A self-toughened epoxy resin with high temperature resistance and a preparation method thereof

Abstract

The present application belongs to the field of polymer materials, and particularly relates to a self-toughened epoxy resin with high temperature resistance and a preparation method thereof. The modifier is a multifunctional epoxy resin containing a polyetherimide structure. The modifier is dissolved and blended with a bisphenol A type epoxy resin. The curing agent comprises one or more of methyl nadic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, dodecenyl succinic anhydride and pyromellitic anhydride. The curing accelerator comprises one or more of dimethylaminomethylphenol, ortho-hydroxybenzyl dimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, triethylamine and triethanolamine. The multifunctional epoxy resin containing a polyetherimide structure not only has good solubility in the bisphenol A type epoxy resin, but also can participate in the curing reaction of the bisphenol A type epoxy resin, so that the toughness and temperature resistance of the bisphenol A type epoxy resin can be significantly improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of high polymer materials, and particularly relates to a self-toughened epoxy resin with high temperature resistance and a preparation method thereof. BACKGROUND

[0002] Epoxy resin is a kind of low molecular weight compound containing two or more high activity epoxy groups in the molecule. Because of its good chemical stability, mechanical properties, adhesion, insulation and UV aging resistance, it can be used as a resin matrix for composite materials, coatings, adhesives and other resins, and is widely used in shipbuilding, aerospace, microelectronics, electrical, automotive, machinery and other fields, and plays an important role in the development of national economy. The bisphenol A type epoxy resin (such as E44, E51, etc.) commonly used in the domestic market is dense in crosslinked network after curing and crosslinking, and has high internal stress, resulting in high brittleness, easy cracking and poor wear resistance. In addition, the glass transition temperature of the bisphenol A type epoxy resin of the conventional curing system (such as ordinary amine or acid anhydride curing) is usually in the range of 80-100℃, and the temperature resistance is limited, which is difficult to meet the high temperature application requirements (such as aerospace, electronic packaging and other fields). Therefore, improving the heat resistance and toughness of the general bisphenol A epoxy resin has always been a research hotspot in the industry and academia.

[0003] However, the method commonly used by the industry to toughen the epoxy resin is to add reactive liquid rubber, such as carboxyl-terminated nitrile rubber, hydroxyl-terminated nitrile rubber, hydroxyl-terminated polybutadiene, etc., to the epoxy system. During the curing reaction, these reactive liquid rubbers participate in the curing reaction, thereby playing a toughening modification role. Although these liquid rubbers have good toughening effect, they reduce the temperature resistance of the epoxy resin. In order to balance the toughness and temperature resistance of the epoxy resin, researchers use the method of physical blending to add high temperature resistant resins to the epoxy resin system, such as polyaryletherketone, polyimide, polyphenyl ether, polyurethane, polyether sulfone, hyperbranched polymer and other special engineering plastics. However, the compatibility of these special materials with bisphenol A type epoxy resin is not good, and it is necessary to add appropriate organic solvents to dissolve and blend them with epoxy resin. In the processing process, the organic solvent also needs to be removed, which leads to complicated process procedures, increased manufacturing cost and environmental pollution, thereby limiting the application of this method. Therefore, it is necessary to design a self-toughened epoxy resin with high temperature resistance and a preparation method to solve the above problems. SUMMARY

[0004] In view of the above problems, the present application provides a self-toughened epoxy resin with high temperature resistance and a preparation method thereof to solve the problems raised in the background art.

[0005] To achieve the above purpose, the present application provides the following technical scheme: a self-toughened epoxy resin with high temperature resistance, comprising:

[0006] a modifier, the modifier being configured to contain a polyetherimide structure;

[0007] a bisphenol A type epoxy resin, the modifier being dissolved and blended with the bisphenol A type epoxy resin.

[0008] Further, the polyetherimide structure containing multifunctional epoxy resin has at least one structure as shown in the formula:

[0009] ;

[0010] ;

[0011] ;

[0012] ;

[0013] ;

[0014] ;

[0015] ;

[0016] ;

[0017] ;

[0018] ;

[0019] ;

[0020] ;

[0021] wherein n = 0-5.

[0022] Further, the bisphenol A type epoxy resin comprises:

[0023] one or more of E-31, E-35, E-42, E-44, E-51, E-54.

[0024] Further, the mass ratio of the modifier to the bisphenol A type epoxy resin is: 10-40: 60-90.

[0025] Further, the self-toughened epoxy resin with high temperature resistance further comprises:

[0026] a curing agent, the curing agent comprising one or more of methyl nadic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, dodecenyl succinic anhydride, pyromellitic anhydride.

[0027] Further, the self-toughened epoxy resin with high temperature resistance further comprises:

[0028] A curing accelerator, the curing accelerator comprising one or more of dimethylaminomethylphenol, ortho-hydroxybenzyl dimethylamine (DMP-10), 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), triethylamine, and triethanolamine.

[0029] Further, the amount of substance of the curing agent is 0.85-1 of the amount of substance of the epoxy groups in the modifier and the bisphenol A type epoxy resin.

[0030] The application further provides a preparation method of the self-toughened epoxy resin with high temperature resistance, for preparing the self-toughened epoxy resin with high temperature resistance as described above, comprising the following steps:

[0031] Step S1, placing the epoxy resin and the modifier in a glass instrument in proportion, and ultrasonically forming a homogeneous transparent solution;

[0032] Step S2, placing the glass instrument in a 60℃ vacuum drying box to remove air and moisture in the glass instrument for 60 min;

[0033] Step S3, adding the curing agent and the curing accelerator to the transparent solution and stirring uniformly to obtain a liquid mixture;

[0034] Step S4, preheating a unidirectional composite material mold in a 80℃ vacuum drying box;

[0035] Step S5, placing the liquid mixture in the preheated unidirectional composite material mold, and after closing the mold, heating to a curing temperature for curing;

[0036] Step S6, after the curing is completed, naturally cooling to room temperature, demolding, and taking out the prepared sample.

[0037] Further, the curing temperature is heating to 100-120℃ for 2 hours, then heating to 130-150℃ for 2 hours, and then heating to 150-180℃ for 2 hours.

[0038] The application has the following technical effects and advantages:

[0039] The multifunctional epoxy resin containing a polyetherimide structure as the modifier not only has good solubility in the bisphenol A type epoxy resin, but also can participate in the curing reaction of the bisphenol A type epoxy resin, and can significantly improve the toughness and temperature resistance of the bisphenol A type epoxy resin.

[0040] Additional features and advantages of the present application will be set forth in the description that follows, and in part will be apparent from the description, or can be learned by practice of the present application. The objectives and other advantages of the present application will be realized and attained by the structure particularly pointed out in the written description and claims thereof as well as the appended drawings. BRIEF DESCRIPTION OF DRAWINGS

[0041] In order to more clearly illustrate the technical solutions of the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or the prior art description will be briefly introduced as follows. Obviously, the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative effort on the basis of these drawings.

[0042] Figure 1 A structural schematic diagram of a multifunctional epoxy resin containing a polyetherimide structure of an embodiment of the present application is shown;

[0043] Figure 2 A glass transition temperature spectrum of an epoxy resin cured product of embodiment 1 of the present application is shown;

[0044] Figure 3 A flow chart of a preparation method of a self-toughened high-temperature-resistant epoxy resin of an embodiment of the present application is shown. DETAILED DESCRIPTION

[0045] In order to make the objectives, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be described clearly and completely in the following with reference to the drawings of the embodiments of the present application. Obviously, the described embodiments are some embodiments of the present application, but not all the embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without creative effort fall within the scope of protection of the present application.

[0046] A self-toughened high-temperature-resistant epoxy resin of an embodiment of the present application comprises a modifier and a bisphenol A type epoxy resin. The modifier is a multifunctional epoxy resin containing a polyetherimide structure. The modifier is dissolved and blended with the bisphenol A type epoxy resin.

[0047] As shown in the formula, the multifunctional epoxy resin containing a polyetherimide structure has at least one structure as shown in the formula: Figure 1

[0048]

[0049]

[0050] ​​​​

[0051] ;

[0052] ;

[0053] ;

[0054] ;

[0055] ;

[0056] ;

[0057] ;

[0058] ;

[0059] ;

[0060] wherein n = 0-5.

[0061] In the present embodiment, the multifunctional epoxy resin containing polyetherimide structure can be synthesized by the following way: taking p-aminophenol or 4-aminobenzene-1,2-diol as the starting material, first dissolving it with m-phenylenediamine in an organic solvent to form a uniform transparent brownish solution, then slowly adding dianhydride under nitrogen protection to react, and after treatment, a phenolic hydroxyl-terminated polyetherimide intermediate is obtained; then, the intermediate is added to epichlorohydrin with a catalyst, and an etherification reaction is carried out at a specific temperature to obtain an etherified phenolic hydroxyl-terminated polyetherimide; then NaOH solution is added dropwise to the etherification product, and the reaction is continued at a certain temperature to generate an epoxy group through ring closure reaction; finally, the reaction liquid is treated to obtain a multifunctional epoxy resin containing polyetherimide structure.

[0062] Specifically, the synthesis process of the multifunctional epoxy resin containing polyetherimide structure in the present embodiment is shown in the following schematic diagram:

[0063] .

[0064] AR has a structure as shown in formula I to formula VI:

[0065] , formula I;

[0066] , formula II;

[0067] , formula III;

[0068] , formula IV;

[0069] , Formula V;

[0070] , Formula VI.

[0071] The polyetherimide-containing multifunctional epoxy resin (modifier (A) of the present application) synthesized using 4-aminophenol as a raw material is synthesized as follows: Figure 1 The synthesis process of Formula 1 (n=0) in the above formula is as follows:

[0072] Into a flask, 32.7 g (0.3 mol) of p-aminophenol and 332 g of N,N-dimethylacetamide were sequentially added and dissolved by stirring at room temperature. Under nitrogen atmosphere, 78 g (0.15 mol) of dianhydride (Formula I) was slowly added to the system, and 42 mL of toluene was added. Subsequently, the reaction system was warmed to 150°C, and reacted for 8 hours. After the reaction was completed, the temperature was lowered to room temperature, and the mixture was poured into a large amount of anhydrous ethanol, and a large amount of yellow product was precipitated. The product was washed with water several times, and dried at 80°C to obtain a diphenol containing a polyetherimide structure.

[0073] Into a flask, 28.12 g (0.04 mol) of the diphenol containing a polyetherimide structure synthesized above, 1.28 g (0.004 mol) of tetrabutylammonium bromide, and 92.52 g (0.96 mol) of epichlorohydrin were added. The reaction system was warmed to 65°C, and maintained for 5 hours. Subsequently, the temperature was lowered to 50°C, and a base solution prepared by dissolving 3.52 g (0.088 mol) of 20% sodium hydroxide solution in 14.08 g of water was slowly added dropwise, and the reaction was continued at 50°C for 3 hours. After the reaction was completed, the reaction system was washed with distilled water several times, and a powder-like solid was precipitated. The solid was washed with ethanol twice, and dried to obtain a polyetherimide- containing multifunctional epoxy resin, with a yield of 90%.

[0074] The polyetherimide-containing multifunctional epoxy resin (modifier (A) of the present application) synthesized using 4-aminophenol as a raw material is synthesized as follows: Figure 1 The synthesis process of Formula 8 (n=0) in the above formula is as follows:

[0075] Into a flask, 41.74 g (0.3 mol) of 4-aminophenol-1,2-diol and 359 g of N,N-dimethylacetamide were sequentially added and dissolved by stirring at room temperature. Under nitrogen atmosphere, 78 g (0.15 mol) of dianhydride (Formula I) was slowly added to the system, and 45 mL of toluene was added. Subsequently, the reaction system was warmed to 150°C, and reacted for 8 hours. After the reaction was completed, the temperature was lowered to room temperature, and the mixture was poured into a large amount of anhydrous ethanol, and a large amount of yellow product was precipitated. The product was washed with water several times, and dried at 80°C to obtain a tetraphenol containing a polyetherimide structure.

[0076] The above-synthesized tetraol 29.36 g (0.04 mol) containing polyetherimide structure, tetrabutylammonium bromide 1.28 g (0.004 mol) and epichlorohydrin 92.52 g (0.96 mol) were added into a flask. The reaction system was heated to 65°C and maintained for 5 hours. Then, the temperature was lowered to 50°C, and a base solution prepared from 3.52 g (0.088 mol) of 20% sodium hydroxide solution and 14.08 g of water was slowly added dropwise, and the reaction was continued at 50°C for 3 hours. After the reaction was completed, the reaction system was washed with distilled water several times, and a powdery solid was precipitated. The solid was washed with ethanol twice, and after drying, a multifunctional epoxy resin containing polyetherimide structure was obtained with a yield of 86%.

[0077] Alternatively, the bisphenol A type epoxy resin comprises:

[0078] one or more of E-31, E-35, E-42, E-44, E-51, E-54.

[0079] In this embodiment, the bisphenol A type epoxy resin is an epoxy resin capable of modification, which can be one or several of commercially available general-purpose bisphenol A type epoxy resins such as E-31, E-35, E-42, E-44, E-51, E-54, etc.

[0080] Alternatively, the mass ratio of the modifier to the bisphenol A type epoxy resin is 10-40:60-90.

[0081] Alternatively, the self-toughening and high-temperature resistant epoxy resin further comprises:

[0082] The curing agent comprises one or more of methyl nadic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, dodecenyl succinic anhydride, pyromellitic anhydride.

[0083] In this embodiment, the curing agent can be one or several of curing agents such as methyl nadic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, dodecenyl succinic anhydride, pyromellitic anhydride, etc.

[0084] Alternatively, the self-toughening and high-temperature resistant epoxy resin further comprises:

[0085] The curing accelerator comprises one or more of dimethylaminomethylphenol, ortho-hydroxybenzyl dimethylamine (DMP-10), 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), triethylamine, triethanolamine.

[0086] In the embodiment, the curing accelerator is one or more of dimethylaminomethylphenol, ortho-hydroxybenzyl dimethylamine (DMP-10), 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), triethylamine, triethanolamine, and the like.

[0087] Optionally, the amount of substance of the curing agent is 0.85-1 of the amount of substance of the epoxy groups in the modifier and the bisphenol A type epoxy resin.

[0088] In the embodiment, the amount of substance of the curing agent is 0.85-1 of the amount of substance of all the epoxy groups in the modifier and the bisphenol A type epoxy resin. The mass of the epoxy groups in the modifier and the bisphenol A type epoxy resin and the mass of the curing agent can be obtained by calculation and measurement.

[0089] As shown in Figure 3 Another embodiment of the present application discloses a preparation method of a self-toughened high-temperature-resistant epoxy resin, for preparing the self-toughened high-temperature-resistant epoxy resin as described above, comprising the following steps:

[0090] Step S1, placing the epoxy resin and the modifier in a glass instrument in proportion, and ultrasonically forming a homogeneous transparent solution;

[0091] Step S2, placing the glass instrument in a 60℃ vacuum drying box to extract bubbles for 60 min, so as to remove the air and moisture in the glass instrument;

[0092] Step S3, adding the curing agent and the curing accelerator to the transparent solution and stirring uniformly to obtain a liquid mixture;

[0093] Step S4, preheating a unidirectional composite material mold in a 80℃ vacuum drying box;

[0094] Step S5, placing the liquid mixture in the preheated unidirectional composite material mold, and after closing the mold, heating to a curing temperature for curing;

[0095] Step S6, after the curing is completed, naturally cooling to room temperature, demolding, and taking out the prepared sample.

[0096] Specifically, the embodiment of the present application synthesizes a series of multifunctional epoxy resins containing polyetherimide structures. In the molecular main chain of the resin, the rigid imide ring endows it with high glass transition temperature and excellent thermal stability, and the flexible ether bond significantly improves the toughness of the material by effectively absorbing stress. The synergistic effect of the two makes the resin realize the unity of temperature resistance and toughness in structure. In addition, its molecular structure design is highly compatible with bisphenol A type epoxy resin, and a homogeneous composite system can be formed without adding a solvent.

[0097] Based on this, another embodiment of the present application discloses a method for preparing a self-toughened high-temperature-resistant epoxy resin by introducing a polyetherimide structure-containing multifunctional epoxy resin into a bisphenol A type epoxy resin.

[0098] Optionally, the curing temperature is raised to 100-120 DEG C for 2 hours, then raised to 130-150 DEG C for 2 hours, and then raised to 150-180 DEG C for 2 hours.

[0099] Specifically, the modifier structure used in the embodiments 1-8 is any one of Figure 1 The embodiments are divided into two groups, one group adding the modifier and the other group not adding the modifier, and the product performances of the two groups are compared, as shown in Tables 1-4.

[0100] The specific implementation is as follows (parts by mass).

[0101] Embodiment 1:

[0102] The epoxy resin containing the modifier is prepared by using E-44 epoxy resin (epoxy value: 0.44 mol / 100g): 90 parts, the modifier (Formula 1 (n=0) in Figure 1 (epoxy value: 0.19 mol / 100g): 10 parts, methyl nadic anhydride: 63 parts and DMP-30: 1.26 parts;

[0103] The epoxy resin without the modifier is prepared by using E-44 epoxy resin: 100 parts, methyl nadic anhydride: 67 parts and DMP-30: 1.34 parts;

[0104] The curing temperature is raised to 120 DEG C for 2 hours, then raised to 140 DEG C for 2 hours, and then raised to 160 DEG C for 2 hours. Figure 2 As shown in the figure, the glass transition temperature spectrum of the epoxy resin cured product with and without the modifier is shown.

[0105] Embodiment 2:

[0106] The epoxy resin containing the modifier is prepared by using E-35 epoxy resin (epoxy value: 0.35 mol / 100g): 80 parts, the modifier (Formula 2 (n=2) in Figure 1 (epoxy value: 0.16 mol / 100g): 20 parts, methyl nadic anhydride: 47 parts and DMP-30: 0.94 parts;

[0107] An epoxy resin without a modifier was prepared using E-35 epoxy resin: 100 parts, methyl nadic anhydride: 53 parts, DMP-30: 1.06 parts.

[0108] The curing temperature was 100°C for 2 hours, 140°C for 2 hours, and 160°C for 2 hours.

[0109] Example 3:

[0110] An epoxy resin with a modifier was prepared using E-31 epoxy resin (epoxy value: 0.31 mol / 100 g): 80 parts, a modifier (Formula 3 (n=4) in the above Table 1 (epoxy value: 0.03 mol / 100 g): 20 parts, methyltetrahydrophthalic anhydride: 36 parts, and DMP-10: 0.72 parts. Figure 1 An epoxy resin without a modifier was prepared using E-31 epoxy resin: 100 parts, methyltetrahydrophthalic anhydride: 44 parts, and DMP-10: 0.88 parts.

[0111] The curing temperature was 100°C for 2 hours, 140°C for 2 hours, and 160°C for 2 hours.

[0112] Example 4:

[0113] An epoxy resin with a modifier was prepared using E-51 epoxy resin (epoxy value: 0.51 mol / 100 g): 85 parts, a modifier (Formula 4 (n=1) in the above Table 1 (epoxy value: 0.12 mol / 100 g): 15 parts, methylhexahydrophthalic anhydride: 65 parts, and DMP-10: 1.3 parts.

[0114] Figure 1 An epoxy resin without a modifier was prepared using E-51 epoxy resin: 100 parts, methylhexahydrophthalic anhydride: 73 parts, and DMP-10: 1.46 parts.

[0115] The curing temperature was 120°C for 2 hours, 140°C for 2 hours, and 180°C for 2 hours.

[0116] Example 5:

[0117] An epoxy resin with a modifier was prepared using E-54 epoxy resin (epoxy value: 0.54 mol / 100 g): 80 parts, a modifier (Formula 5 (n=0) in the above Table 1 (epoxy value: 0.18 mol / 100 g): 20 parts, methyl nadic anhydride: 71 parts, and triethanolamine: 1.42 parts.

[0118] An epoxy resin without a modifier was prepared using E-54 epoxy resin: 100 parts, methyl nadic anhydride: 71 parts, and triethanolamine: 1.42 parts. Figure 1 The curing temperature was 120°C for 2 hours, 140°C for 2 hours, and 180°C for 2 hours.​

[0119] An epoxy resin without a modifier was prepared using E-54 epoxy resin: 100 parts, methyl nadic anhydride: 82 parts, and triethanolamine: 1.64 parts.

[0120] The curing temperature was 120°C for 2 hours, 140°C for 2 hours, and 180°C for 2 hours.

[0121] Example 6:

[0122] An epoxy resin with a modifier was prepared using E-42 epoxy resin (epoxy value: 0.42 mol / 100 g): 85 parts, a modifier (Formula 6 (n=0) (epoxy value: 0.2 mol / 100 g): 15 parts, dodecenyl succinic anhydride: 88 parts, and triethanolamine: 1.76 parts. Figure 1

[0123] An epoxy resin without a modifier was prepared using E-42 epoxy resin: 100 parts, dodecenyl succinic anhydride: 95 parts, and triethanolamine: 1.9 parts.

[0124] The curing temperature was 120°C for 2 hours, 140°C for 2 hours, and 180°C for 2 hours.

[0125] Example 7:

[0126] An epoxy resin with a modifier was prepared using E-44 epoxy resin (epoxy value: 0.44 mol / 100 g): 80 parts, a modifier (Formula 7 (n=2) (epoxy value: 0.25 mol / 100 g): 20 parts, methyl tetrahydrophthalic anhydride: 57 parts, and DMP-30: 1.14 parts. Figure 1

[0127] An epoxy resin without a modifier was prepared using E-44 epoxy resin: 100 parts, methyl tetrahydrophthalic anhydride: 62 parts, and DMP-30: 1.24 parts.

[0128] The curing temperature was 120°C for 2 hours, 140°C for 2 hours, and 180°C for 2 hours.

[0129] Example 8:

[0130] An epoxy resin with a modifier was prepared using E-44 epoxy resin (epoxy value: 0.44 mol / 100 g): 90 parts, a modifier (Formula 8 (n=5) (epoxy value: 0.04 mol / 100 g): 10 parts, methyl hexahydrophthalic anhydride: 57 parts, and DMP-10: 1.14 parts. Figure 1 An epoxy resin without a modifier was prepared using E-44 epoxy resin: 100 parts, methyl hexahydrophthalic anhydride: 57 parts, and DMP-10: 1.14 parts.​​

[0131] The epoxy resin without modifier was prepared by using E-44 epoxy resin: 100 parts, methyl hexahydrophthalic anhydride: 63 parts, DMP-10: 1.26 parts;

[0132] The curing temperature was as follows: heating to 120°C for 2 hours, then heating to 140°C for 2 hours, and then heating to 180°C for 2 hours.

[0133] Preferably, the products prepared in Examples 1 to 8 of the present application were subjected to performance tests, and the results are shown in Tables 1 to 4.

[0134] Flexural property: the epoxy resin in the implementation case was modified by the following method: the epoxy resin and the modifier were placed in a glass instrument in proportion, and ultrasonic was used to form a homogeneous transparent solution. The glass instrument was placed in a 60°C vacuum drying oven for 60 min to remove the air or moisture inside. The curing agent and the curing accelerator were added to the transparent solution and stirred uniformly. Meanwhile, the unidirectional composite material mold was preheated in an 80°C vacuum drying oven. The liquid mixture stirred uniformly above was placed in the preheated mold, and after the mold was closed, the temperature was raised for curing. The curing process was as follows: heating to 100-120°C for 2 hours, then heating to 130-150°C for 2 hours, and then heating to 150-180°C for 2 hours. After curing, the sample was naturally cooled to room temperature, and the prepared sample was taken out after demolding. The sample was tested according to GB / T 3356-1999.

[0135] Flexural property: tested according to GB / T 3356-1999.

[0136] Thermodynamic property: tested according to GB / T 19466.2-2004.

[0137] Table 1: Comparison of flexural properties of epoxy resins with and without modifier

[0138] .

[0139] Table 2: Comparison of temperature resistance of epoxy resins with and without modifier

[0140] .

[0141] Table 3: Comparison of impact properties of epoxy resins with and without modifier

[0142] .

[0143] Table 4: Comparison of compression properties of epoxy resins with and without modifier

[0144] .

[0145] From the above table, it can be seen that the epoxy resin samples prepared by adding the modifier in the embodiments 1 to 8 of the present application have better toughness and high temperature resistance compared with the epoxy resin sample prepared without adding the modifier.

[0146] The process has simple formulation and is suitable for large-scale production, and the multifunctional epoxy resin containing polyetherimide structure can be used as one of the best candidate modifiers for improving the temperature resistance and toughness of commercially available general-purpose epoxy resins.

[0147] Although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that the technical solutions recorded in the foregoing embodiments can still be modified, or some of the technical features can be replaced by equivalents; 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. A high-temperature resistant and toughened epoxy resin, characterized in that, include: A modifier, wherein the modifier is configured as a multifunctional epoxy resin containing a polyetherimide structure; Bisphenol A type epoxy resin, wherein the modifier is dissolved and blended with the bisphenol A type epoxy resin; The multifunctional epoxy resin containing a polyetherimide structure has at least one structure as shown in the formula: ； ； ； ； ； ； ； ； ； ； ； ； Where n = 0-5.

2. The high-temperature resistant and toughened epoxy resin according to claim 1, characterized in that, The bisphenol A type epoxy resin includes one or more of E-31, E-35, E-42, E-44, E-51, and E-54.

3. The high-temperature resistant and toughened epoxy resin according to claim 2, characterized in that, The mass ratio of the modifier to the bisphenol A epoxy resin is 10-40:60-90.

4. The high-temperature resistant and toughened epoxy resin according to claim 3, characterized in that, Also includes: The curing agent includes one or more of methyl nadic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, dodecenyl succinic anhydride, and pyromellitic anhydride.

5. The high-temperature resistant and toughened epoxy resin according to claim 4, characterized in that, Also includes: A curing accelerator, wherein the curing accelerator comprises one or more of dimethylaminomethylphenol, o-hydroxybenzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, triethylamine, and triethanolamine.

6. The high-temperature resistant and toughened epoxy resin according to claim 5, characterized in that, The amount of the curing agent is 0.85-1 times the amount of the epoxy groups in the modifier and the bisphenol A epoxy resin.

7. A method for preparing a high-temperature resistant and toughened epoxy resin, characterized in that, The method for preparing the high-temperature toughening epoxy resin as described in any one of claims 1 to 6 comprises the following steps: Step S1: Place epoxy resin and modifier in a glass instrument in a certain proportion and sonicate to form a homogeneous transparent solution. Step S2: Place the glass instrument in a 60℃ vacuum drying oven for 60 minutes to remove air and moisture. Step S3: Add the curing agent and curing accelerator to the transparent solution and stir until homogeneous to obtain a liquid mixture; Step S4: Preheat the unidirectional composite material mold in an 80°C vacuum drying oven; Step S5: Place the liquid mixture into the preheated unidirectional composite material mold, close the mold, and then heat it to the curing temperature for curing. Step S6: After curing, allow the sample to cool naturally to room temperature, then demold and remove the prepared sample.

8. The method for preparing the high-temperature resistant and toughened epoxy resin according to claim 7, characterized in that, The curing temperature is raised to 100-120℃ and held for 2 hours, then raised to 130-150℃ and held for 2 hours, and then raised to 150-180℃ and held for 2 hours.

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