Modified epoxy resin energetic adhesive composition, modified epoxy resin energetic adhesive as well as preparation method and application of modified epoxy resin energetic adhesive

Abstract

The invention provides a modified epoxy resin energetic adhesive composition. The composition comprises the following components: an epoxy resin matrix and a curing agent, the curing agent is a first curing agent or a curing agent combination A with the number-average molecular weight not greater than 400g / mol; the curing agent composition A is a composition of any one of an alicyclic amine curing agent, an aromatic amine curing agent and a first curing agent with the number-average molecular weight of not more than 400g / mol and a second curing agent with the number-average molecular weight of not less than 600g / mol; in the composition, the mass ratio of the epoxy resin matrix to the curing agent based on the active hydrogen equivalent is 1: (0.3-0.75). The modified epoxy resin energetic adhesive prepared from the composition provided by the invention has the characteristics of good adhesive property, high structural strength, high combustion rate, sufficient combustion reaction and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of solid propellants, in particular to an energetic adhesive, a modified epoxy resin energetic adhesive composition, a modified epoxy resin energetic adhesive, and a preparation method and application thereof. Background Art

[0002] Energetic adhesives are typically made by mixing energetic compounds (such as nitroglycerin and RDX) with polymers (such as polyethers and polyesters). These adhesives not only exhibit excellent bonding properties but also release significant amounts of energy under specific conditions. Consequently, they are widely used in propellants, explosives, and high-performance composite materials.

[0003] Epoxy resins are corrosion-resistant and have excellent mechanical properties, making them widely used as matrix adhesives in composite matrices and energetic materials. While conventional epoxy resins offer excellent mechanical properties, they suffer from high oxygen balance during combustion, leading to incomplete combustion.

[0004] While traditional energetic adhesives have good combustion effects and sufficient energy release, their mechanical properties are generally poor, with tensile strengths below 10 MPa, which cannot meet structural requirements. For example, Luo Yunjun et al. (Research Progress of Energetic Thermoplastic Elastomer Propellants, Solid Rocket Technology, 2024, 47(2):143-153) reported on the various properties of a variety of common energetic thermoplastic elastomers. It can be seen from this that the tensile strength of existing energetic thermoplastic elastomers is not high, and most do not exceed 10 MPa.

[0005] Therefore, developing an energetic adhesive that has both mechanical properties and combustion properties is of great significance for promoting the industrial application of energetic adhesives. Summary of the Invention

[0006] The main purpose of the present invention is to provide a modified epoxy resin energetic adhesive composition, a modified epoxy resin energetic adhesive and a preparation method and application thereof, so as to solve the problem that existing energetic adhesives cannot have both mechanical properties and combustion effects.

[0007] To achieve the above object, the present invention provides a modified epoxy resin energetic adhesive composition, which comprises the following components: epoxy resin matrix and curing agent; The curing agent is a first curing agent or a curing agent combination A having a number average molecular weight of no more than 400 g / mol; The curing agent combination A is a combination of any one of an alicyclic amine curing agent, an aromatic amine curing agent, a first curing agent with a number average molecular weight not greater than 400 g / mol, and a second curing agent with a number average molecular weight not less than 600 g / mol; In the composition, the mass ratio of the epoxy resin matrix to the curing agent calculated on the basis of active hydrogen equivalent is 1:0.3-0.75.

[0008] Furthermore, the first curing agent has a structure represented by formula (I) or formula (II): , formula (I); in formula (I), 1≤n1<5; , formula (II); in formula (II), 2≤x1+y1+z1<6; The second curing agent has a structure represented by formula (I') or formula (II'): , formula (I'); in formula (I'), 5≤n2≤35; , formula (II'); in formula (II'), 6≤x2+y2+z2≤50.

[0009] Furthermore, the epoxy resin matrix is selected from at least one of glycidyl ether epoxy resin and glycidyl ester epoxy resin.

[0010] Furthermore, the alicyclic amine curing agent is selected from at least one of IPDA, DMDC, and HMDA.

[0011] Furthermore, the aromatic amine curing agent is selected from at least one of DDM, DDS, and MPD.

[0012] Furthermore, the composition further contains 0-5 wt% of an auxiliary agent, and the auxiliary agent is selected from at least one of a curing accelerator, an anti-aging agent and an energetic diluent.

[0013] Preferably, the curing accelerator is selected from at least one of imidazole accelerators, phenol accelerators, and substituted urea accelerators.

[0014] Preferably, the antioxidant is selected from at least one of an antioxidant, an ultraviolet absorber, and a light stabilizer.

[0015] Preferably, the energetic diluent is selected from at least one of azides, nitrates, and glycidyl ethers.

[0016] The present invention also provides a method for preparing a modified epoxy resin energetic adhesive, which comprises: sequentially contacting, mixing and curing the components in the composition.

[0017] Furthermore, the contact mixing conditions at least include: a temperature of 20-40°C.

[0018] Furthermore, the curing treatment conditions include at least: a temperature of 80-150° C. and a time of 1-12 hours.

[0019] The present invention also provides a modified epoxy resin energetic adhesive prepared by the method.

[0020] Furthermore, the modified epoxy resin energetic adhesive contains a characteristic segment of the following formula (III) or formula (IV); , formula (III); in formula (III), n' is 1-35; , formula (IV); in formula (IV), 2≤x'+y'+z'≤50.

[0021] The present invention also provides a use of the modified epoxy resin energetic adhesive in solid propellants.

[0022] Compared with the prior art, the present invention has the following beneficial effects: The composition provided by the present invention mixes an epoxy resin matrix with an amine curing agent within a specific molecular weight range in a certain proportion, thereby improving both the mechanical properties and the combustion properties of the epoxy resin, thereby obtaining an energetic adhesive having both mechanical strength and combustion properties.

[0023] The modified epoxy resin energetic adhesive prepared using the composition provided by the present invention has the characteristics of good bonding performance, high structural strength, high combustion rate, and sufficient combustion reaction. Its cured product is an epoxy resin cured product with excellent mechanical properties and combustion properties. The preparation method is simple, the operation is convenient, and it is easy to synthesize.

[0024] The modified epoxy resin energetic adhesive prepared by the invention has a wide range of uses and can be used as a matrix material of energetic composite materials and solid propellants to improve the combustion rate and reaction degree of the materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying any creative work.

[0026] Figure 1The figures are photos of the modified epoxy resin energetic adhesives prepared in the examples of the present invention after curing. Figure a shows the cured product of the modified epoxy resin energetic adhesive prepared in Example 1, figure b shows the cured product of the modified epoxy resin energetic adhesive prepared in Example 3, figure c shows the cured product of the modified epoxy resin energetic adhesive prepared in Example 5, and figure d shows the cured product of the modified epoxy resin energetic adhesive prepared in Comparative Example 2.

[0027] The realization of the objectives, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0028] The following will be combined with the accompanying drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0029] In addition, the terms "first," "second," and so on, used in this disclosure are for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Therefore, features specified as "first" or "second" may explicitly or implicitly include at least one of these features.

[0030] Moreover, the technical solutions between the various embodiments of the present invention may be combined with each other, but this must be based on the fact that ordinary technicians in this field can implement them. When the combination of technical solutions is mutually contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0031] It should be noted that the room temperature or normal temperature mentioned in the present invention refers to 25±2°C.

[0032] As mentioned above, the present invention provides a modified epoxy resin energetic adhesive composition, which comprises the following components: epoxy resin matrix and curing agent; The curing agent is a first curing agent or a curing agent combination A having a number average molecular weight of no more than 400 g / mol; The curing agent combination A is a combination of any one of an alicyclic amine curing agent, an aromatic amine curing agent, a first curing agent with a number average molecular weight not greater than 400 g / mol, and a second curing agent with a number average molecular weight not less than 600 g / mol; In the composition, the mass ratio of the epoxy resin matrix to the curing agent calculated on the basis of active hydrogen equivalent is 1:0.3-0.75.

[0033] The reaction between epoxy resin and amine curing agents is based on a chemical reaction between the epoxy groups and amine groups in the epoxy resin. This reaction is an addition reaction, forming a crosslinked structure through the bonding of epoxy and amine groups, thereby transforming the epoxy resin from a liquid to a solid thermosetting polymer. During the reaction, the amine groups (primary and secondary amines) in the amine curing agent react with the epoxy groups in the epoxy resin to form a polymer network connected by methylene bridges (-CH2-). The main chemical reaction formulas involved in the reaction are as follows:

[0034] This crosslinking reaction not only improves the material's mechanical properties but also imparts excellent thermal stability and chemical resistance. Therefore, the composition provided by the present invention, by mixing an epoxy resin matrix with an amine curing agent within a specific molecular weight range in a suitable proportion, can simultaneously improve both the mechanical and combustion properties of the epoxy resin, resulting in an energetic adhesive with both mechanical strength and combustion performance.

[0035] In some embodiments, the number average molecular weight of the first curing agent is 100-400 g / mol.

[0036] In some embodiments, the second curing agent has a number average molecular weight of 600-3000 g / mol.

[0037] In some embodiments, the first curing agent has a structure represented by formula (I) or formula (II): , formula (I); in formula (I), 1≤n1<5; , formula (II); in formula (II), 2≤x1+y1+z1<6; The second curing agent has a structure represented by formula (I') or formula (II'): , formula (I'); in formula (I'), 5≤n2≤35; , formula (II'); in formula (II'), 6≤x2+y2+z2≤50.

[0038] Through research, the inventors found that when using a short-chain polyetheramine curing agent alone (such as a number average molecular weight of no more than 400 g / mol), due to the short molecular chain of the short-chain polyetheramine curing agent, the cross-linking points formed after curing are relatively dense and the intermolecular force is relatively strong, which makes the cured product have higher tensile strength and modulus; at the same time, the short molecular chain also makes its pyrolysis product more flammable.

[0039] The inventors also unexpectedly discovered that combining other amine curing agents with long-chain polyetheramine curing agents (e.g., with a number-average molecular weight of no less than 600 g / mol) can achieve a balance between mechanical and combustion properties, resulting in better overall performance. The short-chain polyetheramine provides a higher crosslink density and strength, while the long-chain polyetheramine provides flexibility and elongation at break. While maintaining a high crosslink density, the introduction of flexible segments improves combustion performance.

[0040] In order to obtain an energetic adhesive with excellent mechanical and combustion properties, the selection of an epoxy resin matrix is also crucial. In some specific embodiments, the epoxy resin matrix is selected from at least one of a glycidyl ether epoxy resin and a glycidyl ester epoxy resin.

[0041] In some specific embodiments, the first curing agent is selected from at least one of polyetheramine D230, polyetheramine D400, and polyetheramine T403.

[0042] In some specific embodiments, the second curing agent is selected from at least one of polyetheramine T3000 and polyetheramine D2000.

[0043] According to a particularly preferred embodiment of the present invention, the alicyclic amine curing agent is at least one selected from isophorone diamine (IPDA), 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (DMDC), and 4,4'-diaminodicyclohexylmethane (HMDA). More preferably, isophorone diamine (IPDA) is used in combination with a long-chain polyetheramine curing agent. IPDA itself has a high crosslink density and flexural strength, but is also relatively brittle. Long-chain polyetheramine curing agents (such as polyetheramine T3000) provide flexibility and elongation at break. Furthermore, the addition of a long-chain polyetheramine curing agent can improve the combustion performance of the cured product to a certain extent.

[0044] According to a particularly preferred embodiment of the present invention, the aromatic amine curing agent is at least one selected from 4,4'-diaminodiphenylmethane (DDM), 4,4'-diaminodiphenylsulfone (DDS), and meta-phenylenediamine (MPD). 4,4'-diaminodiphenylmethane (DDM) is more preferred. When used in combination with a long-chain polyetheramine curing agent, a modified epoxy resin energetic adhesive cured product with excellent tensile and flammability properties can be obtained.

[0045] In order to obtain an energetic adhesive with better comprehensive performance, in some embodiments, the composition further contains 0-5 wt % of an auxiliary agent, and the auxiliary agent is selected from at least one of a curing accelerator, an antioxidant and an energetic diluent.

[0046] The primary function of a curing accelerator is to accelerate the curing reaction of energetic adhesives, lower the curing temperature, and shorten the curing time. In energetic adhesives, curing accelerators promote the chemical reaction between the epoxy resin and the curing agent, forming a crosslinked network structure, thereby improving the mechanical properties and stability of the adhesive. According to a particularly preferred embodiment of the present invention, the curing accelerator is selected from at least one of an imidazole accelerator, a phenolic accelerator, and a substituted urea accelerator.

[0047] The primary function of an antioxidant is to improve the durability and stability of energetic adhesives, preventing degradation due to oxidation, thermal degradation, or UV exposure during long-term use. Antiaging agents extend the service life of energetic adhesives by capturing free radicals, inhibiting oxidation reactions, or absorbing UV rays, thereby maintaining their mechanical and combustion properties. According to a particularly preferred embodiment of the present invention, the antioxidant is selected from at least one of an antioxidant, a UV absorber, and a light stabilizer.

[0048] The primary function of an energetic diluent is to reduce the viscosity of the energetic adhesive, improving its processing and coating properties. Furthermore, the energetic diluent itself possesses a certain amount of energy, which can participate in chemical reactions during the curing process, thereby improving the adhesive's combustion performance. According to a particularly preferred embodiment of the present invention, the energetic diluent is selected from at least one of azides, nitrates, and glycidyl ethers.

[0049] As mentioned above, the present invention also provides a method for preparing a modified epoxy resin energetic adhesive, which comprises: sequentially contacting, mixing, and curing the components in the above composition.

[0050] In some specific embodiments, the contact mixing conditions at least include: a temperature of 20-40°C.

[0051] In order to further improve the performance and process stability of the energetic adhesive, in some specific embodiments, the method further includes: after the contact mixing, allowing the resulting solution to stand for a period of time before performing a curing treatment; the standing conditions include at least: a temperature of 60-80°C and a time of 2-8 hours.

[0052] The standing temperature can be, for example, 60° C., 65° C., 70° C., 75° C., 80° C., or any value between 60-80° C., and the standing time can be, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, or any value between 2-8 hours. After mixing the epoxy resin and the curing agent, standing them in an air atmosphere at 60-80° C. for 2-8 hours allows bubbles introduced during the mixing process to escape naturally, allowing the two to be better mixed, allowing the chemical components in the system to reach a certain equilibrium state, reducing defects after curing, and improving the uniformity and mechanical properties of the material.

[0053] In some specific embodiments, the curing treatment conditions at least include: a temperature of 80-150° C. and a time of 1-12 hours.

[0054] The curing temperature can be, for example, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, or any value between 80°C and 150°C. If the curing temperature is too high, the cured product will experience thermal aging, resulting in reduced mechanical and combustion properties. Conversely, if the curing temperature is too low, the resin may not fully cure within the specified time. The inventors have discovered that curing the composition provided by the present invention at a temperature between 80°C and 150°C produces a cured modified epoxy resin energetic adhesive with superior mechanical and combustion properties.

[0055] According to a particularly preferred embodiment of the present invention, when the curing agent is curing agent combination A, the method comprises the following steps: (1) The epoxy resin matrix is first contacted and mixed with the second curing agent having a number average molecular weight of not less than 600 g / mol, and then vacuumed until the absolute vacuum reaches 10 2 Pa below, the mixed glue A is obtained; (2) The mixed glue A is subjected to a second contact mixing with any one of the alicyclic amine curing agent, the aromatic amine curing agent, and the first curing agent with a number average molecular weight of not more than 400 g / mol, and then vacuumed until the absolute vacuum reaches 10 2 Pa below, the mixed glue B is obtained; (3) Curing the mixed glue B in an air atmosphere.

[0056] It should be noted that when other amine curing agents are used in combination with long-chain polyetheramine curing agents (such as those with a number average molecular weight of not less than 600 g / mol), in the process of synthesizing the adhesive, the long-chain polyetheramine curing agent with a large molecular weight is first added, and then the short-chain polyetheramine curing agent, alicyclic amine curing agent, aromatic amine curing agent and other small molecular weight curing agents are added. The inventors have found that the use of a specific implementation method under this preferred case can be more conducive to the subsequent curing reaction of the two curing agents, avoiding the premature curing of the small molecular weight amine curing agent, making it difficult for the glue to flow and affecting the curing effect.

[0057] To further optimize the mechanical and combustion properties of the adhesive, in some specific embodiments, the curing process sequentially includes a low-temperature curing stage and a high-temperature curing stage. In some specific embodiments, the conditions of the low-temperature curing stage include at least: a temperature of 80-100°C and a time of 1-6 hours; the conditions of the high-temperature curing stage include at least: a temperature of 100-150°C and a time of 1-6 hours. The inventors have discovered that low-temperature curing can ensure that the adhesive initially forms a network structure at a lower temperature, avoiding the concentration of thermal stress caused by high temperatures, which helps to improve the toughness and adhesion of the adhesive. High-temperature curing further improves the cross-linked network and increases the tensile strength and modulus of the adhesive.

[0058] As mentioned above, the present invention also provides a modified epoxy resin energetic adhesive prepared by the above method.

[0059] In some embodiments, the modified epoxy resin energetic adhesive contains a characteristic segment represented by the following formula (III) or formula (IV); , formula (III); in formula (III), n' is 1-35; , formula (IV); in formula (IV), 2≤x'+y'+z'≤50.

[0060] It should be noted that when the first curing agent and the second curing agent are linear polyetheramine curing agents, the modified epoxy resin energetic adhesive contains a characteristic segment shown in the following formula (III); conversely, when the first curing agent and the second curing agent are branched polyetheramine curing agents, the modified epoxy resin energetic adhesive contains a characteristic segment shown in the following formula (IV).

[0061] As mentioned above, the present invention also provides a use of the modified epoxy resin energetic adhesive in solid propellants.

[0062] The present invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, all raw materials and instruments used are commercially available.

[0063] The mass ratio of the epoxy resin matrix to the curing agent in the following examples is the mass ratio of the epoxy resin matrix to the curing agent calculated on an active hydrogen equivalent basis.

[0064] The epoxy resin matrix used in the following examples is E51 bisphenol A epoxy resin purchased from Weihai Huixing Fiber Products Co., Ltd. First curing agent-1: linear polyetheramine curing agent D230, the general structural formula is , where n = 1.69, purchased from Shanghai Huntsman Polyurethane Co., Ltd.; First curing agent-2: branched polyetheramine curing agent T403, the general structural formula is , where x1+y1+z1=5.33, purchased from Shanghai Huntsman Polyurethane Co., Ltd.; First curing agent-3: linear polyetheramine curing agent D400, the general structural formula is , where n1=4.62, purchased from Shanghai Huntsman Polyurethane Co., Ltd.; Second curing agent-1: branched polyetheramine curing agent T3000, the general structural formula is , where x2+y2+z2=48.62, purchased from Shanghai Huntsman Polyurethane Co., Ltd.; Second curing agent-2: linear polyetheramine curing agent D2000, the general structural formula is , where n2=32.21, purchased from Shanghai Huntsman Polyurethane Co., Ltd.; Alicyclic amine curing agent: IPDA, purchased from MacLean Biochemical Technology Co., Ltd.; Aromatic amine curing agent: DDM, purchased from MacLean Biochemical Technology Co., Ltd.

[0065] Example 1 This embodiment provides a method for preparing a modified epoxy resin energetic adhesive, comprising the following steps: (1) Under normal temperature and air atmosphere, E51 bisphenol A epoxy resin and the first curing agent-1 (straight-chain polyetheramine curing agent D230) were added to a beaker in a mass ratio of 1:0.306 and then evenly mixed. The mixture was then vacuumed until the absolute vacuum reached 10 2 Pa below, a mixed glue solution is obtained; (2) The obtained mixed adhesive solution was poured into a mold that had been preheated at 80°C and cured at 80°C for 1 hour to obtain a cured product of the modified epoxy resin energetic adhesive.

[0066] Example 2 This embodiment provides a method for preparing a modified epoxy resin energetic adhesive, comprising the following steps: (1) Under normal temperature and air atmosphere, add E51 bisphenol A epoxy resin and the first curing agent-2 (branched polyetheramine curing agent T403) in a beaker in a mass ratio of 1:0.413 and mix them evenly. Then vacuum the beaker until the absolute vacuum reaches 10 2 Pa below, a mixed glue solution is obtained; (2) The obtained mixed adhesive solution was poured into a mold that had been preheated at 80°C, and cured at 80°C for 4 hours to obtain a cured product of the modified epoxy resin energetic adhesive.

[0067] Example 3 This embodiment provides a method for preparing a modified epoxy resin energetic adhesive, comprising the following steps: (1) Under normal temperature and air atmosphere, first prepare E51 bisphenol A epoxy resin, first curing agent-2 (branched polyetheramine curing agent T403) and second curing agent-1 (branched polyetheramine curing agent T3000) in a mass ratio of 1:0.362:0.338. First, add E51 bisphenol A epoxy resin and second curing agent-1 (branched polyetheramine curing agent T3000) into a beaker, mix them evenly, and evacuate until the absolute vacuum reaches 10 2 Pa below, to obtain a mixed glue solution A; after the obtained mixed glue solution A was allowed to stand for 4 hours in an air atmosphere at 60°C, the first curing agent-2 (branched polyetheramine curing agent T403) was added and mixed evenly, and then vacuum treatment was performed until the absolute vacuum degree reached 10 2 Pa below, the mixed glue solution B is obtained; (2) The obtained mixed glue solution B was poured into a mold that had been preheated at 80°C, and cured at 80°C for 2 hours and at 120°C for 3 hours to obtain a cured product of the modified epoxy resin energetic adhesive.

[0068] Example 4 This embodiment provides a method for preparing a modified epoxy resin energetic adhesive, comprising the following steps: (1) Under normal temperature and air atmosphere, first prepare E51 bisphenol A epoxy resin, alicyclic amine curing agent IPDA and second curing agent-1 (branched polyetheramine curing agent T3000) in a mass ratio of 1:0.174:0.539. First, add E51 bisphenol A epoxy resin and second curing agent-1 (branched polyetheramine curing agent T3000) into a beaker, mix them evenly, and vacuum until the absolute vacuum reaches 10 2 Pa below, to obtain a mixed glue A; the obtained mixed glue A was allowed to stand for 4 hours in an air atmosphere at 80 ° C, and then an alicyclic amine curing agent IPDA was added and mixed evenly, and then vacuumed until the absolute vacuum reached 10 2 Pa below, the mixed glue solution B is obtained; (2) The obtained mixed glue solution B was poured into a mold that had been preheated at 80°C, and cured at 60°C for 1 hour and at 120°C for 3 hours to obtain a cured product of the modified epoxy resin energetic adhesive.

[0069] Example 5 This embodiment provides a method for preparing a modified epoxy resin energetic adhesive, comprising the following steps: (1) Under normal temperature and air atmosphere, first prepare E51 bisphenol A epoxy resin, aromatic amine curing agent DDM and second curing agent-1 (branched polyetheramine curing agent T3000) in a mass ratio of 1:0.202:0.117. First, add E51 bisphenol A epoxy resin and second curing agent-1 (branched polyetheramine curing agent T3000) into a beaker, mix them evenly, and vacuum until the absolute vacuum reaches 10 2 Pa below, to obtain a mixed glue A; the obtained mixed glue A was placed in an air atmosphere of 80 ° C for 2 h, and then the aromatic amine curing agent DDM was added and mixed evenly, and then vacuumed until the absolute vacuum reached 10 2 Pa below, the mixed glue solution B is obtained; (2) The obtained mixed glue liquid B was poured into a mold that had been preheated at 80°C, and cured at 80°C for 1 hour, 120°C for 2 hours, and 150°C for 3 hours to obtain a cured product of the modified epoxy resin energetic adhesive.

[0070] Comparative Example 1 This comparative example provides a method for preparing a modified epoxy resin energetic adhesive, comprising the following steps: (1) Under normal temperature and air atmosphere, add E51 bisphenol A epoxy resin and second curing agent-2 (straight-chain polyetheramine curing agent D2000) in a beaker at a mass ratio of 1:2.62 and mix them evenly. Then vacuum the beaker until the absolute vacuum reaches 10 2 Pa below, a mixed glue solution is obtained; (2) The obtained mixed adhesive solution was poured into a mold that had been preheated at 80°C, and cured at 80°C for 2 hours to obtain a cured product of the modified epoxy resin energetic adhesive.

[0071] Comparative Example 2 This comparative example provides a method for preparing a modified epoxy resin energetic adhesive, comprising the following steps: (1) Under normal temperature and air atmosphere, add E51 bisphenol A epoxy resin and second curing agent-1 (branched polyetheramine curing agent T3000) in a beaker at a mass ratio of 1:2.70 and mix them evenly. Then vacuum the beaker until the absolute vacuum reaches 10 2 Pa below, a mixed glue solution is obtained; (2) The obtained mixed adhesive solution was poured into a mold that had been preheated at 80°C, and cured at 80°C for 2 hours to obtain a cured product of the modified epoxy resin energetic adhesive.

[0072] Analysis example 1 The properties of the cured products of the modified epoxy resin energetic adhesives obtained in Examples 1-5 and Comparative Examples 1-2 were tested, including tensile strength, tensile modulus, initial pyrolysis temperature, and other properties. The specific test results are shown in Table 1.

[0073] Among them, the test method for tensile strength is: ISO 527-2 Test method for tensile properties of plastics; The test method for tensile modulus is: ISO 527-2 Test method for tensile properties of plastics; Differential scanning calorimetry (DSC) was used to measure the initial pyrolysis temperature of the cured product of the modified epoxy resin energetic adhesive.

[0074] Table 1

[0075] By comparing Example 1 and Example 2, it can be seen that the present invention uses only a short-chain polyetheramine curing agent, which makes the cured product have higher tensile strength and modulus; at the same time, the short molecular chain also makes its pyrolysis product more flammable.

[0076] By comparing Examples 3 to 5, it can be seen that the present invention uses other amine curing agents in combination with long-chain polyetheramine curing agents, which can achieve a balance between mechanical properties and combustion properties and achieve better overall performance.

[0077] It can be seen that the modified epoxy resin energetic adhesive composition provided by the present invention, after being treated by a specific method, can simultaneously improve the mechanical properties and combustion properties of the epoxy resin, thereby obtaining an energetic adhesive having both mechanical strength and combustion properties.

[0078] Analysis example 2 The appearance of the cured products of the modified epoxy resin energetic adhesives obtained in Examples 1, 3, 5 and Comparative Example 2 was observed. Figure 1 .

[0079] Specifically, a is a physical picture of the cured product of the modified epoxy resin energetic adhesive prepared in Example 1, b is a physical picture of the cured product of the modified epoxy resin energetic adhesive prepared in Example 3, c is a physical picture of the cured product of the modified epoxy resin energetic adhesive prepared in Example 5, and d is a physical picture of the cured product of the modified epoxy resin energetic adhesive prepared in Comparative Example 2.

[0080] from Figure 1 It can be seen that the solidified material prepared in Example 1 is a uniform colorless transparent solid, the solidified material prepared in Comparative Example 2 is a uniform light yellow transparent solid, the solidified material prepared in Example 3 is a uniform white solid, and the solidified material prepared in Example 5 is a uniform yellow-white solid.

[0081] It should be noted that, in this article, the terms "comprises", "includes" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or apparatus that includes a series of elements includes not only those elements, but also includes other elements not explicitly listed, or also includes elements that are inherent to such process, method, article or apparatus.

[0082] The above technical solutions of the present invention are only preferred embodiments of the present invention and do not limit the patent scope of the present invention. All equivalent structural transformations made by using the contents of the present invention's description and drawings under the technical concept of the present invention, or directly / indirectly applied in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. A modified epoxy resin energetic adhesive composition, characterized in that: The composition contains the following components: epoxy resin matrix and curing agent; The curing agent is a first curing agent or a curing agent combination A having a number average molecular weight of no more than 400 g / mol; The curing agent combination A is a combination of any one of an alicyclic amine curing agent, an aromatic amine curing agent, a first curing agent with a number average molecular weight not greater than 400 g / mol, and a second curing agent with a number average molecular weight not less than 600 g / mol; In the composition, the mass ratio of the epoxy resin matrix to the curing agent calculated on the basis of active hydrogen equivalent is 1:0.3-0.

75.

2. The composition according to claim 1, characterized in that The first curing agent has a structure represented by formula (I) or formula (II): , formula (I); in formula (I), 1≤n1<5; , formula (II); in formula (II), 2≤x1+y1+z1<6; The second curing agent has a structure represented by formula (I') or formula (II'): , formula (I'); in formula (I'), 5≤n2≤35; , formula (II'); in formula (II'), 6≤x2+y2+z2≤50.

3. The composition according to claim 1, characterized in that The epoxy resin matrix is selected from at least one of glycidyl ether epoxy resin and glycidyl ester epoxy resin; and / or the alicyclic amine curing agent is selected from at least one of IPDA, DMDC, and HMDA; And / or the aromatic amine curing agent is selected from at least one of DDM, DDS, and MPD.

4. The composition according to any one of claims 1 to 3, characterized in that The composition further contains 0-5 wt% of an auxiliary agent, and the auxiliary agent is selected from at least one of a curing accelerator, an anti-aging agent and an energetic diluent; and / or the curing accelerator is selected from at least one of imidazole accelerators, phenolic accelerators, and substituted urea accelerators; and / or the antioxidant is selected from at least one of an antioxidant, an ultraviolet absorber, and a light stabilizer; And / or the energetic diluent is selected from at least one of azides, nitrates, and glycidyl ethers.

5. A method for preparing a modified epoxy resin energetic adhesive, characterized in that: The method comprises: sequentially contacting, mixing and curing the components in the composition according to any one of claims 1 to 4.

6. The method according to claim 5, characterized in that The contact mixing conditions at least include: a temperature of 20-40°C.

7. The method according to claim 5, characterized in that The curing treatment conditions at least include: a temperature of 80-150° C. and a time of 1-12 hours.

8. A modified epoxy resin energetic adhesive prepared by the method according to any one of claims 5 to 7.

9. The modified epoxy resin energetic adhesive according to claim 8, characterized in that The modified epoxy resin energetic adhesive contains a characteristic segment of the following formula (III) or formula (IV); , formula (III); in formula (III), n' is 1-35; , formula (IV); in formula (IV), 2≤x'+y'+z'≤50.

10. Use of the modified epoxy resin energetic adhesive according to claim 8 or 9 in solid propellants.

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