An epoxy resin material for a resin mold, a method for producing the same, and an application thereof

Abstract

The present application relates to a kind of epoxy resin material for resin mold and its preparation method and application, belong to epoxy resin composite material technical field.The resin mold epoxy resin material includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyamide curing agent, three rhodamine epoxy curing agent, accelerator and water phase filler;The preparation of the three rhodamine epoxy curing agent is: three rhodamine based on triphenylamine is mixed with ethylenediamine uniformly and is reacted at 150~170 ℃ for 10~18 h, is filtered, washed and dried, and three rhodamine epoxy curing agent is prepared.The three rhodamine epoxy curing agent used in the resin mold epoxy resin material in the present application provides visualization in addition to stress response, and the three rhodamine epoxy curing agent helps to improve the overall mechanical properties of epoxy resin composite material.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of epoxy resin composites, and particularly relates to an epoxy resin material for resin molds and a preparation method and application thereof. BACKGROUND

[0002] Epoxy resin is widely used as a mold material in numerous industrial applications due to its excellent mechanical properties, bonding properties, and chemical stability. However, the overall mechanical properties of traditional epoxy resin molds are still relatively low, and existing epoxy resin curing agents cannot fully improve the overall mechanical properties of resin molds, resulting in that epoxy resin molds are not suitable for high-load and complex application environments. In addition, the stress monitoring of existing epoxy resin molds is not intuitive, and it is difficult to accurately monitor the stress distribution of the mold during use. It is often difficult to intuitively monitor the internal stress during use, which limits its application in occasions with high precision requirements. At present, there is a lack of a curing agent that can provide visualization of the internal stress of epoxy resin composites, so that the operator cannot intuitively understand the changes of the epoxy resin composite structure under stress. Although the introduction of hyperbranched polymers in the resin mold epoxy resin material in Chinese Patent Application CN 117843952 A can improve the strength of the resin mold, the curing agent used is still a traditional epoxy curing agent, which does not have the characteristics of stress response, resulting in that the stress monitoring method of the prepared resin mold is not intuitive, and the resin mold epoxy resin material in the patent application also has the problems of low strength and hardness.

[0003] In summary, it is necessary to provide an epoxy resin material for resin molds and a preparation method and application thereof. SUMMARY

[0004] In order to solve one or more technical problems existing in the prior art, the present application provides an epoxy resin material for resin molds and a preparation method and application thereof.

[0005] In a first aspect, the present application provides an epoxy resin material for resin molds, which comprises bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyamide curing agent, trirhodamine epoxy curing agent, accelerator and water phase filler; the preparation of the trirhodamine epoxy curing agent is as follows: trirhodamine based on triphenylamine is uniformly mixed with ethylenediamine and reacted at 150-170℃ for 10-18h, and then filtered, washed and dried to obtain the trirhodamine epoxy curing agent.

[0006] Preferably, the curing of the epoxy resin material for resin molds is as follows: first curing at 30-40℃ for 10-15h, and then curing at 110-130℃ for 1-3h.

[0007] Preferably, the molar ratio of the triphenylamine-based trirhodamine to the ethylenediamine is 1:(5-20).

[0008] Preferably, the mass ratio of the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, the polyamide curing agent, the trirhodamine epoxy curing agent, the accelerator and the water phase filler is 10:(2-8):(3-8):(0.5-2):(0.5-2):(50-80).

[0009] Preferably, the mass ratio of the polyamide curing agent to the trirhodamine epoxy curing agent is (4-8):1.

[0010] Preferably, the bisphenol A type epoxy resin is E51 liquid epoxy resin; the bisphenol F type epoxy resin is Epikote 862 liquid bisphenol F type epoxy resin; the polyamide curing agent is polyamide epoxy curing agent 5140 and / or polyamide epoxy curing agent 2636; and / or the accelerator is 2,4,6-tris(dimethylaminomethyl)phenol.

[0011] Preferably, the water phase filler comprises hydrophilic fumed silica, precipitated white carbon black, nano titanium dioxide and water in a mass ratio of (15-25):(5-15):(5-15):(20-30).

[0012] The present application provides, in a second aspect, a preparation method of the resin mold epoxy resin material described in the first aspect of the present application, the method comprising the following steps:

[0013] (1) mixing hydrophilic fumed silica, precipitated white carbon black and nano titanium dioxide with water to obtain a water phase filler;

[0014] (2) mixing bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyamide curing agent, trirhodamine epoxy curing agent and accelerator uniformly, then adding the water phase filler and mixing uniformly to obtain the resin mold epoxy resin material.

[0015] Preferably, in step (1) and / or step (2), the uniform mixing is performed by stirring uniformly at a rotation speed of 400-800 r / min.

[0016] The present application provides, in a third aspect, the use of the resin mold epoxy resin material described in the first aspect of the present application or prepared by the preparation method described in the second aspect of the present application in the preparation of a resin mold.

[0017] Compared with the prior art, the present application has at least the following beneficial effects:

[0018] (1) The present application introduces a new type of tri-rhodamine epoxy curing agent into the resin mold epoxy resin material through chemical design, which can change the photophysical properties under stress, has the force-induced fluorescence color change (stress response) characteristics, so that the resin mold epoxy resin material can intuitively show the stress distribution through the fluorescence color change when subjected to different degrees of force, providing immediate feedback and adjustment possibilities, this force-induced fluorescence color change characteristic can realize the intuitive monitoring of stress for the resin mold epoxy resin material, so that the operator can identify and monitor the stress damage of the resin mold epoxy resin material in real time, thereby optimizing the product quality and safety, improving the response ability and visual monitoring of the resin mold epoxy resin material under stress, solving the problem that the stress monitoring of the existing epoxy resin mold is not intuitive and it is difficult to accurately monitor the stress distribution of the resin mold during use.

[0019] (2) The present application creatively reacts triphenylamine-based tri-rhodamine with ethylenediamine to obtain a tri-rhodamine epoxy curing agent which can be used as a curing agent, and there is no prior art report on the application of tri-rhodamine in curing agents; and the present application finds that the triphenylamine-based tri-rhodamine involved in the preparation of the tri-rhodamine epoxy curing agent has a synergistic effect with ethylenediamine, and the ethylenediamine combined on the molecular structure of the triphenylamine-based tri-rhodamine can effectively endow the tri-rhodamine with the force-induced fluorescence color change characteristic, and the three rhodamine groups combined in the triphenylamine-based tri-rhodamine are effectively fused together, which can also effectively improve the effect of the ethylenediamine epoxy curing agent. The present application applies the tri-rhodamine epoxy curing agent in the resin mold epoxy resin material, and uses it with the polyamide curing agent, which can significantly increase the hardness and bending strength of the resin mold epoxy resin material, solving the problem that the existing epoxy resin curing agent cannot fully improve the overall mechanical properties of the resin mold; that is, in addition to providing visualization of stress response, the tri-rhodamine epoxy curing agent also helps to improve the overall mechanical properties of the resin mold epoxy resin material. The possible reason is that the structure of the curing agent is optimized at the molecular level, the crosslinking density of the epoxy resin is improved, thereby enhancing the hardness, toughness, bending strength and durability of the final product, which also enables the prepared resin mold to withstand higher working load and have a longer service life.

[0020] (3) The tri-rhodamine epoxy curing agent used in the resin mold epoxy resin material of the present application can be compatible with various existing epoxy resin systems, simplifying the processing and application process, without the need for large-scale modification of the existing production line, and is suitable for the existing production line and process; in addition, the synthesis process of the tri-rhodamine epoxy curing agent used in the present application is simple and easy to mass produce, which helps to reduce production costs. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 Figure 1 is a color change result chart of a cured sample of the resin mold epoxy material prepared in Example 1 of the present application under ultraviolet light; (a) is the sample before pressure test; (b) is the force-induced fluorescence color change result of the sample under 7 MPa pressure. DETAILED DESCRIPTION

[0022] In order to make the objectives, technical solutions and advantages of the present application clearer, the technical solutions of the present application will be described clearly and completely below in combination with the embodiments in the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.

[0023] The present application provides, in a first aspect, a resin mold epoxy material, which comprises a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a polyamide curing agent, a trirhodamine epoxy curing agent, an accelerator and a water phase filler; the trirhodamine epoxy curing agent is prepared by mixing a trirhodamine based on triphenylamine with ethylenediamine uniformly and reacting at 150-170°C (for example, 150°C, 160°C or 170°C) for 10-18h (for example, 10, 12, 14, 16 or 18h), and then by filtering, washing and drying to obtain the trirhodamine epoxy curing agent; in the present application, the obtained filter cake is washed with distilled water more than three times using a Buchner funnel, and finally vacuum dried at 50-70°C for 12h; in the present application, the reaction between the trirhodamine based on triphenylamine and ethylenediamine is, for example, as shown in the following formula I;

[0024]

[0025] In the present application, the preparation of the trirhodamine based on triphenylamine comprises the following steps:

[0026] (a) mixing m-methoxyaniline, 3-bromoanisole and 1,10-phenanthroline with toluene uniformly, then adding potassium tert-butoxide and cuprous iodide under nitrogen atmosphere, and reacting at 130°C for 48h to obtain a reaction product, and then filtering, extracting, concentrating and purifying by column chromatography in sequence after cooling the obtained reaction product to room temperature of 15-35°C to obtain tris(3-methoxyphenyl)amine; wherein the molar ratio of m-methoxyaniline, 3-bromoanisole, 1,10-phenanthroline, potassium tert-butoxide and cuprous iodide is 1:3:0.04:3:0.04, and the mass ratio of toluene to m-methoxyaniline is 9:1; in the present application, the extraction can be performed using, for example, ethyl acetate, and when purifying by column chromatography, the eluent used is, for example, a mixed solvent mixed by ethyl acetate and n-hexane in a volume ratio of 2:98;

[0027] (b) dissolving tri(3-methoxyphenyl)amine in pyridine hydrochloride and reacting at 200℃ for 12h, then cooling to room temperature and adding water to precipitate, followed by filtration, drying, column chromatography purification to obtain tri(3-hydroxyphenyl)amine, wherein the mass ratio of the tri(3-methoxyphenyl)amine to the pyridine hydrochloride is 1:10, and when performing column chromatography purification, an eluent such as a mixed solvent mixed by methanol and dichloromethane in a volume ratio of 3:97 is used;

[0028] (c) mixing 3-hydroxy-N,N-diethyl aniline and phthalic anhydride uniformly with toluene, then refluxing at 140℃ under nitrogen atmosphere for 3h, cooling to 55℃, adding a 35% mass fraction sodium hydroxide aqueous solution, reacting at 90℃ for 6h, then diluting the product with water and adjusting the pH to 7 with hydrochloric acid and placing at room temperature for 2h, followed by filtration, washing, suction filtration and vacuum drying to obtain a keto acid compound; wherein the molar ratio of 3-hydroxy-N,N-diethyl aniline to phthalic anhydride is 1:1.05, the mass ratio of toluene to 3-hydroxy-N,N-diethyl aniline is 5.23:1, and the volume ratio of the sodium hydroxide aqueous solution, toluene and water is 1:1:10; the amount of hydrochloric acid is not specifically limited in the present application, and the pH can be adjusted to the target value;

[0029] (d) mixing tri(3-hydroxyphenyl)amine with the keto acid compound uniformly with trifluoroacetic acid, and reacting at 95℃ for 12h, after the reaction is completed, pouring the obtained reaction mixture into an ice water mixture, neutralizing with a saturated sodium bicarbonate solution, followed by filtration, drying and column chromatography purification to obtain tri-rhodamine based on triphenylamine, wherein the molar ratio of tri(3-hydroxyphenyl)amine to the keto acid compound is 1:2, and the mass amount of the trifluoroacetic acid is 10 times the mass of the tri(3-hydroxyphenyl)amine, and when performing column chromatography purification, an eluent such as a mixed solvent mixed by methanol and chloroform in a volume ratio of 3:97 is used; the amount of the ice water mixture is not specifically limited in the present application, and can be routinely selected by those skilled in the art, for example, the mass ratio of the ice water mixture to the obtained reaction mixture is (10-20):1.

[0030] The present application introduces a new type of tri-rhodamine epoxy curing agent in the resin mold epoxy material through chemical design, in the present application, the tri-rhodamine epoxy curing agent formed by the reaction of triphenylamine-based tri-rhodamine and ethylenediamine can directly act on the chemical bond along the high molecular chain from both ends of the weak bond (C-N bond) under stress, realizing the conversion of rhodamine molecules from the almost non-fluorescent closed ring form to the colored fluorescent open ring form, the tri-rhodamine epoxy curing agent can change the photophysical properties when stressed, has the stress-induced fluorescence color change (stress response) characteristic, so that the resin mold epoxy material can directly show the stress distribution through the fluorescence color change when subjected to different degrees of force, providing immediate feedback and adjustment possibility, this stress-induced fluorescence color change characteristic can realize the intuitive monitoring of stress for the resin mold epoxy material in use, so that the operator can identify and monitor the stress damage of the resin mold epoxy material in real time, thereby optimizing the product quality and safety, can improve the response ability and visual monitoring of the resin mold epoxy material under stress, solves the problem that the stress monitoring of the existing epoxy resin mold is not intuitive and it is difficult to accurately monitor the stress distribution of the resin mold in the use process.

[0031] The present application creatively reacts triphenylamine-based tri-rhodamine with ethylenediamine to obtain a tri-rhodamine epoxy curing agent which can be used as a curing agent, and there is no prior art report on the application of tri-rhodamine in curing agents; and the present application finds that the triphenylamine-based tri-rhodamine and ethylenediamine involved in the preparation of the tri-rhodamine epoxy curing agent have a synergistic effect, the combination of ethylenediamine on the molecular structure of triphenylamine-based tri-rhodamine can effectively endow the tri-rhodamine with the stress-induced fluorescence color change characteristic, and the combination of three rhodamine groups of triphenylamine-based tri-rhodamine can effectively improve the effect of the ethylenediamine epoxy curing agent, the application of the tri-rhodamine epoxy curing agent in the resin mold epoxy material in combination with the polyamide curing agent can significantly increase the hardness and bending strength of the resin mold epoxy material, while the direct use of tri-rhodamine or the direct use of ethylenediamine in combination with the polyamide curing agent cannot effectively increase the hardness and bending strength of the resin mold epoxy material, and does not have the stress-induced fluorescence color change characteristic; the person skilled in the art knows that 4,4'-diaminodiphenyl methane (DDM curing agent) is usually used to enhance the hardness and bending strength of the epoxy resin composite material, and the effect of the tri-rhodamine epoxy curing agent in the present application on enhancing the hardness and bending strength of the epoxy resin composite material is even better than that of the DDM curing agent.

[0032] According to some preferred embodiments, the curing of the resin mold epoxy resin material is: first curing at 30-40℃ for 10-15h, and then curing at 110-130℃ for 1-3h, which is beneficial to make the trirhodamine epoxy curing agent more fully participate in the reaction of the epoxy resin, so as to more effectively improve the crosslinking density of the epoxy resin, and make the resin mold epoxy resin material after curing have higher hardness and bending strength.

[0033] According to some preferred embodiments, the molar ratio of the trirhodamine based on triphenylamine to the ethylenediamine is 1:(5-20); in the present application, the excess of ethylenediamine is beneficial to improve the yield of the target product.

[0034] According to some preferred embodiments, the mass ratio of the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, the polyamide curing agent, the trirhodamine epoxy curing agent, the accelerator and the water phase filler is 10:(2-8):(3-8):(0.5-2):(0.5-2):(50-80).

[0035] According to some preferred embodiments, the mass ratio of the polyamide curing agent to the trirhodamine epoxy curing agent is (4-8):1 (for example 4:1, 5:1, 6:1, 7:1 or 8:1); in the present application, it is preferred to add appropriate trirhodamine epoxy curing agent in the epoxy resin system, and it is found that if the amount of the trirhodamine epoxy curing agent is insufficient, it cannot effectively improve the crosslinking density of the epoxy resin, resulting in lower strength and hardness of the cured product and poor mechanical properties, and if the amount of the trirhodamine epoxy curing agent is too much, internal stress and local overheating are easily generated during the curing process, resulting in internal defects such as cracks or bubbles in the cured product, and the cured product becomes hard and brittle, although this can make the epoxy resin composite have high hardness, but its toughness and bending strength will decrease.

[0036] According to some preferred embodiments, the bisphenol A type epoxy resin is E51 liquid epoxy resin; and / or the bisphenol F type epoxy resin is Epikote 862 liquid bisphenol F type epoxy resin.

[0037] According to some preferred embodiments, the polyamide curing agent is polyamide epoxy curing agent 5140 and / or polyamide epoxy curing agent 2636; and / or the accelerator is 2,4,6-tris(dimethylaminomethyl) phenol (accelerator DMP-30).

[0038] According to some preferred embodiments, the polyamide curing agent is mixed by polyamide epoxy curing agent 5140 and polyamide epoxy curing agent 2636 in a mass ratio of 4:(1-3).

[0039] According to some preferred embodiments, the water phase filler comprises hydrophilic fumed silica, precipitated silica, nano-titanium dioxide and water in a mass ratio of (15-25):(5-15):(5-15):(20-30); the particle size of the hydrophilic fumed silica, the precipitated silica and the nano-titanium dioxide is not specifically limited in the present application and can be routinely selected by those skilled in the art; in the present application, the hydrophilic fumed silica is of type HDK T30, the precipitated silica is of type ZEODENT 103 and the nano-titanium dioxide is of type R-FC5.

[0040] The present application provides in a second aspect a method for preparing the epoxy resin material for resin mold as described in the first aspect of the present application, the method comprising the following steps:

[0041] (1) mixing the hydrophilic fumed silica, the precipitated silica and the nano-titanium dioxide with water to obtain a water phase filler;

[0042] (2) mixing the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, the polyamide curing agent, the trirhodamine epoxy curing agent and the accelerator uniformly, then adding the water phase filler and mixing uniformly to obtain the epoxy resin material for resin mold.

[0043] According to some preferred embodiments, in step (1) and / or step (2), the uniform mixing is performed by stirring at a rotation speed of 400-800 r / min.

[0044] According to some specific embodiments, the preparation of the epoxy resin material for resin mold comprises:

[0045] (1) preparation of the water phase filler: adding the hydrophilic fumed silica, the precipitated silica and the nano-titanium dioxide into water gradually and stirring at a rotation speed of 600 r / min until all the inorganic particles are uniformly dispersed to form a uniform suspension, thereby obtaining the water phase filler;

[0046] (2) mixing the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, the polyamide curing agent, the trirhodamine epoxy curing agent and the accelerator uniformly at a rotation speed of 600 r / min to obtain a resin phase, then adding the water phase filler into the resin phase at a rotation speed of 600 r / min and continuing to mix uniformly, thereby obtaining the epoxy resin material for resin mold; in the present application, the operations of step (1) and step (2) are performed at room temperature of 25°C.

[0047] The present application provides, in a third aspect, a use of the resin mold epoxy material described in the first aspect of the present application or the resin mold epoxy material prepared by the preparation method described in the second aspect of the present application in preparing a resin mold; the resin mold is cured by using the resin mold epoxy material, specifically, when the resin mold is prepared by using the resin mold epoxy material, the resin mold epoxy material can be placed in a forming mold designed according to the structure of the resin mold in advance (a layer of release agent is uniformly coated on the inner surface of the forming mold in advance), then after curing and demolding, the resin mold can be prepared; the curing is first curing at 30-40℃ for 10-15h, and then curing at 110-130℃ for 1-3h, which is beneficial to make the trirhodamine epoxy curing agent more fully participate in the reaction of the epoxy resin, so as to more effectively improve the crosslinking density of the epoxy resin, and is beneficial to improve the hardness and bending strength of the resin mold.

[0048] The present application will be further described below by way of examples, but the protection scope of the present application is not limited to these examples.

[0049] In the following examples and comparative examples, the hydrophilic fumed silica used is HDK T30, the precipitated white carbon black used is ZEODENT 103, and the nano titanium dioxide used is R-FC5.

[0050] Example 1

[0051] ①Trirhodamine based on triphenylamine and ethylenediamine were mixed uniformly according to a molar ratio of 1:8 and reacted at 160℃ for 12h, then the obtained filter cake was washed with distilled water for three times using a Buchner funnel, and finally placed in a vacuum drying oven at 60℃ for 12h, thereby preparing a trirhodamine epoxy curing agent.

[0052] hydrophilic fumed silica, precipitated white carbon black and nano titanium dioxide are mixed uniformly under the condition of 600 r / min, to obtain the water phase filler, wherein the mass ratio of the hydrophilic fumed silica, the precipitated white carbon black, the nano titanium dioxide and the water is 20:10:10:25; the bisphenol A type epoxy resin (E51 liquid epoxy resin), the bisphenol F type epoxy resin (Epikote 862 liquid bisphenol F type epoxy resin), the polyamide curing agent, the trirhodamine epoxy curing agent obtained in step 1 and the accelerator DMP-30 are mixed uniformly under the condition of 600 r / min according to the mass ratio of 10:5:6:1:1 to obtain the resin phase, and the water phase filler is added into the resin phase under the condition of 600 r / min and then mixed uniformly under the condition of 600 r / min to obtain the epoxy resin material for resin mold; wherein the polyamide curing agent is obtained by mixing the polyamide epoxy curing agent 5140 and the polyamide epoxy curing agent 2636 according to the mass ratio of 4:2; the mass ratio of the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, the polyamide curing agent, the trirhodamine epoxy curing agent, the accelerator DMP-30 and the water phase filler is 10:5:6:1:1:65.

[0053] In this example, the epoxy resin material for resin mold is first cured at 35℃ for 12h and then cured at 120℃ for 2h to obtain the cured sample of the epoxy resin material for resin mold, and the bending strength, the Shore hardness and the stress-induced fluorescence color change characteristics are tested, and the results are shown in Table 1; in the test process of the stress-induced fluorescence color change characteristics of the epoxy resin material for resin mold in this example, the tablet press is used to apply a stress of 7MPa to the sample for 5min, and the color change of the sample under the irradiation of ultraviolet light (ultraviolet light wavelength 365nm) is recorded, which directly shows the stress distribution and change of the sample during the stress process, and the results are shown in Figure 1 Figure 1 From the figures (a) and (b) of

[0054] Example 2

[0055] Example 2 is basically the same as Example 1, except that:

[0056] ​hydrophilic fumed silica, precipitated white carbon black and nano titanium dioxide are mixed uniformly under the condition of 600 r / min, to obtain the water phase filler, wherein the mass ratio of the hydrophilic fumed silica, the precipitated white carbon black, the nano titanium dioxide and water is 20:10:10:25; the bisphenol A type epoxy resin (E51 liquid epoxy resin), the bisphenol F type epoxy resin (Epikote 862 liquid bisphenol F type epoxy resin), the polyamide curing agent, the trirhodamine epoxy curing agent obtained in step 1 and the accelerator DMP-30 are mixed uniformly under the condition of 600 r / min according to the mass ratio of 10:5:6:0.6:1, to obtain the resin phase; the water phase filler is added into the resin phase under the condition of 600 r / min and is continuously mixed uniformly under the condition of 600 r / min, to obtain the epoxy resin material for resin mold; wherein the polyamide curing agent is obtained by mixing the polyamide epoxy curing agent 5140 and the polyamide epoxy curing agent 2636 according to the mass ratio of 4:2; the mass ratio of the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, the polyamide curing agent, the trirhodamine epoxy curing agent, the accelerator DMP-30 and the water phase filler is 10:5:6:0.6:1:65.

[0057] In this example, the epoxy resin material for resin mold is first cured at 35℃ for 12 h and then cured at 120℃ for 2 h, to obtain the cured sample of the epoxy resin material for resin mold, and the bending strength, the Shore hardness and the fluorescence color change characteristics caused by force of the cured sample are tested, and the results are shown in Table 1.

[0058] Example 3

[0059] Example 3 is basically the same as Example 1, except that:

[0060] ② Hydrophilic fumed silica, precipitated white carbon black and nano titanium dioxide were mixed uniformly under the condition of 600 r / min using water as the phase, wherein the mass ratio of hydrophilic fumed silica, precipitated white carbon black, nano titanium dioxide and water was 20:10:10:25; bisphenol A type epoxy resin (E51 liquid epoxy resin), bisphenol F type epoxy resin (Epikote 862 liquid bisphenol F type epoxy resin), polyamide curing agent, the trirhodamine epoxy curing agent obtained in step ① and accelerator DMP-30 were mixed uniformly under the condition of 600 r / min according to the mass ratio of 10:5:6:2:1 to obtain the resin phase, and the water phase filler was added to the resin phase under the condition of 600 r / min and then mixed uniformly under the condition of 600 r / min to obtain the epoxy resin material for resin mold; wherein the polyamide curing agent was obtained by mixing polyamide epoxy curing agent 5140 and polyamide epoxy curing agent 2636 according to the mass ratio of 4:2; the mass ratio of bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyamide curing agent, trirhodamine epoxy curing agent, accelerator DMP-30 and water phase filler was 10:5:6:2:1:65.

[0061] In this example, the epoxy resin material for resin mold was first cured at 35℃ for 12h and then cured at 120℃ for 2h to obtain the cured sample of the epoxy resin material for resin mold, and the bending strength, Shore hardness and the fluorescence color change characteristics caused by force were tested, and the results are shown in Table 1.

[0062] Example 4

[0063] ① The trirhodamine based on triphenylamine was mixed with ethylenediamine according to the molar ratio of 1:8, and then reacted at 160℃ for 12h, and then the filter cake was washed with distilled water for three times using a Buchner funnel, and finally dried at 60℃ under vacuum for 12h to obtain the trirhodamine epoxy curing agent.

[0064] hydrophilic fumed silica, precipitated white carbon black and nano titanium dioxide are stirred and mixed uniformly at a rotation speed of 600 r / min to obtain the water phase filler, wherein the mass ratio of the hydrophilic fumed silica, the precipitated white carbon black, the nano titanium dioxide and water is 20:10:10:25; the bisphenol A type epoxy resin (E51 liquid epoxy resin), the bisphenol F type epoxy resin (Epikote 862 liquid bisphenol F type epoxy resin), the polyamide curing agent, the trirhodamine epoxy curing agent obtained in step 1 and the accelerator DMP-30 are stirred and mixed uniformly at a rotation speed of 600 r / min according to a mass ratio of 10:5:6:1:1 to obtain the resin phase, the water phase filler is added into the resin phase under the condition of a rotation speed of 600 r / min and the stirring and mixing are continued at a rotation speed of 600 r / min to obtain the epoxy resin material for resin mold; wherein the polyamide curing agent is obtained by mixing the polyamide epoxy curing agent 5140 and the polyamide epoxy curing agent 2636 according to a mass ratio of 4:2; the mass ratio of the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, the polyamide curing agent, the trirhodamine epoxy curing agent, the accelerator DMP-30 and the water phase filler is 10:5:6:1:1:65.

[0065] In this example, the epoxy resin material for resin mold is cured at 35℃ for 12h to obtain the cured sample of the epoxy resin material for resin mold, and the bending strength, Shore hardness and the force-induced fluorescence color change characteristics of the cured sample are tested, and the results are shown in Table 1.

[0066] Comparative Example 1

[0067] hydrophilic fumed silica, precipitated white carbon black and nano titanium dioxide are stirred and mixed uniformly at a rotation speed of 600 r / min to obtain the water phase filler, wherein the mass ratio of the hydrophilic fumed silica, the precipitated white carbon black, the nano titanium dioxide and water is 20:10:10:25; the bisphenol A type epoxy resin (E51 liquid epoxy resin), the bisphenol F type epoxy resin (Epikote 862 liquid bisphenol F type epoxy resin), the polyamide curing agent, the trirhodamine epoxy curing agent obtained in step 1 and the accelerator DMP-30 are stirred and mixed uniformly at a rotation speed of 600 r / min according to a mass ratio of 10:5:6:1:1 to obtain the resin phase, the water phase filler is added into the resin phase under the condition of a rotation speed of 600 r / min and the stirring and mixing are continued at a rotation speed of 600 r / min to obtain the epoxy resin material for resin mold; wherein the polyamide curing agent is obtained by mixing the polyamide epoxy curing agent 5140 and the polyamide epoxy curing agent 2636 according to a mass ratio of 4:2; the mass ratio of the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, the polyamide curing agent, the trirhodamine epoxy curing agent, the accelerator DMP-30 and the water phase filler is 10:5:6:1:1:65.

[0068] The resin mold epoxy material was first cured at 35℃ for 12h, and then cured at 120℃ for 2h to obtain a cured sample of the resin mold epoxy material, and the bending strength, Shore hardness and force-induced fluorescence color change characteristics were tested, and the results are shown in Table 1.

[0069] Comparative Example 2

[0070] The hydrophilic fumed silica, precipitated white carbon black and nano titanium dioxide were mixed uniformly under stirring at a rotation speed of 600r / min with water to obtain an aqueous phase filler, wherein the mass ratio of the hydrophilic fumed silica, precipitated white carbon black, nano titanium dioxide and water was 20:10:10:25; the bisphenol A type epoxy resin (E51 liquid epoxy resin), bisphenol F type epoxy resin (Epikote 862 liquid bisphenol F type epoxy resin), polyamide curing agent, ethylenediamine and accelerator DMP-30 were mixed uniformly under stirring at a rotation speed of 600r / min according to a mass ratio of 10:5:6:1:1 to obtain a resin phase, and the aqueous phase filler was added to the resin phase under stirring at a rotation speed of 600r / min and mixed uniformly under stirring at a rotation speed of 600r / min to obtain a resin mold epoxy material; wherein the polyamide curing agent was mixed according to a mass ratio of 4:2 from polyamide epoxy curing agent 5140 and polyamide epoxy curing agent 2636; the mass ratio of the bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyamide curing agent, ethylenediamine, accelerator DMP-30 and aqueous phase filler was 10:5:6:1:1:65.

[0071] The resin mold epoxy material was first cured at 35℃ for 12h, and then cured at 120℃ for 2h to obtain a cured sample of the resin mold epoxy material, and the bending strength, Shore hardness and force-induced fluorescence color change characteristics were tested, and the results are shown in Table 1.

[0072] Comparative Example 3

[0073] The hydrophilic fumed silica, the precipitated white carbon black and the nano titanium dioxide were mixed uniformly under stirring at a rotation speed of 600 r / min with water to obtain the water phase filler, wherein the mass ratio of the hydrophilic fumed silica, the precipitated white carbon black, the nano titanium dioxide and water was 20:10:10:25; the bisphenol A type epoxy resin (E51 liquid epoxy resin), the bisphenol F type epoxy resin (Epikote 862 liquid bisphenol F type epoxy resin), the polyamide curing agent, the tri-rhodamine based on triphenylamine and the accelerator DMP-30 were mixed uniformly under stirring at a rotation speed of 600 r / min according to a mass ratio of 10:5:6:1:1 to obtain the resin phase, the water phase filler was added into the resin phase under stirring at a rotation speed of 600 r / min and the mixture was continuously stirred at a rotation speed of 600 r / min to obtain the resin mold epoxy resin material; wherein the polyamide curing agent was obtained by mixing the polyamide epoxy curing agent 5140 and the polyamide epoxy curing agent 2636 according to a mass ratio of 4:2; the mass ratio of the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, the polyamide curing agent, the tri-rhodamine based on triphenylamine, the accelerator DMP-30 and the water phase filler was 10:5:6:1:1:65.

[0074] The resin mold epoxy resin material was cured at 35℃ for 12h to obtain a resin mold epoxy resin material cured sample, and the bending strength, Shore hardness and force-induced fluorescence color change characteristics of the sample were tested, and the results are shown in Table 1.

[0075] Comparative Example 4

[0076] ①The trimesoyl chloride and rhodamine B hydrazide were added to dichloromethane and reacted at 85℃ for 8h; after the reaction was completed, the product (pink solid trimesorhodamine amide) was obtained by column chromatography (petroleum ether: ethyl acetate volume ratio of 10:1); wherein the molar ratio of trimesoyl chloride, rhodamine B hydrazide and dichloromethane was 1:4:780.

[0077] hydrophilic fumed silica, precipitated white carbon black and nano titanium dioxide are stirred and mixed uniformly at a rotation speed of 600 r / min to obtain the water phase filler, wherein the mass ratio of the hydrophilic fumed silica, the precipitated white carbon black, the nano titanium dioxide and water is 20:10:10:25; the bisphenol A type epoxy resin (E51 liquid epoxy resin), the bisphenol F type epoxy resin (Epikote 862 liquid bisphenol F type epoxy resin), the polyamide curing agent, the tris-rhodamine amide obtained in step 1 and the accelerator DMP-30 are stirred and mixed uniformly at a rotation speed of 600 r / min according to a mass ratio of 10:5:6:1:1 to obtain the resin phase, the water phase filler is added into the resin phase under the condition of a rotation speed of 600 r / min and the stirring and mixing are continued at a rotation speed of 600 r / min to obtain the epoxy resin material for resin mold; wherein the polyamide curing agent is obtained by mixing the polyamide epoxy curing agent 5140 and the polyamide epoxy curing agent 2636 according to a mass ratio of 4:2; the mass ratio of the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, the polyamide curing agent, the tris-rhodamine amide, the accelerator DMP-30 and the water phase filler is 10:5:6:1:1:65.

[0078] The epoxy resin material for resin mold obtained in the example is cured at 35℃ for 12 h to obtain a cured sample of the epoxy resin material for resin mold, and the flexural strength, the Shore hardness and the stress-induced fluorescence color change characteristics of the cured sample are tested, and the results are shown in Table 1.

[0079] Comparative Example 5

[0080] hydrophilic fumed silica, precipitated white carbon black and nano titanium dioxide are stirred and mixed uniformly at a rotation speed of 600 r / min to obtain the water phase filler, wherein the mass ratio of the hydrophilic fumed silica, the precipitated white carbon black, the nano titanium dioxide and water is 20:10:10:25; the bisphenol A type epoxy resin (E51 liquid epoxy resin), the bisphenol F type epoxy resin (Epikote 862 liquid bisphenol F type epoxy resin), the polyamide curing agent and the accelerator DMP-30 are stirred and mixed uniformly at a rotation speed of 600 r / min according to a mass ratio of 10:5:6:1 to obtain the resin phase, the water phase filler is added into the resin phase under the condition of a rotation speed of 600 r / min and the stirring and mixing are continued at a rotation speed of 600 r / min to obtain the epoxy resin material for resin mold; wherein the polyamide curing agent is obtained by mixing the polyamide epoxy curing agent 5140 and the polyamide epoxy curing agent 2636 according to a mass ratio of 4:2; the mass ratio of the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, the polyamide curing agent, the accelerator DMP-30 and the water phase filler is 10:5:6:1:65.

[0081] The resin mold epoxy material is cured at 35℃ for 12h to obtain a cured sample of the resin mold epoxy material, and the bending strength, Shore hardness and stress-induced fluorescence color change characteristics of the cured sample are tested, and the results are shown in Table 1.

[0082] Table 1

[0083]

[0084] As can be seen from the data in Table 1, the resin mold epoxy material prepared by using the trirhodamine epoxy curing agent has the stress-induced fluorescence color change (stress response) characteristics, which can realize the intuitive monitoring of stress during the use of the resin mold epoxy material, so that the operator can identify and monitor the stress damage of the resin mold epoxy material in real time, thereby optimizing the product quality and safety, and the trirhodamine epoxy curing agent also helps to improve the overall mechanical properties of the epoxy resin composite; the bending strength of the resin mold epoxy material prepared by using the trirhodamine epoxy curing agent in the embodiment of the present application is as high as 12MPa or more, indicating that it has good structural integrity and bending resistance when subjected to external pressure, indicating that the resin mold epoxy material has high toughness, and the hardness is as high as 61D or more, indicating that the material has high hardness and wear resistance, and is suitable for manufacturing ceramic molds for bearing large mechanical loads; in the preferred embodiment of the present application, the bending strength of the prepared resin mold epoxy material can even reach 14MPa or more, and the hardness can reach 70D or more.

[0085] The part of the present application not described in detail is the technology known to those skilled in the art.

[0086] Finally, it should be pointed out that: the above embodiments are only used to illustrate the technical solutions of the present application, and not to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacement for part of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. An epoxy resin material for resin molds, characterized in that, The epoxy resin material for the resin mold comprises bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyamide curing agent, trolidine epoxy curing agent, accelerator, and aqueous filler; the mass ratio of the bisphenol A type epoxy resin, the bisphenol F type epoxy resin, the polyamide curing agent, the trolidine epoxy curing agent, the accelerator, and the aqueous filler is 10:(2~8):(3~8):(0.5~2):(0.5~2):(50~80); the aqueous filler comprises hydrophilic fumed silica, precipitated silica, nano titanium dioxide, and water in a mass ratio of (15~25):(5~15):(5~15):(20~30). The preparation of the trirodamine epoxy curing agent is as follows: trirodamine based on triphenylamine is mixed evenly with ethylenediamine and reacted at 150~170℃ for 10~18h. After filtration, washing and drying, the trirodamine epoxy curing agent is obtained.

2. The epoxy resin material for resin molds according to claim 1, characterized in that: The epoxy resin material used for the resin mold is cured as follows: first at 30~40℃ for 10~15h, and then at 110~130℃ for 1~3h.

3. The epoxy resin material for resin molds according to claim 1, characterized in that: The molar ratio of trirodamine based on triphenylamine to ethylenediamine is 1:(5~20).

4. The epoxy resin material for resin molds according to claim 1, characterized in that: The mass ratio of the polyamide curing agent to the trirodamine epoxy curing agent is (4~8):

1.

5. The epoxy resin material for resin molds according to claim 1, characterized in that: The bisphenol A type epoxy resin is E51 liquid epoxy resin; The bisphenol F epoxy resin is Epikote 862 liquid bisphenol F epoxy resin; The polyamide curing agent is polyamide epoxy curing agent 5140 and / or polyamide epoxy curing agent 2636; and / or The accelerator is 2,4,6-tris(dimethylaminomethyl)phenol.

6. A method for preparing the epoxy resin material for resin molds according to any one of claims 1 to 5, characterized in that, The method includes the following steps: (1) Use water to mix hydrophilic fumed silica, precipitated silica and nano titanium dioxide evenly to obtain aqueous filler; (2) Mix bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyamide curing agent, trirodamine epoxy curing agent and accelerator evenly, then add aqueous filler and mix evenly to obtain epoxy resin material for resin mold.

7. The preparation method according to claim 6, characterized in that: In step (1) and / or step (2), the mixing is carried out by stirring at a speed of 400~800 r / min.

8. The use of the epoxy resin material for resin molds according to any one of claims 1 to 5, or the epoxy resin material for resin molds prepared by the preparation method according to claim 6 or 7, in the preparation of resin molds.

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