Photocuring 3D printing resin and preparation method thereof
阅读说明：本技术 一种光固化3d打印树脂及其制备方法 (Photocuring 3D printing resin and preparation method thereof ) 是由 付文彬 于 2020-08-31 设计创作，主要内容包括：本发明涉及光固化树脂材料技术领域,尤其涉及一种光固化3D打印树脂及其制备方法。传统贵金属首饰制作工艺多采用失蜡铸造工艺,蜡模材料材质较软表面易出现划痕,影响铸型制作的精确度,传统失蜡铸造工艺需要在100℃-700℃的阶梯高温下将铸型烧透,用以去除蜡模,耗时又耗能,针对上述问题,本发明提供一种光固化3D打印树脂,本法所制备的树脂模板尺寸精确且硬度较高,表面不易出现划痕,120℃时在DMSO溶液中超声溶解即可去除树脂模板,本发明节能环保具有良好的应用前景。(The invention relates to the technical field of light-cured resin materials, in particular to light-cured 3D printing resin and a preparation method thereof. The traditional precious metal jewelry manufacturing process mostly adopts a lost wax casting process, scratches are prone to occurring on the soft surface of a wax mould material, the accuracy of casting mould manufacturing is affected, the casting mould needs to be completely burnt at the high temperature of 100-700 ℃ in the traditional lost wax casting process to remove the wax mould, time and energy are consumed, and aiming at the problems, the invention provides the photocuring 3D printing resin.)
1. The photocuring 3D printing resin is characterized by comprising the following components in parts by weight:
70-80 parts of polymerized monomer
3-5 parts of photoinitiator
0.5 to 1 portion of light absorbent,
the polymerization monomer comprises the following components in parts by weight:
0 to 50 portions of polymerized monomer I
50-100 parts of a polymerization monomer II.
2. The photocurable 3D printing resin as claimed in claim 1, wherein the molecular structural formulas of the polymerized monomer I and the polymerized monomer II are as follows:
wherein, the structural formulas of R1 and R2 are shown in the specification
The structural formulas of R3, R4 and R5 are shown in the specification
3. The photocurable 3D printing resin as claimed in claim 1, wherein the monomer i is prepared by the following method:
(1) 30g of 2, 5-dioxapyrrole-1-carboxylic acid, 70g of furancarboxylic acid, 25mg of dibutylhydroxytoluene, 650mL of toluene, 145mL of glycidyl methacrylate, 0.1mmol of TiCl catalyst3(OTf) was added to a two-necked flask and mixed well in N2The reaction is carried out for 24 hours at the room temperature,
(2) after the reaction in the step (1) is finished, heating to 60 ℃ for reaction for 40 min;
(3) and (3) cooling the solution after the reaction in the step (2) is finished by ice, filtering precipitates in the solution, and washing the precipitates with cold toluene to obtain a monomer I.
4. The photocurable 3D printing resin as claimed in claim 1, wherein the monomer ii is prepared by the following method:
(1) 3.5g of monomer I was dissolved in 20mL of toluene solution;
(2) slowly adding 37mg of 4-dimethylaminopyridine into the solution obtained in the step (1) at room temperature, and stirring for reaction for 10 min;
(3) adding 290mg of 1,3, 5-tricarbonyl benzene trichloride and 5mL of triethylamine into the reaction solution obtained in the step (2), stirring and reacting for 72 hours at 100 ℃, wherein an infrared spectrogram shows that a stretching vibration peak of-OH disappears, and the reaction is finished;
(4) cooling the reaction solution obtained in the step (3) to room temperature, evaporating under reduced pressure to remove volatile substances, and dissolving in 50mLCH2Cl2Washing with water for 3 times, and passing through a chromatographic column to obtain a monomer II.
5. The photocurable 3D printing resin as recited in claim 1, wherein: the photoinitiator is camphorquinone or 784.
6. The photocurable 3D printing resin as recited in claim 1, wherein: the light absorbent is carotene.
Technical Field
The invention relates to the technical field of light-cured resin materials, in particular to light-cured 3D printing resin and a preparation method thereof.
Background
The lost wax casting process has a long history in the metal casting history of China, and physical demonstration shows that the lost wax casting process of China appears in early spring, autumn and middle period. The lost wax casting process has become the precision casting supported by modern science and technology, is widely applied to the jewelry industry in the 70 s, fundamentally solves the problem that the jewelry manufacturing industry is only dependent on low-efficiency labor of manufacturing processes such as filing, repairing, filing, welding, pinching and the like, greatly improves the manufacturing efficiency of the jewelry industry, solves the problem that the jewelry is single in style and style, and forms a situation that the style is changeable following the trend of the times.
Although the lost wax casting process has a plurality of advantages, certain defects exist, in the process of manufacturing the precious metal jewelry, the wax mold material is usually a mixed material of beeswax, rosin and vegetable oil, the wax mold material is soft, the surface of the wax mold material is easy to scratch, and the accuracy of the casting mold manufacturing is influenced, the traditional lost wax casting process needs to burn the casting mold through at the step high temperature of 100-700 ℃ to remove the wax mold, the time and the energy are consumed, and the wax mold material cannot be recycled, so that certain resource waste is caused (the application research of the lost wax casting process in the precious metal jewelry manufacturing [ D ]. Hebei university, 2017 ].
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the traditional precious metal jewelry manufacturing process mostly adopts a lost wax casting process, the wax pattern material is usually a mixed material of beeswax, rosin and vegetable oil, the wax pattern material is soft, scratches are easy to appear on the surface, the casting mold manufacturing accuracy and the jewelry appearance are affected, the traditional lost wax casting process needs to completely burn the casting mold at the step high temperature of 100-700 ℃, the invention is used for removing a wax mould to obtain a complete wax tree cavity, is time-consuming and energy-consuming, and aims at solving the problems, the invention provides a photocuring 3D printing resin, the method can be used for printing and manufacturing the resin template with accurate size and shape and higher hardness by adopting a photocuring 3D printing technology, the high-temperature-resistant casting mold can be manufactured by pouring casting powder into the resin template, and the resin template can be removed by placing the casting mold in a DMSO solution at 120 ℃ for ultrasonic dissolution.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the reaction of the present invention is schematically as follows:
the invention provides a photocuring 3D printing resin which comprises the following components in parts by weight:
70-80 parts of polymerized monomer
3-5 parts of photoinitiator
0.5 to 1 portion of light absorbent,
the polymerization monomer comprises the following components in parts by weight:
0 to 50 portions of polymerized monomer I
50-100 parts of a polymerization monomer II.
Specifically, the molecular structural formulas of the polymerized monomer I and the polymerized monomer II are as follows:
wherein, the structural formulas of R1 and R2 are shown in the specification
The structural formulas of R3, R4 and R5 are shown in the specification
Specifically, the monomer I is prepared according to the following method:
(1) 30g of 2, 5-dioxapyrrole-1-carboxylic acid, 70g of furancarboxylic acid, 25mg of dibutylhydroxytoluene, 650mL of toluene, 145mL of glycidyl methacrylate, 0.1mmol of TiCl catalyst3(OTf) was added to a two-necked flask and mixed well in N2The reaction is carried out for 24 hours at the room temperature,
(2) after the reaction in the step (1) is finished, heating to 60 ℃ for reaction for 40 min;
(3) and (3) cooling the solution after the reaction in the step (2) is finished by ice, filtering precipitates in the solution, and washing the precipitates with cold toluene to obtain a monomer I.
Specifically, the monomer II is prepared according to the following method:
(1) 3.5g of monomer I was dissolved in 20mL of toluene solution;
(2) slowly adding 37mg of 4-dimethylaminopyridine into the solution obtained in the step (1) at room temperature, and stirring for reaction for 10 min;
(3) adding 290mg of 1,3, 5-tricarbonyl benzene trichloride and 5mL of triethylamine into the reaction solution obtained in the step (2), stirring and reacting for 72 hours at 100 ℃, wherein an infrared spectrogram shows that a stretching vibration peak of-OH disappears, and the reaction is finished;
(4) the reaction solution obtained in step (3) was cooled to room temperature, evaporated under reduced pressure to remove volatile substances, and dissolved in 50mL of CH2Cl2The mixture was washed with water 3 times, and then purified by a chromatography column (n-hexane/ethyl acetate 20:1) to obtain monomer ii.
Specifically, the photoinitiator is camphorquinone or 784.
Specifically, the light absorber is carotene.
The invention has the beneficial effects that:
(1) according to the invention, a polymerization monomer I and a polymerization monomer II, a photoinitiator and a light absorber are printed by adopting a photocuring 3D printing technology to form various, complex and accurate resin templates, so that a wax mold in the traditional lost wax casting process can be replaced, a high-temperature-resistant casting mold can be manufactured by pouring casting powder into the resin template, the resin template can be rapidly and completely removed by placing the casting mold in a DMSO solution at 120 ℃ for ultrasonic dissolution, and a complete resin template cavity is obtained, so that the time and labor are saved, and the energy and the consumption are reduced;
(2) after the ethanol is removed from the cleaning solution of the resin template, the temperature is slowly reduced to the room temperature from high temperature, so that the resin material can be obtained again, and the resin template can be applied to the field of ultraviolet curing coatings;
(3) the photocuring 3D printing resin template prepared by the invention has better hardness, and the surface is not easy to scratch.
Drawings
FIG. 1: of monomers 11HNMR nuclear magnetic mass spectrogram.
FIG. 2: of monomers II1HNMR nuclear magnetic mass spectrogram.
Detailed Description
The present invention will now be described in further detail with reference to the accompanying drawings.
An example of the preparation of monomer I is as follows:
(1) 30g of 2, 5-dioxapyrrole-1-carboxylic acid, 70g of furancarboxylic acid, 25mg of dibutylhydroxytoluene, 650mL of toluene, 145mL of glycidyl methacrylate, 0.1mmol of TiCl catalyst3(OTf) was added to a two-necked flask and mixed well in N2The reaction is carried out for 24 hours at the room temperature,
(2) after the reaction in the step (1) is finished, heating to 60 ℃ for reaction for 40 min;
(3) cooling the solution after the reaction in step (2) with ice, filtering the precipitate in the solution, and washing with cold toluene to obtain the polymerized monomer I, which has a structure shown in the attached figure 11The HNMR was confirmed to be,1HNMR(CDCl3400MHz) (ppm): 1.73-1.93(m, 2H, cyclo-CH-), 1.99(s,6H, -CH)3) (ii) a 2.6-2.8(m, 4H, cyclo-CH)2-N-)；3.5-3.6(m,3H, -O-CH-CH2-O-),3.8-3.9(dd,4H,-O-C＝CH2),3.95-4.2(m,4H,-C-CH2-O-C＝),5.54(s,2H, -O-CH2-O-)；5.56(s,2H,-O-CH2-O-N-); 5.78(dd,2H, ring-CH ═ CH-).
Preparation examples of the polymerization monomers II are as follows:
(1) 3.5g of monomer I was dissolved in 20mL of toluene solution;
(2) slowly adding 37mg of 4-dimethylaminopyridine into the solution obtained in the step (1) at room temperature, and stirring for reaction for 10 min;
(3) adding 290mg of 1,3, 5-tricarbonyl benzene trichloride and 5mL of triethylamine into the reaction solution obtained in the step (2), stirring and reacting for 72 hours at 100 ℃, wherein an infrared spectrogram shows that a stretching vibration peak of-OH disappears, and the reaction is finished;
(4) the reaction solution obtained in step (3) was cooled to room temperature, evaporated under reduced pressure to remove volatile substances, and dissolved in 50mL of CH2Cl2Washing with water for 3 times, and separating with chromatographic column to obtain polymerized monomer II with structure shown in figure 21The HNMR was confirmed to be,1H NMR(CDCl3400MHz) (ppm): 1.73-1.93(m, 6H, cyclo-CH-), 1.99(s,9H, -CH)3) (ii) a 2.6-2.8(m, 12H, cyclo-CH)2-N-)；3.5-3.6(m,9H,-O-CH-CH2-O-)；3.8-3.9(dd,12H, -O-C＝CH2)；3.95-4.2(m,12H,-C-CH2-O-C＝)；4.24-4.49(m,6H,-C-CH2-O-C＝O)；5.54(s,6H,-O-CH2-O-)；5.56(s,6H,-O-CH2-O-N-); 5.78(dd,6H, ring-CH ═ CH-); 8.44(s,3H, Ph-H).
Preparation examples of photocurable 3D printing resins are as follows:
uniformly mixing a polymerization monomer, a photoinitiator and a light absorber, injecting the mixture into a liquid tank of a printer, after the liquid level of the mixture is naturally leveled, starting to print a resin template for manufacturing jewelry, pouring casting powder into the resin template to manufacture a high-temperature-resistant casting mold, and putting the casting mold into a DMSO solution at 120 ℃ to perform ultrasonic treatment to completely remove the resin template to obtain a complete resin template cavity.