3D printing heat-resistant resin as well as preparation method and application thereof

Abstract

The invention provides 3D printing heat-resistant resin as well as a preparation method and application thereof. The 3D printing heat-resistant resin is prepared from a component A and a component B, the component A comprises the following components in parts by weight: 35-53 parts of cyanate ester resin; 2 to 8 parts of epoxy acrylate; the component B is prepared from the following component: 12 to 35 parts of epoxy acrylate; 0.5 to 1.5 parts of an initiator; 0.5 to 1.5 parts of a toughening agent; 4-29 parts of epoxy resin; 15 to 40 parts of an acrylate monomer; and 0.001 to 1 part of a catalyst. According to the invention, the characteristics that the epoxy acrylate, the epoxy resin and the acrylate monomer are easy to photocure and form and low in reaction activity with the cyanate ester resin under a mild condition are utilized, and the cyanate ester resin which does not participate in photocuring or hardly participates in photocuring is wrapped in a formed photocuring matrix resin sample under a relatively mild photocuring reaction condition; therefore, the purpose of reducing the difficulty of the light curing condition of the cyanate ester resin is achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials and relates to a 3D printing heat-resistant resin and a preparation method and application thereof. Background Art

[0002] Cyanate esters (CE) are widely used in aerospace, electronics, automobiles and transportation due to their excellent dielectric properties, heat resistance, dimensional stability, corrosion resistance and mechanical properties. However, due to the chemical structure characteristics of cyanate esters themselves, they generally have low reactivity and incomplete curing in photocuring. In order to improve the photocuring performance of cyanate esters, they are usually modified, such as blending with other resins, or introducing specific functional groups, etc. Among them, it is more common to modify them with epoxy resin (EP) which is relatively cheap, has a relatively low curing temperature, and has a curing process that is easier to operate and control. However, due to the different compatibility and reactivity of the two, problems such as uneven or incomplete curing, cracks or deformation of the material are prone to occur.

[0003] Therefore, how to improve the modification of EP to CE with low cost and high efficiency becomes increasingly important. Summary of the invention

[0004] In view of the deficiencies in the prior art, the object of the present invention is to provide a 3D printing heat-resistant resin and a preparation method and application thereof.

[0005] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0006] In a first aspect, the present invention provides a 3D printing heat-resistant resin, wherein the raw materials for preparing the 3D printing heat-resistant resin include component A and component B;

[0007] The component A comprises the following components in parts by weight:

[0008] 35-53 parts of cyanate resin;

[0009] Epoxy acrylate 2-8 parts;

[0010] The B component comprises the following components in parts by weight:

[0011]

[0012] The present invention utilizes the characteristics of epoxy acrylate, epoxy resin, and acrylate monomers that are easy to photocured and have low reaction activity with cyanate resin under mild conditions. Under relatively mild photocuring reaction conditions, the cyanate resin that does not participate in or rarely participates in photocuring is entrained in the molded photocurable matrix resin sample, thereby achieving the purpose of reducing the difficulty of photocuring conditions for the cyanate resin, thereby ensuring that most of the cyanate resin only reacts with the photocurable matrix resin during thermosetting, thereby reducing the occurrence of side reactions.

[0013] The present invention does not use expensive, unevenly performing modified cyanate resins with complex photocuring conditions, but allows the cyanate resin to be encapsulated in the photocurable material to participate in the thermosetting reaction, which can reduce costs and side reactions, thereby ensuring material quality.

[0014] In the present invention, the amount of cyanate ester resin in component A can be 35 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts, 48 ​​parts, 50 parts, 52 parts, or 53 parts by weight.

[0015] In the present invention, the amount of epoxy acrylate in component A can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, etc., based on parts by weight.

[0016] In the present invention, the amount of epoxy acrylate in component B can be 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 35 parts, etc., based on parts by weight.

[0017] In the present invention, the amount of the initiator in component B can be 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, etc., based on parts by weight.

[0018] In the present invention, the amount of the toughening agent in component B can be 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 parts, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, etc., based on parts by weight.

[0019] In the present invention, the amount of epoxy resin in component B can be 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 29 parts, etc., based on parts by weight.

[0020] In the present invention, the amount of the acrylic acid ester monomer in component B can be 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, etc., based on parts by weight.

[0021] In the present invention, the amount of the catalyst used in component B can be 0.001 part, 0.003 part, 0.005 part, 0.008 part, 0.01 part, 0.03 part, 0.05 part, 0.08 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, etc., calculated by weight.

[0022] Preferably, the cyanate ester resin includes any one of bisphenol F cyanate ester resin, bisphenol M cyanate ester resin, bisphenol E cyanate ester resin, novolac cyanate ester resin, dicyclopentadiene cyanate ester resin, and bisphenol A cyanate ester resin, or a combination of at least two thereof.

[0023] Preferably, the epoxy acrylates in the A component and the B component each independently include any one of bisphenol A epoxy acrylate, novolac epoxy acrylate, epoxidized acrylate, and modified epoxy acrylate, or a combination of at least two thereof.

[0024] Preferably, the initiator includes any one of TPO, photoinitiator 819, photoinitiator 2959, photoinitiator 1173, photoinitiator 369, photoinitiator 184, photoinitiator 907, photoinitiator 651, and photoinitiator 250, or a combination of at least two of them.

[0025] Preferably, the toughening agent includes any one of polyethersulfone, polyetherimide, polyetherketone, natural rubber, chloroprene rubber, polyisoprene, carboxyl-terminated nitrile, nano-silicon dioxide, and nano-titanium dioxide, or a combination of at least two thereof.

[0026] Preferably, the epoxy resin includes any one of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, aliphatic epoxy resin, and glycidylamine epoxy resin, or a combination of at least two thereof.

[0027] Preferably, the acrylate monomer includes any one of trimethylolpropane triacrylate (TMPTA), pentaerythritol triacrylate (PETA), ethoxylated trimethylolpropane triacrylate (ETPTA), dipentaerythritol pentaacrylate (DPHA), propoxylated neopentyl glycol diacrylate (PONPGDA), 1,6-hexanediol diacrylate (HDDA), hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate (HPMA), dipropylene glycol diacrylate (DPGDA), polyethylene glycol diacrylate (PEGDA), tripropylene glycol diacrylate, and a combination of at least two thereof.

[0028] Preferably, the catalyst includes any one of stannous octoate, stannous oleate, and dibutyltin dilaurate, or a combination of at least two thereof.

[0029] Preferably, the mass ratio of component A to component B is 1:(1-4), for example, 1:1, 2:3, 1:2, 1:3, 1:4, etc.

[0030] In a second aspect, the present invention provides a method for preparing the 3D printing heat-resistant resin as described in the first aspect, the preparation method comprising the following steps:

[0031] (1) mixing cyanate resin and epoxy acrylate to obtain component A;

[0032] (2) mixing the initiator and the acrylate monomer, then adding the catalyst and the toughening agent for a second mixing, and then adding the epoxy resin and the epoxy acrylate for a third mixing to obtain component B;

[0033] (3) Component A and component B are mixed to obtain a mixed solution, and a primary photocuring product is obtained by primary photocuring printing, and then secondary photocuring and thermal curing are performed to obtain the 3D printing heat-resistant resin.

[0034] Preferably, the mixing speed in step (1) is 400-800 r / min, for example, 400 r / min, 500 r / min, 600 r / min, 700 r / min, 800 r / min, etc., and the mixing time is 30-60 min, for example, 30 min, 40 min, 50 min, 60 min, etc.

[0035] Preferably, the mixing speed in step (2) is 200-500 r / min, for example, 200 r / min, 300 r / min, 400 r / min, 500 r / min, etc., and the mixing time is 30-60 min, for example, 30 min, 40 min, 50 min, 60 min, etc.

[0036] Preferably, the second mixing time in step (2) is 30 to 60 min, for example, 30 min, 40 min, 50 min, 60 min, etc.

[0037] Preferably, the rotation speed of the third mixing in step (2) is 800-1400 r / min, for example, 800 r / min, 900 r / min, 1000 r / min, 1100 r / min, 1200 r / min, 1300 r / min, 1400 r / min, etc., and the time of the third mixing is 0.5-1.5 h, for example, 0.5 h, 1 h, 1.5 h, etc.

[0038] Preferably, the mixing speed in step (3) is 800-1400 r / min, for example, 800 r / min, 900 r / min, 1000 r / min, 1100 r / min, 1200 r / min, 1300 r / min, 1400 r / min, etc., and the mixing time is 0.5-1 h, for example, 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h, 1 h, etc.

[0039] Preferably, step (3) further includes a filtering step after the mixing.

[0040] Preferably, the parameters of the primary light-curing printing in step (3) include: the wavelength of the light source used is 360-430 nm, such as 360 nm, 370 nm, 385 nm, 400 nm, 410 nm, 430 nm, etc., and the light intensity is 5000-8000 uw / cm 2 , for example 5000uw / cm 2 、6000uw / cm 2 、7000uw / cm 2 、8000uw / cm 2 The time of each primary light curing is 5 to 15 seconds, such as 5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 12 seconds, 13 seconds, 15 seconds, etc. The thickness of the light-cured product after each primary light curing is 1 to 3 mm, such as 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, etc. That is, the primary light curing printing is performed in several times, and the time of each primary light curing is 5 to 15 seconds, until the printing is completed.

[0041] Preferably, the illumination intensity of the secondary light curing in step (3) is 8000 to 10000 uw / cm 2 , for example 8000uw / cm 2 、8500uw / cm 2 、9000uw / cm 2 、9500uw / cm 2 、10000uw / cm2 The time for secondary light curing is 8 to 20 minutes, for example, 8 minutes, 10 minutes, 13 minutes, 15 minutes, 18 minutes, 20 minutes, etc.

[0042] The photocuring conditions and ultraviolet light intensity in the present invention are relatively common, that is, the present invention only needs relatively conventional photocuring conditions to prepare the photocurable material encapsulating the cyanate ester resin, which greatly reduces the difficulty of the photocuring reaction of the cyanate ester resin.

[0043] Preferably, the heat curing conditions of step (3) are: curing at 50-70°C (e.g., 50°C, 60°C, 70°C, etc.) for 0.5-1.5h (e.g., 0.5h, 1h, 1.5h, etc.), curing at 80-120°C (e.g., 80°C, 90°C, 100°C, 110°C, 120°C, etc.) for 2-4h (e.g., 2h, 3h, 4h, etc.), curing at 140-160°C (e.g., 140°C, 150°C, 160°C, etc.) for 1-2h. 3h (e.g. 1h, 2h, 3h, etc.), at 170-190°C (e.g. 170°C, 180°C, 190°C, etc.) for 1-3h (e.g. 1h, 2h, 3h, etc.), at 195-205°C (e.g. 195°C, 200°C, 205°C, etc.) for 1-3h (e.g. 1h, 2h, 3h, etc.), at 210-220°C (e.g. 210°C, 215°C, 220°C, etc.) for 1-3h (e.g. 1h, 2h, 3h, etc.). As a preferred technical solution of the present invention, by controlling the thermosetting temperature and time for staged thermosetting, a network interpenetrating structure is formed by using cyanate resin and photocurable matrix resin to prepare a high temperature resistant resin material with good mechanical properties.

[0044] Taking the epoxy acrylate as bisphenol A epoxy acrylate and the cyanate resin as bisphenol A cyanate resin as an example, the schematic diagram of the synthesis mechanism of the 3D printing heat-resistant resin provided by the present invention is as follows: Figure 1 As shown, It is a base resin formed by photocuring of acrylate monomers and bisphenol A epoxy acrylate.

[0045] In a third aspect, the present invention provides a use of the 3D printing heat-resistant resin as described in the first aspect in 3D printing.

[0046] Compared with the prior art, the present invention has the following beneficial effects:

[0047] The present invention utilizes the characteristics of epoxy acrylate, epoxy resin, and acrylate monomers that are easy to photocured and have low reaction activity with cyanate resin under mild conditions. Under relatively mild photocuring reaction conditions, the cyanate resin that does not participate in or rarely participates in photocuring is entrained in the molded photocurable matrix resin sample, thereby achieving the purpose of reducing the difficulty of photocuring conditions for the cyanate resin, thereby ensuring that most of the cyanate resin only reacts with the photocurable matrix resin during thermosetting, thereby reducing the occurrence of side reactions. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 This is a schematic diagram of the synthesis mechanism of the 3D printing heat-resistant resin provided by the present invention, taking the epoxy acrylate as bisphenol A epoxy acrylate and the cyanate ester resin as bisphenol A type cyanate ester resin as an example.

[0049] Figure 2 This is the infrared spectrum of the cyanate resin stock solution used in Example 1.

[0050] Figure 3 This is the infrared spectrum of the primary photocurable product provided in Example 1. DETAILED DESCRIPTION

[0051] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0052] Example 1

[0053] In this embodiment, a 3D printing heat-resistant resin is provided, and the raw materials for preparing the 3D printing heat-resistant resin include component A and component B; wherein the specific components and amounts of component A and component B are shown in Table 1 below.

[0054] Table 1

[0055]

[0056]

[0057] The preparation method comprises the following steps:

[0058] S1: 36.8 parts of bisphenol A cyanate resin and 3.2 parts of bisphenol A epoxy acrylate were weighed at room temperature and stirred at 500 r / min for 60 min to prepare component A;

[0059] S2: Weigh 0.8 parts of 819, 0.2 parts of 184, 15.2 parts of pentaerythritol triacrylate, 12 parts of ethoxylated trimethylolpropane triacrylate, and 3 parts of 1,6-hexanediol diacrylate, and stir at 300 r / min for 30 min at room temperature to dissolve, then add 0.001 parts of stannous octoate, 0.5 parts of polyetherimide and 0.3 parts of nano-silica and continue stirring for 60 min, then add 21 parts of bisphenol A epoxy acrylate and 7 parts of ERL-4221 and stir thoroughly at 1200 r / min for 1.5 h to obtain component B;

[0060] S3: Stir components A and B at room temperature at 1400 r / min for 0.5 h, mix them evenly, and filter (mesh size is 100 mesh) to obtain a mixed solution;

[0061] S4: Performing primary photocuring printing on the mixed solution, the wavelength of the ultraviolet light source used is 385nm, and the light intensity is 6000uw / cm 2 The time of each primary light curing is 6 seconds, and the thickness of the light-cured product after each primary light curing is 1 mm. Repeat several times and directly finish printing to obtain the primary light-cured product.

[0062] S5: Clean the primary light-cured product with isopropyl alcohol, then irradiate with a light intensity of 9000uw / cm 2 The primary light-cured product was secondary light-cured for 15 minutes under the following conditions, and finally the secondary light-cured product was heat-cured according to a heat-curing process of 60°C×1h+100°C×3h+150°C×2h+180°C×2h+200°C×2h+210°C×2h to obtain the 3D printing heat-resistant resin.

[0063] The infrared spectra of the cyanate resin stock solution used in this embodiment and the primary photocurable product provided in this embodiment are shown in Figures 1 and 2. Figure 2 and Figure 3 As shown in the figure, it can be seen that the infrared spectrum of the primary photocurable product does not have infrared characteristic absorption peaks such as isotriazine, and the characteristic absorption peaks of cyanate (2265, 2236 cm -1 ) is obviously retained, indicating that cyanate ester does not participate in the reaction during the photocuring process, but is entrained into the product.

[0064] Example 2

[0065] The bisphenol A cyanate resin in Example 1 was replaced with an equal weight portion of phenolic cyanate resin (CAS No. 309244-92-4, Model 0006, Hubei Jiahui Xingcheng Biotechnology Co., Ltd.), and the other conditions were the same.

[0066] Example 3

[0067] The bisphenol A cyanate resin in Example 1 was replaced with an equal weight portion of bisphenol E cyanate resin (CAS No. 47073-92-7, molecular formula C 16 H 12 N2O2, molecular weight 264.28, Hubei Jiahui Xingcheng Biotechnology Co., Ltd.), and the other conditions were the same.

[0068] Example 4

[0069] In this embodiment, a 3D printing heat-resistant resin is provided, and the raw materials for preparing the 3D printing heat-resistant resin include component A and component B; wherein the specific components and amounts of component A and component B are shown in Table 2 below.

[0070] Table 2

[0071]

[0072]

[0073] The preparation method comprises the following steps:

[0074] S1: Weigh 46 parts of bisphenol A cyanate resin and 4 parts of bisphenol A epoxy acrylate at room temperature, and stir at 500 r / min for 60 minutes to prepare component A;

[0075] S2: Weigh 0.8 parts of 819, 0.2 parts of 184, 12 parts of pentaerythritol triacrylate, 11.2 parts of ethoxylated trimethylolpropane triacrylate, and 3 parts of 1,6-hexanediol diacrylate, and stir at 300 r / min at room temperature for 30 min to dissolve. Then add 0.001 parts of stannous octoate, 0.5 parts of polyetherimide and 0.3 parts of nano-silica and continue stirring for 60 min. Subsequently, add 17 parts of bisphenol A epoxy acrylate and 5 parts of ERL-4221 and stir thoroughly at 1200 r / min for 1.5 h to obtain component B.

[0076] The remaining steps are the same as those in Example 1.

[0077] Comparative Example 1

[0078] In this comparative example, a 3D printing heat-resistant resin is provided, and the raw materials for preparing the 3D printing heat-resistant resin include component A and component B; wherein the specific components and amounts of component A and component B are shown in Table 3 below.

[0079] Table 3

[0080]

[0081]

[0082] The preparation method comprises the following steps:

[0083] S1: 37 parts of bisphenol A cyanate and 3 parts of 1,6-hexanediol diacrylate were weighed at room temperature and stirred at 500 r / min for 60 min to prepare component A;

[0084] S2: Weigh 0.8 parts of 819, 0.2 parts of 184, 15.2 parts of pentaerythritol triacrylate, and 12 parts of ethoxylated trimethylolpropane triacrylate, stir at 300 r / min at room temperature for 30 minutes to dissolve, then add 0.001 parts of stannous octoate, 0.5 parts of polyetherimide and 0.3 parts of nano-silicon dioxide and continue stirring for 60 minutes, then add 31 parts of bisphenol A epoxy acrylate and stir thoroughly at 1200 r / min for 1.5 hours to obtain component B;

[0085] The remaining steps are the same as in Example 1.

[0086] Comparative Example 2

[0087] In this comparative example, a 3D printing heat-resistant resin is provided, and the raw materials and amounts of the 3D printing heat-resistant resin are shown in Table 4 below.

[0088] Table 4

[0089]

[0090] The preparation method comprises the following steps:

[0091] Weigh 0.8 parts of 819, 0.2 parts of 184, 13.7 parts of pentaerythritol triacrylate, 11 parts of ethoxylated trimethylolpropane triacrylate, and 2.75 parts of 1,6-hexanediol diacrylate, stir at 300 r / min at room temperature for 30 minutes to dissolve, then add 0.001 parts of stannous octoate, 0.45 parts of polyetherimide and 0.27 parts of nano-silica and continue stirring for 60 minutes, then add 45 parts of bisphenol A cyanate and 25.83 parts of ERL-4221 and stir well at 1200 r / min for 1.5 hours, mix well, and filter (mesh size is 100 mesh) to obtain a mixed solution.

[0092] The remaining steps are the same as in Example 1.

[0093] Comparative Example 3

[0094] In this comparative example, a 3D printing heat-resistant resin is provided, and the raw materials for preparing the 3D printing heat-resistant resin include component A and component B; wherein the specific components and amounts of component A and component B are shown in Table 5 below.

[0095] Table 5

[0096]

[0097] The preparation method comprises the following steps:

[0098] S1: 55.2 parts of bisphenol A cyanate and 4.8 parts of bisphenol A epoxy acrylate were weighed at room temperature and stirred at 500 r / min for 60 min to prepare component A;

[0099] S2: Weigh 0.8 parts of 819, 0.2 parts of 184, 10 parts of pentaerythritol triacrylate, 7.8 parts of ethoxylated trimethylolpropane triacrylate and 2 parts of 1,6-hexanediol diacrylate, stir at 300 r / min at room temperature for 30 minutes to dissolve, then add 0.001 parts of stannous octoate, 0.37 parts of polyetherimide and 0.2 parts of nano-silica and continue stirring for 60 minutes, then add 14 parts of bisphenol A epoxy acrylate and 4.63 parts of ERL-4221 and stir thoroughly at 1200 r / min for 1.5 hours to obtain component B.

[0100] The remaining steps are the same as in Example 1.

[0101] The 3D printing heat-resistant resin provided in the embodiments of the present invention and the comparative examples was tested for performance, and the testing method was as follows:

[0102] (1) Stability test: After standing for one week, observe whether the solution is stable;

[0103] (2) Viscosity test: After light curing, the residual liquid viscosity was tested using Anton Paar according to ISO 3219 standard;

[0104] (3) Appearance test: observe the product status after thermal curing;

[0105] (4) Mechanical properties test:

[0106] Tensile strength, tensile modulus, elongation at break: in accordance with ASTM D638 "Standard Test Method for Tensile Properties of Plastics";

[0107] Flexural strength and flexural modulus: measured in accordance with ASTM D790 "Standard Test Method for Flexural Properties of Unreinforced and Reinforced Plastics and Electrical Insulating Materials";

[0108] Impact performance: The non-notched impact strength is tested using ASTM D256 "Standard Test Method for Determining Izod Impact Strength of Plastics";

[0109] (5) Thermal performance test:

[0110] Heat deformation temperature (HDT): measured according to ISO 75-1:2013 standard;

[0111] (6) Surface hardness:

[0112] According to ASTM D2240 "Standard Test Method for Durometer Hardness of Rubber and Plastics", the hardness of 3D printing heat-resistant resin materials is measured by using a Shore durometer.

[0113] The performance test results are shown in Table 6.

[0114] Table 6

[0115]

[0116] It can be seen from Table 6 that both component A and component B provided in the embodiment of the present invention have good stability. The material formed by photocuring is relatively compact inside and on the surface, and can well wrap cyanate ester and prevent its thermosetting overflow, and exhibits good performance in stability, mechanical properties and heat resistance.

[0117] The stability of component B provided in Comparative Example 1 is poor, solidification occurs, and the heat resistance of the resin is poor. The possible reasons are that the epoxy acrylate content is too high, the resin viscosity is too high, and the surface and interior of the material formed by photocuring are too tight, which makes it difficult for cyanate ester to enter the interior of the material during the photocuring process. Therefore, the mechanical properties and heat resistance of the material after thermal curing are poor.

[0118] Although the amount of cyanate resin used in Comparative Example 2 is relatively large, because epoxy acrylate is not added, the surface and internal connections of the photocured primary product are relatively loose. Since the thermal curing of cyanate resin and epoxy resin is quite different, the adsorbed and wrapped cyanate resin is easy to overflow during thermal curing, resulting in a rough surface of the material. However, because the overflowed cyanate resin still acts on the surface and the total amount of cyanate resin is relatively high, its heat resistance stability and mechanical properties can still be maintained at a high level.

[0119] In Comparative Example 3, the proportion of cyanate resin is relatively large, but due to the relatively small total amount of bisphenol A epoxy acrylate and monomer, local cyanate resin overflow occurs during the thermosetting process, resulting in an uneven material structure, so the mechanical properties and heat resistance are not as good as those of Examples 1-4.

[0120] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the 3D printing heat-resistant resin and its preparation method and application, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the raw materials selected by the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A 3D printing heat-resistant resin, characterized in that: The raw materials for preparing the 3D printing heat-resistant resin include component A and component B; The component A comprises the following components in parts by weight: 35-53 parts of cyanate resin; Epoxy acrylate 2-8 parts; The B component comprises the following components in parts by weight:

2. The 3D printing heat-resistant resin according to claim 1, characterized in that: The cyanate resin includes any one of bisphenol F cyanate resin, bisphenol M cyanate resin, bisphenol E cyanate resin, novolac cyanate resin, dicyclopentadiene cyanate resin, and bisphenol A cyanate resin, or a combination of at least two thereof; Preferably, the epoxy acrylates in the A component and the B component each independently include any one of bisphenol A epoxy acrylate, novolac epoxy acrylate, epoxidized acrylate, and modified epoxy acrylate, or a combination of at least two thereof.

3. The 3D printing heat-resistant resin according to claim 1 or 2, characterized in that: The initiator includes any one of TPO, photoinitiator 819, photoinitiator 2959, photoinitiator 1173, photoinitiator 369, photoinitiator 184, photoinitiator 907, photoinitiator 651, and photoinitiator 250, or a combination of at least two thereof; Preferably, the toughening agent includes any one of polyethersulfone, polyetherimide, polyetherketone, natural rubber, chloroprene rubber, polyisoprene, carboxyl-terminated nitrile, nano-silicon dioxide, and nano-titanium dioxide, or a combination of at least two thereof.

4. The 3D printing heat-resistant resin according to any one of claims 1 to 3, characterized in that: The epoxy resin includes any one of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, aliphatic epoxy resin, and glycidylamine epoxy resin, or a combination of at least two of them.

5. The 3D printing heat-resistant resin according to any one of claims 1 to 4, characterized in that: The acrylate monomer includes any one of trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, propoxylated neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dipropylene glycol diacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, and a combination of at least two thereof.

6. The 3D printing heat-resistant resin according to any one of claims 1 to 5, characterized in that: The catalyst includes any one of stannous octoate, stannous oleate, and dibutyltin dilaurate, or a combination of at least two of them.

7. The 3D printing heat-resistant resin according to any one of claims 1 to 6, characterized in that: The mass ratio of the A component to the B component is 1:(1-4).

8. A method for preparing a 3D printing heat-resistant resin as claimed in any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: (1) mixing cyanate resin and epoxy acrylate to obtain component A; (2) mixing the initiator and the acrylate monomer, then adding the catalyst and the toughening agent for a second mixing, and then adding the epoxy resin and the epoxy acrylate for a third mixing to obtain component B; (3) Component A and component B are mixed to obtain a mixed solution, and a primary photocuring product is obtained by primary photocuring printing, and then secondary photocuring and thermal curing are performed to obtain the 3D printing heat-resistant resin.

9. The preparation method according to claim 8, characterized in that: The mixing speed in step (1) is 400 to 800 r / min, and the mixing time is 30 to 60 min; Preferably, the mixing speed in step (2) is 200 to 500 r / min, and the mixing time is 30 to 60 min; Preferably, the second mixing time in step (2) is 30 to 60 minutes; Preferably, the rotation speed of the third mixing in step (2) is 800-1400 r / min, and the time of the third mixing is 0.5-1.5 h; Preferably, the mixing speed in step (3) is 800 to 1400 r / min, and the mixing time is 0.5 to 1 h; Preferably, step (3) further comprises a filtering step after the mixing; Preferably, the parameters of the primary light-curing printing in step (3) include: the wavelength of the light source used is 360-430nm, the light intensity is 5000-8000uw / cm 2 The time of each primary light curing is 5 to 15 seconds, and the thickness of the light-cured product after each primary light curing is 1 to 3 mm; Preferably, the illumination intensity of the secondary light curing in step (3) is 8000 to 10000 uw / cm 2 , the secondary light curing time is 8 to 20 minutes; Preferably, the conditions for thermal curing in step (3) are: curing at 50-70°C for 0.5-1.5h, curing at 80-120°C for 2-4h, curing at 140-160°C for 1-3h, curing at 170-190°C for 1-3h, curing at 195-205°C for 1-3h, and curing at 210-220°C for 1-3h.

10. Use of the 3D printing heat-resistant resin according to any one of claims 1 to 7 in 3D printing.

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