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

Abstract

The application provides a 3D printing heat-resistant resin and a preparation method and application thereof, and the preparation raw material of the 3D printing heat-resistant resin comprises A component and B component; the A component comprises the following components: cyanate ester resin 35-53 parts; epoxy acrylate 2-8 parts; the B component comprises the following components: epoxy acrylate 12-35 parts; initiator 0.5-1.5 parts; toughening agent 0.5-1.5 parts; epoxy resin 4-29 parts; acrylate monomer 15-40 parts; catalyst 0.001-1 part. The application utilizes the characteristics that the epoxy acrylate, the epoxy resin and the acrylate monomer are easily photocured and have low reactivity with the cyanate ester resin under mild conditions, and the cyanate ester resin which does not participate or rarely participates in photocuring is wrapped in the photocured matrix resin sample under relatively mild photocuring reaction conditions, so that the purpose of reducing the difficulty of cyanate ester resin photocuring conditions is achieved.

Description

TECHNICAL FIELD

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

[0002] Cyano ester (CE) is widely used in aerospace, electronic appliances, automobile transportation and other fields due to its excellent dielectricity, heat resistance, dimensional stability, corrosion resistance and mechanical properties. However, due to the chemical structure characteristics of cyano ester, it generally has the problems of low reactivity and incomplete curing in photocuring. In order to improve the photocuring performance of cyano ester, it is usually modified, such as blending modification with other resins or introducing specific functional groups. Among them, the relatively common method is to modify cyano ester with epoxy resin (EP) which has relatively low price, relatively low curing temperature, and easier operation and control of curing process. However, due to the difference in compatibility and reactivity between the two, problems such as uneven or incomplete curing, material cracking or deformation are prone to occur.

[0003] Therefore, how to improve the modification of EP to CE at low cost and high efficiency is increasingly important. SUMMARY

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

[0005] To achieve the purpose of the application, the following technical solutions are adopted:

[0006] In a first aspect, the present application provides a 3D printing heat-resistant resin, and the preparation raw materials of the 3D printing heat-resistant resin comprise component A and component B.

[0007] The component A comprises the following components according to weight fraction:

[0008] Cyano ester resin 35-53 parts;

[0009] Epoxy acrylate 2-8 parts;

[0010] The component B comprises the following components according to weight fraction:

[0011]

[0012] The present application utilizes the characteristics of epoxy acrylate, epoxy resin, and acrylate monomer that are easily photocured and have low reactivity with cyanate ester resin under mild conditions, and the cyanate ester resin that does not participate or rarely participates in photocuring is entrapped in the photocured matrix resin sample under relatively mild photocuring reaction conditions, thereby achieving the purpose of reducing the difficulty of cyanate ester resin photocuring conditions, so as to ensure that most of the cyanate ester resin reacts with the photocured matrix resin only when heat curing, thereby reducing the occurrence of side reactions.

[0013] The present application does not use modified cyanate ester resin which is expensive, has good and poor performance, and has complex photocuring conditions, but entraps cyanate ester resin inside the photocured material to participate in heat curing reaction, which can not only reduce the cost, but also reduce the side reactions, thereby ensuring the material quality.

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

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

[0016] In the present application, the amount of epoxy acrylate in the B component 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. by weight.

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

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

[0019] In the present application, the amount of epoxy resin in the B component 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. by weight.

[0020] In the present application, the amount of the acrylic ester monomer in the B component 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. by weight.

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

[0022] Preferably, the cyanate ester resin comprises any one of a bisphenol F type cyanate ester resin, a bisphenol M type cyanate ester resin, a bisphenol E type cyanate ester resin, a phenol formaldehyde type cyanate ester resin, a dicyclopentadiene type cyanate ester resin, a bisphenol A type cyanate ester resin or a combination of at least two thereof.

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

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

[0025] Preferably, the toughening agent comprises any one of a polyether sulfone, a polyether imide, a polyether ketone, a natural rubber, a chloroprene rubber, a polyisoprene, a carboxyl-terminated butyl nitrile, a nano-silicon dioxide, a nano-titanium dioxide or a combination of at least two thereof.

[0026] Preferably, the epoxy resin comprises any one of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol formaldehyde type epoxy resin, an aliphatic epoxy resin, a glycidyl amine type epoxy resin or a combination of at least two thereof.

[0027] Preferably, the acrylate monomer comprises 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, or a combination of at least two thereof.

[0028] Preferably, the catalyst comprises any one of stannous octoate, stannous oleate, dibutyl tin dilaurate, or a combination of at least two thereof.

[0029] Preferably, the mass ratio of the A component and the B component is 1: (1-4), such as 1:1, 2:3, 1:2, 1:3, 1:4, etc.

[0030] In a second aspect, the present application provides a preparation method of the 3D printing heat-resistant resin according to the first aspect, the preparation method comprising the following steps:

[0031] (1) mixing the cyanate ester resin with the epoxy acrylate to obtain an A component;

[0032] (2) mixing the initiator with 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 a B component;

[0033] (3) mixing the A component and the B component to obtain a mixed solution, printing a primary photocured product through primary photocuring, and then performing secondary photocuring and heat curing to obtain the 3D printing heat-resistant resin.

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

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

[0036] Preferably, the second mixing in step (2) is performed for 30-60 minutes, for example 30 minutes, 40 minutes, 50 minutes, 60 minutes, etc.

[0037] Preferably, the third mixing in step (2) is performed at a rotation speed of 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 for 0.5-1.5 hours, for example 0.5 hours, 1 hour, 1.5 hours, etc.

[0038] Preferably, the mixing in step (3) is performed at a rotation speed of 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 for 0.5-1 hour, for example 0.5 hour, 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour, 1 hour, etc.

[0039] Preferably, the mixing in step (3) is followed by a filtration step.

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

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

[0042] In this invention, the photocuring conditions and ultraviolet light intensity are relatively ordinary. That is, this invention only requires relatively conventional photocuring conditions to prepare photocurable materials encapsulating cyanate ester resin, which greatly reduces the difficulty of the photocuring reaction of cyanate ester resin.

[0043] Preferably, the thermosetting conditions in step (3) are as follows: curing sequentially at 50–70°C (e.g., 50°C, 60°C, 70°C, etc.) for 0.5–1.5 h (e.g., 0.5 h, 1 h, 1.5 h, etc.), at 80–120°C (e.g., 80°C, 90°C, 100°C, 110°C, 120°C, etc.) for 2–4 h (e.g., 2 h, 3 h, 4 h, etc.), and at 140–160°C (e.g., 140°C, 150°C, 160°C, etc.) for 1– Curing can be carried out at various temperatures: 3 hours (e.g., 1 hour, 2 hours, 3 hours), 170–190°C (e.g., 170°C, 180°C, 190°C), 195–205°C (e.g., 195°C, 200°C, 205°C), and 210–220°C (e.g., 210°C, 215°C, 220°C). As a preferred embodiment of the invention, high-temperature resistant resin materials with good mechanical properties are prepared by controlling the thermosetting temperature and time for staged thermosetting, utilizing the network interpenetrating structure formed by the cyanate ester resin and the photocurable matrix resin.

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

[0045] Thirdly, the present invention provides an application of the heat-resistant resin for 3D printing 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 application utilizes the characteristics of the epoxy acrylate, the epoxy resin, the acrylate monomer easy photocuring molding and the low reactivity with cyanate ester resin under mild conditions, and the cyanate ester resin which does not participate or rarely participates in the photocuring is entrapped in the molding photocuring matrix resin sample under relatively mild photocuring reaction conditions, so as to reduce the difficulty of cyanate ester resin photocuring conditions, thereby ensuring that most of the cyanate ester resin only reacts with the photocuring matrix resin when heat curing, thereby reducing the occurrence of side reactions. BRIEF DESCRIPTION OF DRAWINGS

[0048] Figure 1 For example, the present application provides a synthesis mechanism diagram of the 3D printing heat-resistant resin, taking the epoxy acrylate as the bisphenol A epoxy acrylate and the cyanate ester resin as the bisphenol A cyanate ester resin.

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

[0050] Figure 3 The infrared spectrum of the primary photocuring product provided in Example 1. DETAILED DESCRIPTION

[0051] The technical solutions of the present application will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only to help understand the present application, and should not be regarded as specific limitations of the present application.

[0052] Example 1

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

[0054] Table 1

[0055]

[0056]

[0057] The preparation method includes the following steps:

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

[0059] S2: take 0.8 parts of 819, 0.2 parts of 184, 15.2 parts of pentaerythritol triacrylate, 12 parts of ethoxylated trimethylolpropane triacrylate, 3 parts of 1,6-hexanediol diacrylate, dissolve at room temperature under 300 r / min stirring for 30 min, 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 min, then add 21 parts of bisphenol A epoxy acrylate and 7 parts of ERL-4221 and fully stir at 1200 r / min for 1.5 h to obtain the B component;

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

[0061] S4: perform primary photocuring printing on the mixed solution, the wavelength of the used ultraviolet light source is 385 nm, the light intensity is 6000 uw / cm 2 , the time for each primary photocuring is 6 s, the thickness of the photocured product after each primary photocuring is 1 mm, repeat several times, directly end the printing to obtain a primary photocured product;

[0062] S5: clean the primary photocured product with isopropyl alcohol, then perform secondary photocuring on the primary photocured product under the condition of a light intensity of 9000 uw / cm 2 for 15 min, finally perform heat curing on the secondary photocured product according to a heat curing process of 60℃×1h+100℃×3h+150℃×2h+180℃×2h+200℃×2h+210℃×2h to obtain the 3D printing heat-resistant resin.

[0063] The infrared spectrum of the cyanate ester resin stock solution used in this example and the primary photocured product provided by this example are shown in Figure 2 and Figure 3 respectively, it can be seen that there is no infrared characteristic absorption peak of s-triazine in the infrared spectrum of the primary photocured product, and the cyanate ester characteristic absorption peaks (2265, 2236 cm -1 ) are obviously retained, indicating that the cyanate ester does not participate in the reaction during photocuring, but is wrapped into the product.

[0064] Example 2

[0065] Replace the bisphenol A cyanate ester resin in Example 1 with an equal weight part of a phenolic cyanate ester resin (CAS No. 309244-92-4, Model No. 0006, Hubei Jiahui Xingcheng Biological Technology Co., Ltd.), and the rest of the conditions are the same.

[0066] Example 3

[0067] The bisphenol A cyanate ester resin in Example 1 is replaced by an equal weight fraction of a bisphenol E cyanate ester resin (CAS No. 47073-92-7, molecular formula C 16 H 12 N2O2, molecular weight 264.28, Hubei Jiahui Xingcheng Biological Technology Co., Ltd.), and the rest of the conditions are the same.

[0068] Example 4

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

[0070] Table 2

[0071]

[0072]

[0073] The preparation method includes the following steps:

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

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

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

[0077] Comparative Example 1

[0078] In this example, a 3D printing heat-resistant resin is provided, and the preparation raw materials of the 3D printing heat-resistant resin include A component and B component; wherein the specific components and amounts of the A component and the B component are shown in Table 2.

[0079] Table 3

[0080]

[0081]

[0082] The preparation method includes the following steps:

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

[0084] S2: 0.8 parts of 819, 0.2 parts of 184, 15.2 parts of pentaerythritol triacrylate, 12 parts of ethoxylated trimethylolpropane triacrylate were weighed out and dissolved by stirring at 300 r / min for 30 min at room temperature, then 0.001 parts of stannous octoate, 0.5 parts of polyetherimide and 0.3 parts of nano-silica were added and stirred for 60 min, and then 31 parts of bisphenol A epoxy acrylate was added and stirred at 1200 r / min for 1.5 h 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 preparation raw materials and amounts of the 3D printing heat-resistant resin are shown in Table 4.

[0088] Table 4

[0089]

[0090] The preparation method comprises the following steps:

[0091] 0.8 parts of 819, 0.2 parts of 184, 13.7 parts of pentaerythritol triacrylate, 11 parts of ethoxylated trimethylolpropane triacrylate, 2.75 parts of 1,6-hexanediol diacrylate were weighed out and dissolved by stirring at 300 r / min for 30 min at room temperature, then 0.001 parts of stannous octoate, 0.45 parts of polyetherimide and 0.27 parts of nano-silica were added and stirred for 60 min, and then 45 parts of bisphenol A cyanate and 25.83 parts of ERL-4221 were added and stirred at 1200 r / min for 1.5 h 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 preparation raw materials of the 3D printing heat-resistant resin comprise component A and component B; wherein the specific components and amounts of component A and component B are shown in Table 5.

[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 are weighed at room temperature and stirred at 500 r / min for 60 min to prepare component A;

[0099] S2: 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 are weighed, dissolved by stirring at 300 r / min for 30 min at room temperature, then 0.001 parts of stannous octoate, 0.37 parts of polyetherimide and 0.2 parts of nano silicon dioxide are added, and stirring is continued for 60 min, and then 14 parts of bisphenol A epoxy acrylate and 4.63 parts of ERL-4221 are added, and stirring is carried out at 1200 r / min for 1.5 h to obtain component B.

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

[0101] The 3D printing heat-resistant resin provided by the examples and the comparative examples of the application is subjected to performance testing, and the testing method is as follows:

[0102] (1) Stability test: observe the solution state after standing for one week;

[0103] (2) Viscosity test: after photocuring, test the residual liquid viscosity according to the standard of ISO 3219 using Anton Paar;

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

[0105] (4) Mechanical property test:

[0106] Tensile strength, tensile modulus and elongation at break: execute according to the standard of ASTM D638 "Standard Test Methods for Tensile Properties of Plastics";

[0107] Flexural strength and flexural modulus: determine according to the standard of ASTM D790 "Standard Test Methods for Flexural Properties of Unreinforced and Reinforced Plastics and Electrical Insulating Materials";

[0108] Impact property: test the non-notched impact strength according to the standard of ASTM D256 "Standard Test Methods for Determining the Izod Pendulum Impact Resistance of Plastics";

[0109] (5) Thermal property test:

[0110] Heat distortion temperature (HDT): determine according to the standard of ISO 75-1:2013;

[0111] (6) Surface hardness:

[0112] The hardness of the 3D printing heat-resistant resin material was measured by using a Shore hardness tester according to ASTM D2240 Standard Test Methods for Rubber and Plastic Hardness by Durometer.

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

[0114] Table 6

[0115]

[0116] As can be seen from Table 6, the A component and the B component provided by the embodiments of the present application both have good stability, the material formed by photocuring is relatively tight inside and on the surface, can well wrap cyanate and prevent it from overflowing during thermal curing, and shows good performance in stability, mechanical properties and heat resistance.

[0117] The stability of the B component provided by Comparative Example 1 is poor, and the resin has poor heat resistance. The possible reason is that the content of epoxy acrylate is too high, the viscosity of the resin is too large, the surface and the inside of the material formed by photocuring are too tight, which makes it difficult for cyanate to enter the inside of the material during photocuring, and thus the mechanical properties and heat resistance of the material after thermal curing are poor.

[0118] Although the amount of cyanate resin is large in Comparative Example 2, the surface and the inside of the photocured primary product are relatively loose due to the absence of epoxy acrylate, and the cyanate resin is easily overflowed during thermal curing due to the large difference between the cyanate resin and the epoxy resin in thermal curing, which leads to a rough material surface. However, the heat resistance and mechanical properties of the material can still be maintained at a high level due to the high total amount of cyanate resin.

[0119] In Comparative Example 3, the proportion of cyanate resin is large, but the total amount of bisphenol A epoxy acrylate and monomer is relatively small, and local cyanate resin is overflowed during thermal curing, which leads to uneven material structure, and thus the mechanical properties and heat resistance are not as good as those of Examples 1-4.

[0120] The applicant declares that the 3D printing heat-resistant resin, the preparation method and the application thereof of the present application are illustrated by the above examples, but the present application is not limited to the above examples, i.e. it does not mean that the present application must rely on the above examples to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of the selected materials, addition of auxiliary ingredients, selection of specific methods, etc. all fall within the protection scope and disclosure scope of the present application.

Claims

1. A 3D printing heat-resistant resin, characterized by, The preparation raw material of the 3D printing heat-resistant resin comprises an A component and a B component; The A component comprises the following components in parts by weight: Cyanate ester resin 35-53 parts; Epoxy acrylate 2-8 parts; The B component comprises the following components in parts by weight: Epoxy acrylate 12-35 parts; Initiator 0.5-1.5 parts; Toughening agent 0.5-1.5 parts; Epoxy resin 4-29 parts; Acrylate monomer 15-40 parts; Catalyst 0.001-1 parts; The epoxy acrylate in the A component and the B component each independently comprises any one or a combination of at least two of bisphenol A epoxy acrylate, phenolic epoxy acrylate; The acrylate monomer comprises any one or a combination of at least two 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, and tripropylene glycol diacrylate. The 3D printing heat-resistant resin is prepared by the following method: (1) mixing the cyanate ester resin and the epoxy acrylate to obtain the A component; (2) mixing the initiator and the acrylate monomer, then adding the catalyst and the toughening agent for secondary mixing, and then adding the epoxy resin and the epoxy acrylate for tertiary mixing to obtain the B component; (3) mixing the A component and the B component to obtain a mixed solution, performing primary photocuring printing to obtain a primary photocuring product, and then performing secondary photocuring and thermal curing to obtain the 3D printing heat-resistant resin; The parameters of the primary light-cured printing in step (3) include: light intensity of 5000-8000 uw / cm 2 ; The light intensity of the secondary photocuring in step (3) is 8000-10000 uw / cm 2 .

2. The 3D printing heat-resistant resin according to claim 1, characterized in that, The cyanate ester resin comprises any one or a combination of at least two of bisphenol F cyanate ester resin, bisphenol M cyanate ester resin, bisphenol E cyanate ester resin, phenolic cyanate ester resin, dicyclopentadiene cyanate ester resin, and bisphenol A cyanate ester resin.

3. The 3D printing heat-resistant resin according to claim 1, characterized in that, The initiator comprises any one or a combination of at least two of TPO, photoinitiator 819, photoinitiator 2959, photoinitiator 1173, photoinitiator 369, photoinitiator 184, photoinitiator 907, photoinitiator 651, and photoinitiator 250.

4. The 3D printing heat-resistant resin according to claim 1, characterized in that, The toughening agent comprises any one or a combination of at least two of polyether sulfone, polyether imide, polyether ketone, natural rubber, chlorobutyl rubber, polyisoprene, carboxyl-terminated butylnitrile, nano-silicon dioxide, and nano-titanium dioxide.

5. The 3D printing heat-resistant resin according to claim 1, characterized in that, The epoxy resin comprises any one or a combination of at least two of bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic epoxy resin, aliphatic epoxy resin, and glycidyl amine epoxy resin.

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

7. The 3D printing heat-resistant resin according to claim 1, wherein, The mass ratio of the A component to the B component is 1:(1-4).

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

9. The production method according to claim 8, characterized by, In step (1), the rotation speed of the mixing is 400-800 r / min, and the mixing time is 30-60 min.

10. The preparation method according to claim 8, characterized in that, In step (2), the rotation speed of the mixing is 200-500 r / min, and the mixing time is 30-60 min.

11. The preparation method according to claim 8, characterized in that, In step (2), the second mixing time is 30-60 min.

12. The method of claim 8, wherein, In step (2), the rotation speed of the third mixing is 800-1400 r / min, and the third mixing time is 0.5-1.5 h.

13. The preparation method according to claim 8, characterized in that, In step (3), the rotation speed of the mixing is 800-1400 r / min, and the mixing time is 0.5-1 h.

14. The preparation method according to claim 8, characterized in that, In step (3), the mixing is further followed by a filtering step.

15. The preparation method according to claim 8, characterized in that, The parameters of the primary photocuring printing in step (3) include: the wavelength of the used light source is 360-430 nm, the light intensity is 5000-8000 uw / cm 2 The time of each primary photocuring is 5-15 s, and the thickness of the photocured product after each primary photocuring is 1-3 mm.

16. The preparation method according to claim 8, characterized in that, The light intensity of the secondary photocuring in step (3) is 8000-10000 uw / cm 2 and the time of the secondary photocuring is 8-20 min.

17. The method of claim 8, wherein the method further comprises, In step (3), the heat curing conditions are as follows: sequentially curing at 50-70℃ for 0.5-1.5 h, at 80-120℃ for 2-4 h, at 140-160℃ for 1-3 h, at 170-190℃ for 1-3 h, at 195-205℃ for 1-3 h, and at 210-220℃ for 1-3 h.

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

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