A method for preparing a mold containing a release agent

Abstract

The present invention belongs to the technical field of mold preparation, and provides a method for preparing a mold containing a mold release agent. The present invention adds a liquid mold release agent and a solid mold release agent to a photocurable composite cyanate ink, respectively. Since the solid mold release agent has an adsorption effect on the liquid mold release agent, and the two types of mold release agents do not participate in the cross-linking polymerization reaction of the photocurable composite cyanate ink, the liquid mold release agent will finally precipitate from the inside of the mold, forming a lubricating film on the surface, significantly reducing the surface energy of the mold, the friction force and adhesion of the mold during demolding, ensuring that the mold does not need to be additionally applied with a mold release agent when in use, that is, efficient and lossless demolding can be achieved and the mold can be recycled. At the same time, after the acid ester monomer in the photocurable composite cyanate ink is subjected to photothermal treatment, a triazine ring structure is formed, so that the mold has excellent mechanical properties and thermal stability. In addition, the present invention adopts 3D printing for mold preparation, with fast molding speed and high precision, while meeting the customization requirements of personalized molds.

Description

Technical Field

[0001] The invention relates to the technical field of mold preparation, and in particular to a method for preparing a mold containing a release agent. Background Art

[0002] With the continuous development of the manufacturing industry, mold manufacturing has received more and more attention. Generally, molds are manufactured by injection molding, extrusion and casting, and the mold surface needs to be further processed afterwards. Therefore, the traditional method of manufacturing molds is time-consuming and costly, and cannot meet the preparation needs of customized molds; and in order to improve the quality and efficiency of demoulding, chemical release agents are often required to reduce the friction and adhesion of the mold surface, which is inconvenient to use. Summary of the invention

[0003] In view of this, an object of the present invention is to provide a method for preparing a mold containing a release agent. The preparation method provided by the present invention is time-saving, low in economic cost, and can meet the preparation requirements of customized molds, and does not require additional use of a release agent during demolding.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] The present invention provides a method for preparing a mold containing a release agent, comprising the following steps:

[0006] Provides light-curable composite cyanate ink;

[0007] According to the designed three-dimensional model, the photocurable composite cyanate ester ink is subjected to photocuring 3D printing to obtain a printing mold;

[0008] The printed mold is subjected to photothermal treatment to obtain the mold containing the release agent;

[0009] The photocurable composite cyanate ink comprises the following components: a cyanate monomer, a crosslinking agent, a diluent, a photoinitiator and a release agent;

[0010] The release agent includes a liquid release agent and a solid release agent.

[0011] Preferably, the cyanate ester monomer includes one or more of bisphenol A cyanate ester, bisphenol F cyanate ester, bisphenol E cyanate ester resin, dicyclopentadiene cyanate ester and bisphenol M cyanate ester.

[0012] Preferably, the cross-linking agent comprises tris(2-hydroxyethyl)isocyanurate triacrylate and / or glycidyl methacrylate; the mass of the cross-linking agent is 5-35% of the mass of the cyanate monomer.

[0013] Preferably, the diluent includes one or more of 4-acryloylmorpholine, N-vinyl pyrrolidone, hydroxyethyl acrylate and hydroxypropyl acrylate; the mass of the diluent is 30-70% of the mass of the cyanate monomer.

[0014] Preferably, the photoinitiator is an oily photoinitiator; the oily photoinitiator includes one or more of 819 photoinitiator, TPO photoinitiator and 1173 photoinitiator; the mass of the photoinitiator is 1-10% of the mass of the cyanate monomer.

[0015] Preferably, the liquid release agent includes perfluoropolyether and / or dimethyl silicone oil; and the solid release agent includes talc and / or silicon dioxide.

[0016] Preferably, the mass percentage of the liquid release agent in the photocurable composite cyanate ester ink is 0.1-5%; the mass percentage of the solid release agent in the photocurable composite cyanate ester ink is 5-25%.

[0017] Preferably, the photocurable composite cyanate ester ink further comprises a dye; the dye comprises Orizol 157h and / or Orizol 365; the mass of the dye is 0.01-0.06% of the mass of the cyanate ester monomer.

[0018] Preferably, the parameters of the light-curing 3D printing include: the wavelength of the light source is 385-405 nm; the exposure time of each layer is 10s-30s; and the slice layer thickness is 0.05mm-0.15mm.

[0019] Preferably, the photothermal treatment comprises sequentially performing ultraviolet light curing and heat treatment;

[0020] The UV curing time is 10 to 30 minutes;

[0021] The heat treatment procedure is: from room temperature to 100°C for 2h, from 100°C to 140°C for 2-4h, from 140°C to 160°C for 1-2h and then keep warm for 2-4h; from 160°C to 180°C for 1-2h, from 180°C to 200°C for 2-4h and then keep warm for 2h.

[0022] The present invention provides a method for preparing a mold containing a release agent, comprising the following steps: providing a photocurable composite cyanate ink; performing photocurable 3D printing on the photocurable composite cyanate ink according to a designed three-dimensional model to obtain a printed mold; performing photothermal treatment on the printed mold to obtain the mold containing a release agent; the photocurable composite cyanate ink comprises the following components: a cyanate monomer, a crosslinking agent, a diluent, a photoinitiator and a release agent; the release agent comprises a liquid release agent and a solid release agent. In the preparation method provided by the present invention, a liquid release agent and a solid release agent are added to the photocurable composite cyanate ink respectively. Since the solid release agent has an adsorption effect on the liquid release agent, and the two types of release agents do not participate in the crosslinking polymerization reaction of the photocurable composite cyanate ink, the liquid release agent will finally precipitate from the inside of the mold and form a lubricating film on the surface, which significantly reduces the surface energy of the mold, the friction force and adhesion force of the mold during demolding, and ensures that the mold does not need to be additionally coated with a release agent when in use, that is, efficient and lossless demolding can be achieved and the mold can be recycled (the mold can still be demolded without loss after repeated demolding for 100 times). At the same time, after the ester monomer in the photocurable composite cyanate ink is subjected to photothermal treatment, a triazine ring structure is formed, so that the mold has excellent mechanical properties and thermal stability. In addition, the present invention adopts 3D printing to prepare the mold. Compared with the traditional mold manufacturing method, its molding speed is fast and the precision is high, which effectively improves the production efficiency and can also meet the customization needs of personalized molds.

[0023] Furthermore, the types of cyanate monomers, crosslinkers, diluents and photoinitiators in the photocurable composite cyanate ink are limited, so that the resulting mold has high hardness, high mechanical strength, stable properties, acid, alkali and high temperature resistance, and the mold will not deform during use to ensure that the accuracy of the produced parts will not change. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 The printing principle diagram of the preparation of the mold containing the release agent of the present invention;

[0025] Figure 2 A mechanism diagram of photothermal treatment during the preparation of a mold containing a release agent provided by the present invention;

[0026] Figure 3 The surface energy and contact angle of the mold obtained in Example 4;

[0027] Figure 4 This is a flow chart of demoulding the mold obtained by Example 1;

[0028] Figure 5 The mold demoulding test diagram provided for Examples 1 and 2;

[0029] Figure 6 The mold demoulding test diagram provided in Example 3;

[0030] Figure 7 This is a demoulding test diagram of the combined mold provided in Example 4;

[0031] Figure 8 This is a demoulding test diagram of the mold obtained in Example 1 after 100 cycles. DETAILED DESCRIPTION

[0032] The present invention provides a method for preparing a mold containing a release agent, comprising the following steps:

[0033] Provides light-curable composite cyanate ink;

[0034] According to the designed three-dimensional model, the photocurable composite cyanate ester ink is subjected to photocuring 3D printing to obtain a printing mold;

[0035] The printed mold is subjected to photothermal treatment to obtain the mold containing the release agent;

[0036] The photocurable composite cyanate ink comprises the following components: a cyanate monomer, a crosslinking agent, a diluent, a photoinitiator and a release agent;

[0037] The release agent includes a liquid release agent and a solid release agent.

[0038] In the present invention, unless otherwise specified, the raw materials used in the present invention are preferably commercially available products.

[0039] The invention provides a photocurable composite cyanate ink.

[0040] In the present invention, the photocurable composite cyanate ink comprises the following components: a cyanate monomer, a crosslinking agent, a diluent, a photoinitiator and a release agent.

[0041] In the present invention, the cyanate ester monomer preferably includes one or more of bisphenol A cyanate ester, bisphenol F cyanate ester, bisphenol E cyanate ester resin, dicyclopentadiene cyanate ester and bisphenol M cyanate ester, and more preferably bisphenol E cyanate ester resin.

[0042] In the present invention, the crosslinking agent preferably includes tris(2-hydroxyethyl)isocyanuric acid triacrylate and / or glycidyl methacrylate, and more preferably a mixture of tris(2-hydroxyethyl)isocyanuric acid triacrylate and glycidyl methacrylate; the mass ratio of tris(2-hydroxyethyl)isocyanuric acid triacrylate to glycidyl methacrylate in the mixture of tris(2-hydroxyethyl)isocyanuric acid triacrylate and glycidyl methacrylate is 2:1. In the present invention, the mass of the crosslinking agent is preferably 5-35% of the mass of the cyanate monomer, and more preferably 20-25%.

[0043] In the present invention, the diluent preferably includes one or more of 4-acryloylmorpholine, N-vinylpyrrolidone, hydroxyethyl acrylate and hydroxypropyl acrylate, and more preferably 4-acryloylmorpholine. In the present invention, the mass of the diluent is preferably 30-70% of the mass of the cyanate monomer, and more preferably 55-65%.

[0044] In the present invention, the photoinitiator is preferably an oily photoinitiator; the oily photoinitiator preferably includes one or more of 819 photoinitiator, TPO photoinitiator and 1173 photoinitiator, and more preferably 819 photoinitiator. In the present invention, the mass of the photoinitiator is preferably 1-10% of the mass of the cyanate monomer, and more preferably 2-5%.

[0045] In the present invention, the release agent includes a liquid release agent and a liquid release agent. In the present invention, the liquid release agent preferably includes perfluoropolyether and / or dimethyl silicone oil, and is more preferably perfluoropolyether. In the present invention, the mass percentage of the liquid release agent in the photocurable composite cyanate ester ink is preferably 0.1-5%, and is more preferably 0.2-1%. In the present invention, the solid release agent preferably includes talcum powder and / or silicon dioxide, and is more preferably talcum powder. In the present invention, the mass percentage of the solid release agent in the photocurable composite cyanate ester ink is preferably 5-25%, and is more preferably 5-10%. In the present invention, the average particle size of the solid release agent is selected to be 100-800nm.

[0046] In the present invention, the photocurable composite cyanate ink preferably further comprises a dye; the dye preferably comprises Orizol 157h and / or Orizol 365. In the present invention, the mass of the dye is preferably 0.01 to 0.06% of the mass of the cyanate monomer, more preferably 0.02 to 0.05%, and more preferably 0.03 to 0.04%.

[0047] In the present invention, the method for preparing the photocurable composite cyanate ester ink preferably comprises the following steps:

[0048] After mixing the crosslinking agent and the diluent, the cyanate monomer and the photoinitiator are added in sequence to obtain the cyanate ink;

[0049] The cyanate ester ink is sequentially mixed with a solid release agent and a liquid release agent to obtain the photocurable composite cyanate ester ink.

[0050] In the present invention, after a crosslinking agent and a diluent are mixed, a cyanate monomer and a photoinitiator are added in sequence to obtain cyanate ink.

[0051] In the present invention, when the crosslinking agent is preferably a mixture of tris(2-hydroxyethyl)isocyanuric acid triacrylate and glycidyl methacrylate; the mixing of the crosslinking agent and the diluent preferably includes the following steps: after the diluent and tris(2-hydroxyethyl)isocyanuric acid triacrylate are mixed for the first time, glycidyl methacrylate is added for the second mixing; the first mixing is preferably carried out under nitrogen atmosphere, oil bath and stirring conditions, and the temperature of the oil bath is preferably 60°C; the stirring time is preferably 6 to 8 hours; after the first mixing, the present invention preferably further includes adding glycidyl methacrylate after the temperature drops to room temperature. In the present invention, the second mixing is preferably carried out under stirring conditions, and the stirring time is preferably 2 to 4 hours.

[0052] In the present invention, after the cyanate monomer is added, a third mixing is preferably performed, and the temperature of the third mixing is preferably room temperature, that is, no additional heating or cooling is required; the third mixing is preferably performed under stirring, and the stirring time is preferably 12 to 18 hours.

[0053] In the present invention, the fourth mixing is preferably carried out after the photoinitiator is added; the temperature of the fourth mixing is preferably room temperature, that is, no additional heating or cooling is required; the fourth mixing is preferably carried out under stirring conditions, and the stirring time is preferably 6 to 10 hours.

[0054] After the fourth mixing, the present invention preferably further comprises degassing; the degassing is preferably vacuum degassing; and the time of the vacuum degassing is preferably 5 to 20 minutes.

[0055] After the cyanate ink is obtained, the present invention sequentially mixes the cyanate ink with a solid release agent and a liquid release agent to obtain the photocurable composite cyanate ink.

[0056] In the present invention, the solid release agent is preferably mixed by first ball milling, the rotation speed of the first ball milling is preferably 3000 rpm, and the time is preferably 3 to 6 minutes; the first ball milling is preferably carried out in a dual-center mixing disperser; the number of the first ball milling is preferably 3 times.

[0057] In the present invention, the liquid release agent is preferably mixed by a second ball milling; the parameters of the second ball milling are preferably consistent with the parameters of the first ball milling, which will not be described in detail here.

[0058] After the second ball milling, the present invention preferably further comprises degassing; the degassing is preferably vacuum degassing; and the time of the vacuum degassing is preferably 5 to 10 minutes.

[0059] After obtaining the photocurable composite cyanate ester ink, the present invention performs photocurable 3D printing on the photocurable composite cyanate ester ink according to the designed three-dimensional model to obtain a printing mold.

[0060] The present invention does not specifically limit the method and parameters for making the three-dimensional model, and those skilled in the art may set them according to actual needs.

[0061] In the present invention, the parameters of the photocuring 3D printing include: the wavelength of the light source is preferably 385-405nm; the exposure time of each layer is preferably 10s-30s, more preferably 15s-25s, and more preferably 20s; the slice layer thickness is preferably 0.05mm-0.15mm, more preferably 0.1mm; the printer power is preferably 250-300mW.

[0062] After the light-curing 3D printing, the present invention preferably further comprises cleaning the obtained print; the cleaning agent is preferably isopropyl alcohol.

[0063] After obtaining the printed mold, the present invention performs photothermal treatment on the printed mold to obtain the mold containing the release agent.

[0064] In the present invention, the photothermal treatment preferably includes sequentially performing ultraviolet light curing and heat treatment.

[0065] In the present invention, the UV curing time is preferably 10 to 30 minutes, more preferably 15 to 25 minutes, and more preferably 20 minutes.

[0066] In the present invention, the heat treatment procedure is preferably: from room temperature to 100°C for 2 hours, from 100°C to 140°C for 2 to 4 hours, from 140°C to 160°C for 1 to 2 hours and then keep at 160°C for 2 to 4 hours; from 160°C to 180°C for 1 to 2 hours, from 180°C to 200°C for 2 to 4 hours and then keep at 160°C for 2 hours.

[0067] In the present invention, the mold containing a release agent is preferably used to produce polydimethylsiloxane (PDMS), polyurethane elastic (PU) and hydrogel.

[0068] Figure 1 This is a printing principle diagram for preparing a mold containing a release agent according to the present invention.

[0069] Figure 2 This is a mechanism diagram of photothermal treatment during the preparation of a mold containing a release agent provided by the present invention.

[0070] The preparation method of the mold containing a release agent provided by the present invention is described in detail below in conjunction with the embodiments, but they should not be understood as limiting the scope of protection of the present invention.

[0071] Example 1

[0072] A method for preparing a mold containing a release agent comprises the following steps:

[0073] A. Modeling: Use Shapr3D software to design the model, and then export the model format as an STL file.

[0074] B. Preparation of photocurable composite cyanate ink: Add 40g N-acryloylmorpholine and 10g tri(2-hydroxyethyl)isocyanuric acid triacrylate to a 500mL flask, then place in a 60°C oil bath and stir for 6h under a nitrogen atmosphere. After the temperature of the reaction system drops to room temperature, add 5g of glycidyl methacrylate and continue stirring for 2h. Then add 65g of bisphenol E cyanate resin and continue stirring at room temperature for 12h. Then add 2.5g of photoinitiator Irgacure 819 and 0.02g of Orisol 365 dye and continue stirring for 6h to make it evenly dispersed. Finally, vacuum treat for 5min to eliminate bubbles in the ink to obtain cyanate ink.

[0075] In the prepared cyanate ink, 10g of talcum powder (average particle size of 500nm) was added, and ball milling was performed at 3000rpm for 3min in a dual-center mixing and dispersing machine, and the treatment was repeated three times to uniformly disperse the talcum powder in the cyanate ink; then 1g of perfluoropolyether was added, and ball milling was performed at 3000rpm for 3min in a dual-center mixing and dispersing machine, and the treatment was repeated three times to uniformly disperse the perfluoropolyether in the cyanate ink system in the form of small droplets. Finally, after vacuum treatment for 5min to remove bubbles, a light-curable composite cyanate ink was obtained.

[0076] C. Printing model: Import the STL format file into the slicing software CHITUBOX64 for slicing and printer settings. The parameters are as follows: the wavelength of the light source is 405nm, the layer thickness is 100μm, the exposure time is 10s, and the printer power is 260mW. After completion, click Start Printing to obtain the printed model.

[0077] D. Photothermal treatment of printed models: After the model is printed, remove the printed model from the support platform and clean it with isopropyl alcohol. After cleaning, put the printed model into a UV curing box for UV curing for 10 minutes. After UV curing, perform heat treatment. The heat treatment is carried out in a programmable temperature-controlled oven, and the heating program is as follows:

[0078] The temperature is raised from room temperature to 100°C for 2h, from 100°C to 140°C for 2h, from 140°C to 160°C for 2h, and kept at 160°C for 2h; the temperature is raised from 160°C to 180°C for 2h, from 180°C to 200°C for 2h, and kept at 200°C for 2h, then the heating is stopped, and the temperature is lowered to room temperature to obtain a mold containing a release agent.

[0079] E. Model demoulding: weigh 20 grams of Sylgard TM 184 silicone and 2 g curing agent (mass ratio of 10:1), fully mixed, and degassed for 5 min under reduced pressure to obtain a prepolymer. The prepared prepolymer was poured into the mold obtained in step D, and then placed in a constant temperature furnace at 60°C, heat treated for 2 h, cooled to room temperature, and then demolded.

[0080] Example 2

[0081] A method for preparing a mold containing a release agent comprises the following steps:

[0082] A. Modeling: Use Shapr3D software to design the model, and then export the model format as an STL file.

[0083] B. Preparation of photocurable composite cyanate ink: Add 40g of 4-acryloylmorpholine and 10g of tri(2-hydroxyethyl)isocyanuric acid triacrylate to a 500mL flask, then place in a 60°C oil bath and stir for 6h under a nitrogen atmosphere. After the temperature of the reaction system drops to room temperature, add 5g of glycidyl methacrylate and continue stirring for 2h. Then add 70g of bisphenol E cyanate resin and continue stirring at room temperature for 12h. Then add 2.5g of photoinitiator Irgacure 819 and 0.02g of Orisol 365 dye and continue stirring for 6h to make it evenly dispersed. Finally, vacuum treat for 10min to eliminate bubbles to obtain cyanate ink.

[0084] 10 g of talcum powder (average particle size of 500 nm) was added to the prepared cyanate ink, and ball milled at 3000 rpm for 3 min in a dual-center mixing and dispersing machine, and the treatment was repeated three times to uniformly disperse the talcum powder in the cyanate ink. Then 1.4 g of perfluoropolyether was added, and ball milled at 3000 rpm for 3 min in a dual-center mixing and dispersing machine, and the treatment was repeated three times to uniformly disperse the perfluoropolyether in the cyanate ink system in the form of small droplets. Finally, after vacuum treatment for 5 min to remove bubbles in the ink, a light-curable composite cyanate ink was obtained.

[0085] C. Printing model: Import the STL format file into the slicing software CHITUBOX64 for slicing and printer settings. The parameters are as follows: the wavelength of the light source is 405nm, the layer thickness is 100μm, the exposure time is 15s, and the printer power is 270mW. After completion, click Start Printing to obtain the printed model.

[0086] D. Photothermal treatment of printed models: After the model is printed, remove the printed model from the support platform and clean it with isopropyl alcohol. After completion, place the printed model in a UV curing box for UV curing for 20 minutes. After UV curing, perform heat treatment. The heat treatment is performed in a programmable temperature-controlled oven, and the heating program is as follows:

[0087] The temperature was raised from room temperature to 100°C for 2h, from 100°C to 140°C for 2h, from 140°C to 160°C for 2h, and kept at 160°C for 2h; the temperature was raised from 160°C to 180°C for 1h, from 180°C to 200°C for 2h, and kept at 200°C for 2h, then the heating was stopped, and the temperature was lowered to room temperature to obtain a mold containing a release agent.

[0088] E. Model demoulding: weigh 20 grams of Sylgard TM 184 silicone and 2 g curing agent (mass ratio of 10:1), fully mixed, and degassed for 10 min under reduced pressure to obtain a prepolymer. The prepared prepolymer was poured into the mold obtained in step D, and then placed in a constant temperature furnace at 70°C, heat treated for 2 h, cooled to room temperature, and then demolded.

[0089] Example 3

[0090] A method for preparing a mold containing a release agent comprises the following steps:

[0091] A. Modeling: Use Shapr3D software to design the model, and then export the model format as an STL file.

[0092] B. Preparation of photocurable composite cyanate ink: Add 40g of 4-acryloylmorpholine and 10g of tri(2-hydroxyethyl)isocyanuric acid triacrylate to a 500mL flask, then place in a 60°C oil bath and stir for 8h under a nitrogen atmosphere. After the temperature of the reaction system drops to room temperature, add 5g of glycidyl methacrylate and continue stirring for 2h. Then add 65g of bisphenol E cyanate resin and continue stirring at room temperature for 12h. Then add 3g of photoinitiator Irgacure 819 and 0.02g of Orisol 365 dye and continue stirring for 6h to make it evenly dispersed. Finally, vacuum treat for 15min to eliminate bubbles in the ink to obtain cyanate ink.

[0093] 10 g of talcum powder (average particle size of 500 nm) was added to the prepared cyanate ink, and ball milled at 3000 rpm for 3 min in a dual-center mixing and dispersing machine, and the treatment was repeated three times to uniformly disperse the talcum powder in the cyanate ink. Then 1.8 g of perfluoropolyether was added, and ball milled at 3000 rpm for 3 min in a dual-center mixing and dispersing machine, and the treatment was repeated three times to uniformly disperse the perfluoropolyether in the cyanate ink system in the form of small droplets. Finally, after vacuum treatment for 10 min to remove bubbles in the ink, a light-curable composite cyanate ink was obtained.

[0094] C. Print model: Import the STL format file into the slicing software CHITUBOX64 for slicing and printer settings. The parameters are as follows: the wavelength of the light source is 405nm, the layer thickness is 100μm, the exposure time is 20s, and the printer power is 280mW. After completion, click Start Printing to obtain the printed model.

[0095] D. Photothermal treatment of printed models: After the model is printed, it is removed from the support platform and cleaned with isopropyl alcohol. After cleaning, the printed model is placed in a UV curing box for UV curing for 20 minutes. After UV curing, heat treatment is performed in a programmable temperature-controlled oven. The heating program is as follows:

[0096] The temperature is raised from room temperature to 100°C for 2h, from 100°C to 140°C for 2h, from 140°C to 160°C for 2h, and kept at 160°C for 2h; the temperature is raised from 160°C to 180°C for 2h, from 180°C to 200°C for 2h, and kept at 200°C for 2h, then the heating is stopped, and the temperature is lowered to room temperature to obtain a mold containing a release agent.

[0097] E. Model demoulding: weigh 20 grams of Sylgard TM 184 silicone and 2 g curing agent (mass ratio of 10:1), fully mixed, and degassed for 10 min under reduced pressure to obtain a prepolymer. The prepared prepolymer was poured into the mold obtained in step D, and then placed in a constant temperature furnace at 80°C, heat treated for 2 h, cooled to room temperature, and then demolded.

[0098] Example 4

[0099] A method for preparing a mold containing a release agent comprises the following steps:

[0100] A. Modeling: Use Shapr3D software to design the model, and then export the model format as an STL file.

[0101] B. Preparation of photocurable composite cyanate ink: Add 40g of 4-acryloylmorpholine and 10g of tri(2-hydroxyethyl)isocyanuric acid triacrylate to a 500mL flask, then place in a 60°C oil bath and stir for 8h under a nitrogen atmosphere. After the temperature of the reaction system drops to room temperature, add 5g of glycidyl methacrylate and continue stirring for 2h. Then add 70g of bisphenol E cyanate resin and continue stirring at room temperature for 12h. Then add 3g of photoinitiator Irgacure 819 and 0.02g of Orisol 365 dye and continue stirring for 6h to make it evenly dispersed. Finally, vacuum treat for 15min to eliminate bubbles in the ink to obtain cyanate ink.

[0102] 10 g of talcum powder (average particle size of 500 nm) was added to the prepared cyanate ester ink, and ball milled at 3000 rpm for 3 min in a dual-center mixing disperser, and the treatment was repeated three times to uniformly disperse the talcum powder in the cyanate ester ink. Then 2.2 g of perfluoropolyether was added, and ball milled at 3000 rpm for 3 min in a dual-center mixing disperser, and the treatment was repeated three times to uniformly disperse the talcum powder in the cyanate ester ink system in the form of small droplets. Finally, after vacuum treatment for 5 min to remove bubbles, a light-curable composite cyanate ester ink was obtained.

[0103] C. Printing model: Import the STL format file into the slicing software CHITUBOX64 for slicing and printer settings. The parameters are as follows: the wavelength of the light source is 405nm, the layer thickness is 100μm, the exposure time is 20s, and the printer power is 280mW. After completion, click Start Printing to obtain the printed model.

[0104] D. Photothermal treatment of printed models: After the model is printed, remove the printed model from the support platform and clean it with isopropyl alcohol. After completion, place the printed model in a UV curing box for UV curing for 20 minutes. After UV curing, perform heat treatment in a programmable temperature-controlled oven. The heating program is as follows:

[0105] The temperature is raised from room temperature to 100°C for 2h, from 100°C to 140°C for 2h, from 140°C to 160°C for 2h, and kept at 160°C for 2h; the temperature is raised from 160°C to 180°C for 2h, from 180°C to 200°C for 2h, and kept at 200°C for 2h, then the heating is stopped, and the temperature is lowered to room temperature to obtain a mold containing a release agent.

[0106] E. Model demoulding: weigh 20 grams of Sylgard TM 184 silicone and 2 g curing agent (mass ratio of 10:1), fully mixed, and degassed for 10 min under reduced pressure to obtain a prepolymer. The prepared prepolymer was poured into the mold obtained in step D, and then placed in a constant temperature furnace at 90°C, heat treated for 2 h, cooled to room temperature, and then demolded.

[0107] Figure 3 The surface energy and contact angle of the mold obtained in Example 4 are shown in FIG. Figure 3 It can be seen that the introduction of perfluoropolyether can effectively reduce the surface energy and help improve the demoulding quality.

[0108] Figure 4 The following is a flow chart of demoulding the mold obtained by using Example 1. Figure 4 It can be seen that the method for manufacturing demoulding molds has low cost, high efficiency and good application prospects.

[0109] Figure 5 This is a mold demoulding test diagram provided for Examples 1 and 2. Figure 6 The mold demoulding test diagram provided for Example 3; Figure 5 and Figure 6 It can be seen that the molds containing release agents obtained in the two embodiments have good demoulding effects.

[0110] Figure 7 Combination mold demoulding test diagram provided for Example 4; Figure 7 It can be seen that the mold has good universality and demoulding effect.

[0111] Figure 8 This is the demoulding test diagram of the mold obtained in Example 1 after 100 cycles. Figure 8 It can be seen that the mold has excellent recyclability.

[0112] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a mold containing a release agent, characterized in that: The following steps are involved: Provides light-curable composite cyanate ink; According to the designed three-dimensional model, the photocurable composite cyanate ester ink is subjected to photocuring 3D printing to obtain a printing mold; The printed mold is subjected to photothermal treatment to obtain the mold containing the release agent; The photocurable composite cyanate ink comprises the following components: a cyanate monomer, a crosslinking agent, a diluent, a photoinitiator and a release agent; The release agent includes a liquid release agent and a solid release agent; The liquid release agent includes perfluoropolyether and / or dimethyl silicone oil; the solid release agent includes talc and / or silicon dioxide; The mass percentage of the liquid release agent in the photocurable composite cyanate ester ink is 0.1-5%; the mass percentage of the solid release agent in the photocurable composite cyanate ester ink is 5-25%.

2. The preparation method according to claim 1, characterized in that: The cyanate monomer includes one or more of bisphenol A cyanate, bisphenol F cyanate, bisphenol E cyanate resin, dicyclopentadiene cyanate and bisphenol M cyanate.

3. The preparation method according to claim 1, characterized in that: The crosslinking agent includes tris(2-hydroxyethyl)isocyanuric acid triacrylate and / or glycidyl methacrylate; the mass of the crosslinking agent is 5-35% of the mass of the cyanate monomer.

4. The preparation method according to claim 1, characterized in that: The diluent comprises one or more of N-acryloylmorpholine, N-vinylpyrrolidone, hydroxyethyl acrylate and hydroxypropyl acrylate; the mass of the diluent is 30-70% of the mass of the cyanate monomer.

5. The preparation method according to claim 1, characterized in that: The photoinitiator is an oily photoinitiator; the oily photoinitiator includes one or more of 819 photoinitiator, TPO photoinitiator and 1173 photoinitiator; the mass of the photoinitiator is 1-10% of the mass of the cyanate monomer.

6. The preparation method according to claim 1, characterized in that: The photocurable composite cyanate ink further comprises a dye; the dye comprises Orizol 157h and / or Orizol 365; the mass of the dye is 0.01-0.06% of the mass of the cyanate monomer.

7. The preparation method according to claim 1, characterized in that: The parameters of the photocuring 3D printing include: the wavelength of the light source is 385-405 nm; the exposure time of each layer is 10s-30s; and the slice layer thickness is 0.05mm-0.15mm.

8. The preparation method according to claim 1, characterized in that: The photothermal treatment includes sequentially performing ultraviolet light curing and heat treatment; The UV curing time is 10 to 30 minutes; The heat treatment procedure is: from room temperature to 100°C for 2h, from 100°C to 140°C for 2-4h, from 140°C to 160°C for 1-2h and then keep warm for 2-4h; from 160°C to 180°C for 1-2h, from 180°C to 200°C for 2-4h and then keep warm for 2h.

Images