High-precision retention rate 3D printing resin and preparation method thereof

Abstract

The invention is applicable to the technical field of printing materials, and particularly relates to high-precision retention rate 3D printing resin and a preparation method thereof, and the high-precision retention rate 3D printing resin comprises 60-80 parts of a fluorine-containing prepolymer, 5-15 parts of a tri-functionality monomer, 5-25 parts of a diluent and 1-5 parts of a photoinitiator. According to the 3D printing resin with the high precision retention rate, provided by the invention, the prepolymer synthesized from perfluoropolyether glycol has relatively high molecular weight and still has relatively low viscosity, so that the dosage of a diluent is reduced, and the effects of low shrinkage rate and high precision are achieved.

Description

Technical Field

[0001] The present invention belongs to the technical field of printing materials, and in particular relates to a high-precision retention rate 3D printing resin and a preparation method thereof. Background Art

[0002] 3D printing resin is a liquid photosensitive polymer material designed for light-curing 3D printing technology. It can quickly harden and take shape when exposed to ultraviolet rays of a specific wavelength. This material is widely favored for its high precision, smooth surface treatment effect and a wide range of material properties (such as transparency, high temperature resistance, flexibility, etc.). It is suitable for making fine models, prototype verification, jewelry design, dental restoration and other application scenarios. With the advancement of technology, the types of 3D printing resins are becoming more and more abundant, and the performance is constantly improving, providing more innovation possibilities for all walks of life.

[0003] Existing 3D printing resins require the addition of a large amount of diluent to ensure printability, but the diluent will increase the shrinkage rate of the 3D printing resin and reduce the accuracy. Summary of the invention

[0004] The purpose of the present invention is to provide a 3D printing resin with a high precision retention rate, aiming to solve the problem that the existing 3D printing resin needs to add a large amount of diluent to ensure printability, but the diluent will increase the shrinkage rate of the 3D printing resin and reduce the precision.

[0005] The present invention is achieved by providing a high-precision retention 3D printing resin, which includes 60-80 parts of a fluorine-containing prepolymer, 5-15 parts of a trifunctional monomer, 5-25 parts of a diluent, and 1-5 parts of a photoinitiator.

[0006] Preferably, the structure of the fluorine-containing prepolymer is:

[0007]

[0008] Preferably, in the fluorine-containing prepolymer, n=m, and the value range is 2-16.

[0009] Preferably, the preparation process of the fluorine-containing prepolymer is that perfluoropolyether diol and isocyanoethyl methacrylate react under the action of a catalyst until the isocyanate group completely disappears in the infrared spectrum to obtain a fluorine-containing prepolymer, the molar ratio of perfluoropolyether diol and isocyanoethyl methacrylate is 1:2, and an inhibitor is added during the reaction.

[0010] Preferably, the trifunctional monomer is ethoxylated trimethylolpropane triacrylate.

[0011] Preferably, the diluent is acryloylmorpholine.

[0012] Another object of the present invention is to provide a method for preparing a 3D printing resin with a high precision retention rate, taking a preset proportion of a fluorine-containing prepolymer, a trifunctional monomer, a diluent and a photoinitiator, and stirring them evenly to obtain a printing photosensitive resin.

[0013] The present invention provides a high-precision retention 3D printing resin, which uses a prepolymer synthesized from perfluoropolyether diol. Although it has a high molecular weight, it still has a low viscosity, reduces the amount of diluent used, and achieves the effects of low shrinkage and high precision. DETAILED DESCRIPTION

[0014] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0015] A high-precision retention rate 3D printing resin, the high-precision retention rate 3D printing resin comprising 60-80 parts of a fluorine-containing prepolymer, 5-15 parts of a trifunctional monomer, 5-25 parts of a diluent, and 1-5 parts of a photoinitiator.

[0016] In this embodiment, the proportion of 3D printing resin is: 60-80g of fluorine-containing prepolymer, 5-15g of trifunctional monomer, 5-25g of diluent, and 1-5g of photoinitiator.

[0017] Fluorinated prepolymer structure:

[0018]

[0019] Where n=m, and its value range is 2-16.

[0020] The synthetic route is:

[0021]

[0022] Perfluoropolyether diol and isocyanoethyl methacrylate react at 45-70 degrees Celsius under the action of a catalyst until the isocyanate group completely disappears in the infrared spectrum. The molar ratio of perfluoropolyether diol and isocyanoethyl methacrylate is 1:2. An inhibitor needs to be added during the reaction to prevent polymerization during the reaction.

[0023] A method for preparing a 3D printing resin with a high precision retention rate is characterized in that a fluorine-containing prepolymer, a trifunctional monomer, a diluent and a photoinitiator in a preset proportion are taken and stirred evenly to obtain a printing photosensitive resin.

[0024] Synthesis principle:

[0025] 1. Low shrinkage is the guarantee of high precision of 3D printing resin. Prepolymers with larger molecular weight have low shrinkage, but the larger the molecular weight, the greater the viscosity of the prepolymer, and more diluent is needed to ensure its printability. The addition of more diluent will increase the shrinkage of 3D printing resin and reduce precision. Perfluoropolyether diol has lower viscosity than alkyl diol or alkyl polyether diol at the same molecular weight equivalent due to the poor polarization ability of fluorinated compounds and weak intermolecular interaction. Therefore, the prepolymer synthesized using perfluoropolyether diol has a higher molecular weight but still has a lower viscosity. Therefore, the amount of diluent can be reduced to achieve low shrinkage and high precision.

[0026] Second, since the atomic volume of fluorine is larger than that of hydrogen, the fluorinated alkyl bond has a certain rigidity, which can reduce the deformation caused by post-curing and improve the accuracy retention rate.

[0027] Example 1

[0028] 1 mol of perfluoropolyether diol (n=m=2) and 2 mol of isocyanoethyl methacrylate were mixed, and then 2 drops of dibutyltin dilaurate were added as a catalyst and 0.5% of the total mass of hydroquinone as an inhibitor. The mixture was stirred at 45°C for 72 hours. The absorption peak of the isocyanate group at 2230° completely disappeared by infrared detection, confirming that the reaction was terminated, and a fluorinated prepolymer F was obtained. 2-2 MA.

[0029] Example 2

[0030] 1 mol of perfluoropolyether diol (n=m=9) and 2 mol of isocyanoethyl methacrylate were mixed, and then 2 drops of dibutyltin dilaurate were added as a catalyst and 0.3% of the total mass of p-methoxyphenol as an inhibitor. The mixture was stirred at 60°C for 48 hours. The absorption peak of the isocyanate group at 2230° completely disappeared by infrared detection, confirming that the reaction was terminated, and a fluorinated prepolymer F was obtained. 9-9 MA.

[0031] Example 3

[0032] 1 mol of perfluoropolyether diol (n=m=16) and 2 mol of isocyanoethyl methacrylate were mixed, and then 2 drops of dibutyltin dilaurate and 0.2% of the total mass of the reactants and p-methoxyphenol were added as an inhibitor. The mixture was stirred at 70°C for 32 hours. The absorption peak of the isocyanate group at 2230° completely disappeared by infrared detection, confirming that the reaction was terminated, and a fluorinated prepolymer F was obtained. 16-16 MA.

[0033] Example 4

[0034] Fluorinated prepolymer F 2-2MA 80 parts, trimethylolpropane triacrylate 5 parts, acryloyl morpholine 15 parts, photoinitiator TPO 2 parts, stir evenly to get 3D printing photosensitive resin. The printed part has a bending strength of 95MPa, a bending modulus of 2.3GPa, an initial retrace accuracy of 93%, and a retrace accuracy of 86% after 2 weeks of placement.

[0035] Example 5

[0036] Fluorinated prepolymer F 9-9 MA 70 parts, ethoxylated trimethylolpropane triacrylate 10 parts, acryloyl morpholine 20 parts, photoinitiator TPO 3 parts, stir evenly to obtain 3D printing photosensitive resin. The printed part has a bending strength of 90MPa, a bending modulus of 2.0GPa, an initial retrace accuracy of 96%, and a retrace accuracy of 90% after 2 weeks of placement.

[0037] Example 6

[0038] Fluorinated prepolymer F 16-16 MA 60 parts, ethoxylated trimethylolpropane triacrylate 15 parts, acryloyl morpholine 25 parts, photoinitiator TPO 3.5 parts, stir evenly to obtain 3D printing photosensitive resin. The printed part has a bending strength of 85MPa, a bending modulus of 1.8GPa, an initial retrace accuracy of 98%, and a retrace accuracy of 93% after 2 weeks of placement.

[0039] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A high-precision retention 3D printing resin, characterized in that: The high-precision retention rate 3D printing resin comprises 60-80 parts of fluorine-containing prepolymer, 5-15 parts of trifunctional monomer, 5-25 parts of diluent, and 1-5 parts of photoinitiator.

2. The high-precision retention 3D printing resin according to claim 1, characterized in that: The structure of the fluorine-containing prepolymer is:

3. The high-precision retention 3D printing resin according to claim 1, characterized in that: In the fluorine-containing prepolymer, n=m, and the value range is 2-16.

4. The high-precision retention 3D printing resin according to claim 1, characterized in that: The preparation process of the fluorine-containing prepolymer is that perfluoropolyether diol and isocyanoethyl methacrylate react under the action of a catalyst until the isocyanate group completely disappears in the infrared spectrum to obtain a fluorine-containing prepolymer, the molar ratio of perfluoropolyether diol and isocyanoethyl methacrylate is 1:2, and an inhibitor is added during the reaction.

5. The high-precision retention 3D printing resin according to claim 1, characterized in that: The trifunctional monomer is ethoxylated trimethylolpropane triacrylate.

6. The high-precision retention 3D printing resin according to claim 1, characterized in that: Diluent: acryloyl morpholine.

7. A method for preparing a high-precision retention 3D printing resin, characterized in that: A preset ratio of fluorine-containing prepolymer, trifunctional monomer, diluent and photoinitiator is taken and stirred evenly to obtain a printing photosensitive resin.

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