S1: 0-10 parts of anhydride and 5-20 parts of polyol are mixed evenly, and reacted at 80-100° C. for 3 hours to obtain a first reaction solution; S2: Add 30-70 parts of isocyanate, 0-15 parts of hydroxy acid monomer, 20-50 parts of UV curing dilution monomer, 0.01-0.06 parts of catalyst, and 0.01-0.06 parts of polymerization inhibitor to the first reaction solution, and react at 70-80° C. for 2-3 hours until the mass concentration of isocyanate ions reaches 2%-6%, to obtain a second reaction solution; S3: adding 20-300 parts of hydroxy acrylate, 0.05-0.1 parts of catalyst, and 0.05-0.1 parts of polymerization inhibitor to the second reaction solution, stirring and reacting at 60-80° C. until the mass concentration of isocyanate ion is less than 0.6%; S4: When the temperature of the solution of S3 drops below 40°C, add 2-15 parts of a neutralizing agent and stir to react for 30-45 minutes. When the temperature begins to drop at a uniform rate, stop stirring to react and obtain a polyurethane acrylate prepolymer. In the third step, 0-55 parts of polyurethane acrylate prepolymer and 0-65 parts of epoxy acrylate prepolymer are evenly mixed to prepare a water-based hyperbranched UV resin for 3D printing.

10. Application of the 3D printing water-based hyperbranched UV resin according to any one of claims 1 to 8 in the fields of aerospace, medical treatment, artwork, shoemaking, automobiles, etc.

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