Epoxy resin lining adhesive, its preparation method and application

Abstract

This application provides an epoxy resin lining adhesive, its preparation method, and its application, belonging to the field of adhesive technology. The epoxy resin lining adhesive is a two-component system comprising component A and component B, with a mixing mass ratio of component A to component B of (1.5-2.5):1. Component A comprises epoxy resin, a liquid toughening agent, toughening particles, microspheres, reinforcing fibers, and a first wear-resistant filler. Component B comprises a curing agent, a curing accelerator, and a second wear-resistant filler. The toughening particles and the microspheres synergistically constitute a biphase composite reinforcement in component A. The epoxy resin lining adhesive provided by this invention possesses excellent high strength and toughness and can be widely used in equipment linings in industries such as mining, power, and chemicals.

Description

Technical Field

[0001] This application relates to the field of adhesive technology, and in particular to an epoxy resin lining adhesive, its preparation method, and its application. Background Technology

[0002] Liner adhesive is mainly used for filling and bonding between liners and the substrate in equipment such as crushers and ball mills. Currently, ball mills and similar equipment are widely used in industries requiring grinding, such as metallurgy and mining, and wear-resistant rubber liners are crucial anti-wear components of ball mills. During use, rubber liners rub against the ore, generating temperature rise. High temperatures alter the rubber molecular structure, reducing wear resistance and affecting the liner's service life. Traditional liner filling techniques also have drawbacks. Liners are frequently subjected to strong impacts, making them prone to wear and requiring regular replacement. Currently, high-temperature zinc alloy casting or room-temperature high-grade cement mortar casting methods are commonly used. However, these methods suffer from drawbacks such as cumbersome procedures, high risk, high cost, high labor intensity, and severe environmental pollution, making them unsuitable for the long-term use requirements of industrial equipment. Summary of the Invention

[0003] This application is made in view of the above-mentioned problems, and its purpose is to provide an epoxy resin liner adhesive, its preparation method and application, to meet the bonding requirements of the liner during long-term operation.

[0004] Specifically, an epoxy resin lining adhesive is provided, which is a two-component system comprising component A and component B, wherein the mass ratio of component A to component B is (1.5-2.5):1; wherein:

[0005] Component A comprises epoxy resin, liquid toughening agent, toughening particles, microspheres, reinforcing fibers, and a first wear-resistant filler;

[0006] Component B comprises a curing agent, a curing accelerator, and a second wear-resistant filler;

[0007] The toughening particles and the microspheres synergistically form a biphase composite reinforcement in component A.

[0008] Furthermore, the average particle size of the toughening particles is 50-500 nm, and the average particle size of the microspheres is 50-500 μm;

[0009] The microspheres are surface-treated glass microspheres or ceramic microspheres;

[0010] The reinforcing fiber includes at least one of aramid pulp fiber and polyimide pulp fiber, with a fiber length of 0.3-1.2 mm;

[0011] The liquid toughening agent is liquid-terminated carboxyl-terminated butadiene-acrylonitrile rubber.

[0012] Further, based on the total mass of component A, component A comprises: 15-22 wt.% epoxy resin, 5-12 wt.% liquid toughening agent, 5-12 wt.% toughening particles, 35-45 wt.% microspheres, 2-5 wt.% reinforcing fibers, 15-25 wt.% first wear-resistant filler, as well as coupling agent and first thixotropic agent;

[0013] Based on the total mass of component B, component B comprises: 18-28 wt.% curing agent, 2-6 wt.% curing accelerator, 60-75 wt.% second wear-resistant filler, and second thixotropic agent.

[0014] Furthermore, the first and second wear-resistant fillers comprise silicon carbide and alumina ceramic balls;

[0015] The silicon carbide has at least two different average particle sizes, including a first silicon carbide with an average particle size of 5-15 μm and a second silicon carbide with an average particle size of 40-100 μm.

[0016] The alumina ceramic balls have an average particle size of 150-500 μm.

[0017] Furthermore, the first and second wear-resistant fillers in component A and / or component B also contain a third silicon carbide with an average particle size of 0.5-2 μm;

[0018] The curing accelerator is a tertiary amine accelerator;

[0019] The curing agent is at least one of modified alicyclic amine curing agents or aromatic amine curing agents;

[0020] The first thixotropic agent is oleophilic silica; the second thixotropic agent is hydrophilic silica.

[0021] A second aspect of the present invention provides a method for preparing an epoxy resin lining adhesive, comprising preparing component A and preparing component B;

[0022] The preparation of component A includes the following steps:

[0023] S1a: Mix epoxy resin with liquid toughening agent to obtain matrix mixture;

[0024] S2a: Add a coupling agent and the first wear-resistant filler of component A to the matrix mixture, and perform a first mixing and dispersion under heating, vacuum and first shear conditions to obtain a primary mixture;

[0025] S3a: Add toughening particles to the primary mixture and perform a second mixing and dispersion under a second shear condition lower than the first shear condition;

[0026] S4a: Add reinforcing fibers for third dispersion;

[0027] S5a: Add microspheres and mix them under conditions lower than the first shear condition;

[0028] S6a: Add the first thixotropic agent, perform final mixing and degassing to obtain component A;

[0029] The preparation of component B includes the following steps:

[0030] S1b: Mix the curing agent and the curing accelerator to obtain a curing agent mixture;

[0031] S2b: The second wear-resistant filler of component B is added to the curing agent mixture and mixed and dispersed under vacuum and shear conditions;

[0032] S3b: Add the second thixotropic agent, mix well, and obtain component B.

[0033] Further, in step S2a, the first shearing conditions include dispersion using a dispersion disk with a rotation speed of 1000-1600 rpm, a vacuum degree of -0.08 ~ -0.1 MPa, and a temperature of 50-60℃;

[0034] In step S3a, the second shearing condition includes dispersion using a dispersion disc with a rotation speed of 600-1000 rpm;

[0035] In step S5a, after adding the microspheres, stir at a speed of 15-40 rpm and avoid using high-speed shearing.

[0036] Furthermore, in step S1b, the mixing temperature is 25-35°C, and the mixing time is 10-20 minutes;

[0037] In step S2b, the mixing temperature is controlled at 25-35℃ and the vacuum degree is -0.08 ~ -0.095 MPa.

[0038] A third aspect of the present invention provides an application of epoxy resin lining adhesive, wherein the epoxy resin lining adhesive is used for lining bonding.

[0039] The method for bonding the lining plate includes the following steps:

[0040] (1) Surface treatment of the liner substrate;

[0041] (2) Mix component A and component B evenly at a mass ratio of (1.5-2.5):1 to obtain the construction colloid;

[0042] (3) Apply the construction adhesive to the surface of the treated lining substrate to form an adhesive layer;

[0043] (4) Curing the coated liner: cure at 20-30℃ for 24-48 hours to complete the curing process.

[0044] The present invention has the following beneficial effects:

[0045] In this invention, component A of the epoxy resin lining adhesive introduces epoxy resin as the matrix material, providing a good foundation for the adhesive layer's bonding strength and chemical stability. Simultaneously, the addition of liquid-terminated carboxyl-terminated nitrile rubber as a liquid toughening agent effectively improves the brittleness of the epoxy resin, enhancing the adhesive layer's impact resistance and flexibility, making it less prone to cracking under vibration and impact during equipment operation. Toughening particles of 50-500 nm and microspheres of 50-500 μm synergistically constitute a biphase composite reinforcement in component A. The toughening particles can toughen and strengthen the matrix at the microscale, preventing the generation and propagation of microcracks; while surface-treated glass microspheres or ceramic microspheres can reduce the adhesive layer density macroscopically, while simultaneously improving its wear resistance and compressive strength. Together, these two components significantly improve the overall mechanical properties of the adhesive layer. The addition of reinforcing fibers such as aramid pulp fibers or polyimide pulp fibers further enhances the tensile strength, flexural strength, and tear resistance of the adhesive layer, effectively transferring stress and preventing crack propagation.

[0046] The first wear-resistant filler uses first silicon carbide with an average particle size of 5-15 μm, second silicon carbide with an average particle size of 40-100 μm, and optional third silicon carbide with an average particle size of 0.5-2 μm, combined with alumina ceramic balls with an average particle size of 150-500 μm, forming a multi-scale particle size distribution. This gradation design can increase the packing density of the filler and reduce the voids inside the adhesive layer, thereby significantly enhancing the wear resistance and hardness of the adhesive layer. This allows the adhesive layer to maintain good surface integrity during long-term friction with materials such as minerals, extending its service life. Detailed Implementation

[0047] To make the objectives, technical solutions, and advantages of this application clearer, the following description and illustration are provided in conjunction with embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application. All other embodiments obtained by those skilled in the art based on the embodiments provided in this application without inventive effort are within the scope of protection of this application.

[0048] Obviously, the following description is merely some examples or embodiments of this application. Those skilled in the art can apply this application to other similar scenarios without any inventive effort. Furthermore, it is understood that although the effort involved in such development may be complex and lengthy, for those skilled in the art related to the content disclosed in this application, any changes to design, manufacturing, or production based on the technical content disclosed in this application are merely conventional technical means and should not be construed as insufficient disclosure of the content of this application.

[0049] An embodiment of the first aspect of this application provides an epoxy resin lining adhesive, which is a two-component system comprising component A and component B, wherein the mass ratio of component A to component B is (1.5-2.5):1; wherein:

[0050] Component A comprises epoxy resin, liquid toughening agent, toughening particles, microspheres, reinforcing fibers, and a first wear-resistant filler;

[0051] Component B comprises a curing agent, a curing accelerator, and a second wear-resistant filler;

[0052] The toughening particles and the microspheres synergistically form a biphase composite reinforcement in component A.

[0053] In this embodiment, the epoxy resin in component A serves as the matrix material, providing basic adhesive properties and mechanical strength for the lining adhesive. The addition of a liquid toughening agent effectively improves the brittleness of the epoxy resin, enhancing its impact resistance and flexibility, making the lining adhesive less prone to cracking under external impact.

[0054] The curing agent and curing accelerator in component B play a crucial role in the curing process of the lining adhesive. Modified alicyclic amine curing agents or aromatic amine curing agents possess good chemical resistance and thermal stability, enabling the lining adhesive to exhibit good chemical stability and heat resistance after curing, thus adapting to complex working environments. The preferred tertiary amine accelerator is DMP-30 (K-54). As a curing accelerator, the tertiary amine accelerator can accelerate the curing reaction, shorten the curing time, and improve production efficiency.

[0055] In practical applications, when this epoxy resin lining adhesive is used for lining bonding, surface treatment of the lining substrate can improve the bond strength between the adhesive and the substrate. Component A and component B are mixed uniformly at a mass ratio of (1.5-2.5):1, preferably 2:1, to obtain a construction adhesive. This adhesive is then applied to the treated lining substrate surface to form an adhesive layer. Finally, a specific curing process is performed to allow the adhesive to achieve the required strength and performance.

[0056] In this embodiment, the toughening particles are MBS resin (methyl methacrylate-butadiene-styrene terpolymer) purchased from Hubei Xingyan New Material Technology Co., Ltd., and the average particle size of the particles is 50-500nm.

[0057] The microspheres are surface-treated glass microspheres or ceramic microspheres; the average particle size of the microspheres is 50-500 μm. The method for surface-treating the glass microspheres is as follows: Glass microspheres are placed in a reaction vessel, and an appropriate amount of silane coupling agent solution is added. The silane coupling agent is a mixture of methyltriisopropoxysilane and 3-(trimethoxysilyl)propyl methacrylate in a volume ratio of 1:1-1.2; the amount of silane coupling agent is 1%-3% of the mass of the glass microspheres. The reaction is stirred at 80-100℃ for 2-4 hours to ensure the silane coupling agent fully bonds to the surface of the glass microspheres. After the reaction, the glass microspheres are repeatedly washed with deionized water to remove unreacted silane coupling agent, and then dried in an oven at 100-120℃ for 6-8 hours to obtain surface-silanized glass microspheres. A similar method can be used for the surface treatment of ceramic microspheres, selecting appropriate silane coupling agents and processing techniques to improve their compatibility and bonding strength with other components.

[0058] The reinforcing fiber includes at least one of aramid pulp fiber and polyimide pulp fiber, with a fiber length of 0.3-1.2 mm.

[0059] The liquid toughening agent is liquid carboxyl-terminated nitrile butadiene rubber (CTBN), purchased from Shanghai Sendi Chemical Co., Ltd.

[0060] In this embodiment, based on the total mass of component A, component A comprises: 15-22 wt.% epoxy resin, 5-12 wt.% liquid toughening agent, 5-12 wt.% toughening particles, 35-45 wt.% microspheres, 2-5 wt.% reinforcing fibers, 15-25 wt.% first wear-resistant filler, 0.5-1 wt.% coupling agent, and 1-3 wt.% first thixotropic agent;

[0061] Based on the total mass of component B, component B comprises: 18-28 wt.% curing agent, 2-6 wt.% curing accelerator, 60-75 wt.% second wear-resistant filler, and 1-3 wt.% second thixotropic agent.

[0062] In this embodiment, the first wear-resistant filler and the second wear-resistant filler include silicon carbide and alumina ceramic balls;

[0063] The silicon carbide has at least two different particle sizes, including a first silicon carbide (F) with an average particle size of 5-15 μm and a second silicon carbide (M) with an average particle size of 40-100 μm, and a third silicon carbide (C) with an average particle size of 0.5-2 μm. This multi-gradient silicon carbide design allows silicon carbide of different particle sizes to better fill with alumina ceramic balls, further optimizing the packing structure of the liner adhesive. The smaller-sized third silicon carbide can fill the gaps between the larger-sized silicon carbide and alumina ceramic balls, making the structure of the liner adhesive more compact, thereby significantly improving its wear resistance.

[0064] The alumina ceramic balls have an average particle size of 150-500 μm.

[0065] In this embodiment, the curing accelerator is a tertiary amine accelerator; the curing agent is preferably at least one of modified alicyclic amine curing agents or aromatic amine curing agents. The alicyclic groups in the molecular structure of the modified alicyclic amine curing agent endow it with good steric hindrance and electronic effects, making the molecular chain arrangement of the cured liner adhesive more regular and orderly, thereby improving its chemical corrosion resistance and thermal stability.

[0066] The first thixotropic agent is oleophilic silica, purchased from Nanjing Tianxing New Materials Co., Ltd.; the second thixotropic agent is hydrophilic silica, purchased from Shandong Haochuang New Materials Technology Co., Ltd.

[0067] A second aspect of the present invention provides a method for preparing an epoxy resin lining adhesive, comprising preparing component A and preparing component B;

[0068] The preparation of component A includes the following steps:

[0069] S1a: Mix epoxy resin with liquid toughening agent to obtain matrix mixture;

[0070] S2a: Add a coupling agent and the first wear-resistant filler of component A to the matrix mixture, and perform a first mixing and dispersion under heating, vacuum and first shear conditions to obtain a primary mixture;

[0071] S3a: Add toughening particles to the primary mixture and perform a second mixing and dispersion under a second shear condition lower than the first shear condition;

[0072] S4a: Add reinforcing fibers for third dispersion;

[0073] S5a: Add microspheres and mix them under conditions lower than the first shear condition;

[0074] S6a: Add the first thixotropic agent, perform final mixing and degassing to obtain component A;

[0075] The preparation of component B includes the following steps:

[0076] S1b: Mix the curing agent and the curing accelerator to obtain a curing agent mixture;

[0077] S2b: The second wear-resistant filler of component B is added to the curing agent mixture and mixed and dispersed under vacuum and shear conditions;

[0078] S3b: Add the second thixotropic agent, mix well, and obtain component B.

[0079] This embodiment also includes a pretreatment step: placing all silicon carbide (total amount required for components A and B) and alumina ceramic balls in a tray, placing it in a forced-air drying oven, and cooling to room temperature. Aramid pulp pretreatment: drying the aramid pulp fibers at 80°C for 2 hours, and then running a low-speed opener at 800 rpm for 3 minutes to eliminate fiber agglomeration.

[0080] Step S1a: Add epoxy resin and liquid toughening agent to a planetary mixer at once, and stir at 30 rpm for 10 minutes to obtain the matrix mixture.

[0081] In this embodiment, in step S2a, coupling agent KH-560 and the first wear-resistant filler of component A, including three-graded silicon carbide and alumina ceramic balls, are added and dispersed in a dispersion disk at a temperature of 50-60℃, a vacuum degree of -0.08 ~ -0.1 MPa, and a rotation speed of 1000-1600 rpm to obtain a primary mixture. The stirring time is 20 minutes.

[0082] In another preferred embodiment, in step S2a, oily pigment and kaolin are also added and mixed.

[0083] In step S3a, toughening particles are added and dispersed using a dispersion disc with a rotation speed of 600-1000 rpm for 10 minutes.

[0084] In step S4a, add reinforcing fiber aramid pulp, reduce the dispersion pan to 600-800 rpm, and stir at 40 rpm while maintaining 50-60°C and vacuum for 5 minutes.

[0085] In step S5a, after adding the microspheres, stir at a speed of 15-40 rpm, avoiding high-speed shearing, maintain 50-60°C and vacuum, and stir for 15 minutes.

[0086] S6a: Add the first thixotropic agent, oleophilic fumed silica, turn on the dispersion disc to 600-700 rpm, and the main stirrer to 30-40 rpm. Maintain a vacuum of -0.08 ~ -0.1 MPa and stir for 15 minutes.

[0087] Finally, the material is cooled and discharged.

[0088] In this embodiment, in step S1b, a high-speed dispersion vessel is used to mix the curing agent and the curing accelerator. The mixing temperature is 25-35℃, the mixing time is 10-20 minutes, and the stirring speed is 300-400 rpm.

[0089] In step S2b, defoamer is added to the middle of the curing agent mixture and stirred evenly at a speed of 300-400 rpm. Then, the second wear-resistant filler of component B is added, and the stirring speed is increased to 400-500 rpm. The mixing temperature is controlled at 25-35℃ and the vacuum degree is -0.08 ~ -0.095 MPa.

[0090] In step S3b, a second thixotropic agent, hydrophilic fumed silica, is added, and a vacuum of -0.08 to -0.095 MPa is maintained. The stirring speed is adjusted to 200-300 rpm. Finally, the material is discharged.

[0091] A third aspect of the present invention provides an application of an epoxy resin lining adhesive, wherein the epoxy resin lining adhesive is used for lining bonding.

[0092] Furthermore, the method for bonding the liner includes the following steps:

[0093] (1) The substrate of the liner is surface treated to achieve a cleanliness level of Sa 2.5 (ISO 8501-1) and a roughness of Ra = 40±5μm;

[0094] (2) Mix component A and component B at a mass ratio of (1.5-2.5):1 using a low-speed paddle mixer at 200-300 rpm for 4-5 minutes to obtain the construction colloid.

[0095] (3) Apply the construction adhesive to the surface of the treated lining substrate to form an adhesive layer;

[0096] (4) Curing the coated liner: cure at 20-30℃ for 24-48 hours to complete the curing process.

[0097] Example

[0098] The following examples describe the disclosure of this invention in more detail. These examples are merely illustrative, as various modifications and variations will be apparent to those skilled in the art within the scope of this disclosure. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are based on weight. Unless otherwise stated, all reagents used in the examples are available commercially or synthesized using conventional methods and are ready for use without further processing. Unless otherwise stated, all instruments used in the examples are available commercially.

[0099] Example 1

[0100] An epoxy resin lining adhesive comprises component A and component B, wherein the mass ratio of component A to component B is 2:1, wherein:

[0101] Component A comprises: 17.5 wt.% epoxy resin (Phoenix E-44), 7 wt.% liquid carboxyl-terminated nitrile butadiene rubber (purchased from Kaiming Plastics (Dongguan) Co., Ltd.), 0.6 wt.% coupling agent KH560, 1.4 wt.% kaolin, 13.5% graded silicon carbide (SiC (2μm) 6.0%, SiC (10μm) 4.3%, SiC (50μm) 3.2%), 6 wt.% toughening particles MBS resin (methyl methacrylate-butadiene-styrene terpolymer, purchased from Hubei Xingyan New Material Technology Co., Ltd.), 4 wt.% aramid pulp fiber, 40.0 wt.% 200μm glass microspheres, 0.5 wt.% oily pigment (purchased from Jinan Yucai Chemical Co., Ltd.), 8 wt.% alumina ceramic balls (300μm), and 1.5 wt.% oleophilic silica (purchased from Nanjing Tianxing New Material Co., Ltd.).

[0102] Component B comprises: 22.5 wt.% modified alicyclic amine curing agent (purchased from Guangzhou Rongchuan Technology Co., Ltd., model B-352), 4.0 wt.% tertiary amine accelerator (DMP-30(K-54) from Chuzhou Huisheng Electronic Materials Co., Ltd.), 11 wt.% graded silicon carbide (SiC(2μm) 5.5 wt.%, SiC(10μm) 3.3 wt.%, SiC(45μm) 2.2 wt.%), 5.0 wt.% talc, 56.0 wt.% alumina ceramic balls (300μm), 1.2 wt.% hydrophilic silica (purchased from Shandong Haochuang Innovation Materials Technology Co., Ltd.), and 0.3 wt.% defoamer (purchased from Jinan Zhongbei Fine Chemical Co., Ltd.).

[0103] The preparation method of the epoxy resin lining adhesive includes preparing component A and preparing component B;

[0104] The preparation of component A includes the following steps:

[0105] S1a: Add epoxy resin and liquid-terminated carboxyl nitrile rubber to a planetary mixer at once, and stir at 30 rpm for 10 minutes to obtain a matrix mixture;

[0106] S2a: Add coupling agent KH-560, oily pigment, kaolin, three-graded silicon carbide, and alumina ceramic balls to the matrix mixture, and disperse it in a dispersion disk at a temperature of 55°C, a vacuum degree of -0.1 MPa, and a rotation speed of 1500 rpm to obtain a primary mixture;

[0107] S3a: Add toughening particles to the primary mixture, disperse using a dispersing disc at 800 rpm for 10 minutes;

[0108] S4a: Add aramid pulp, reduce the dispersion plate to 700 rpm, main stirrer at 40 rpm, maintain 55°C and vacuum, and stir for 5 minutes;

[0109] S5a: Add glass microspheres, stir at a speed of 30 rpm, and avoid using high-speed shearing. Maintain 55°C and vacuum for 15 minutes.

[0110] S6a: Add oleophilic fumed silica, turn on the dispersion plate to 600 rpm, and the main stirrer to 30 rpm. Maintain a vacuum of -0.1 MPa and stir for 15 minutes to obtain component A;

[0111] The preparation of component B includes the following steps:

[0112] S1b: A mixture of modified alicyclic amine curing agent and tertiary amine accelerator is obtained;

[0113] S2b: Add graded silicon carbide, talc powder, alumina ceramic balls and defoamer to the curing agent mixture, and stir at 450 rpm for 10 min under a vacuum of -0.09 Pa and a temperature of 30°C.

[0114] S3b: Add hydrophilic fumed silica, maintain a vacuum of -0.09 MPa, adjust the stirring speed to 260 rpm, mix evenly, and obtain component B.

[0115] Example 2

[0116] This embodiment is basically the same as Example 1, except that in component A: toughening particles 5 wt.%, aramid pulp fiber 4 wt.%, and alumina ceramic balls 9 wt.%.

[0117] Example 3

[0118] This embodiment is basically the same as Example 1, except that in component A: toughening particles 8 wt.%, aramid pulp fiber 4 wt.%, and alumina ceramic balls 6 wt.

[0119] Example 4

[0120] This embodiment is basically the same as Example 1, except that in component A: toughening particles 7 wt.%, aramid pulp fiber 2 wt.%, and alumina ceramic balls 9 wt.%.

[0121] Example 5

[0122] This embodiment is basically the same as Example 1, except that in component A: toughening particles 5 wt.%, aramid pulp fiber 5 wt.%, and alumina ceramic balls 8 wt.%;

[0123] The curing agent used in component B is an aromatic amine curing agent (113C curing agent).

[0124] Comparative Example 1

[0125] This comparative example is basically the same as Example 1, except that in component A: no toughening particles are added, and its mass is increased by an equal amount to 200μm glass microspheres.

[0126] Comparative Example 2

[0127] This comparative example is basically the same as Example 1, except that: in component A, no aramid pulp fiber is added, but its mass is increased to the SiC filler in equal amounts, of which SiC (2μm) is 7.0%, SiC (10μm) is 6.3%, and SiC (50μm) is 4.2%.

[0128] Comparative Example 3

[0129] This comparative example is basically the same as Example 1, except that in component A: alumina ceramic balls are not added, but their mass is added to the glass microspheres in equal amounts.

[0130] Comparative Example 4

[0131] This comparative example is basically the same as Example 1, except that in component A: tertiary amine accelerators are not used, but are added to the modified alicyclic amine curing agent in equal mass.

[0132] Experimental Case

[0133] The following tests were conducted on the epoxy resin lining adhesives of Examples 1-5 and Comparative Examples 1-4:

[0134] Tensile shear strength: According to GB / T 7124-2008 "Determination of tensile shear strength of adhesives (rigid material to rigid material)", the substrate is sandblasted 45# steel, and the curing conditions are 25℃ / 36h;

[0135] Impact strength (simply supported beam): Prepare standard unnotched specimens according to GB / T 1043.1-2008;

[0136] Abrasion resistance: According to GB / T 3960-2016 (wet sand rubber wheel method), under a load of 22.7 N and a rotation of 1000 rpm, the wear is measured by the volumetric wear (cm²) of the sample. 3 The lower the value, the more wear-resistant the product.

[0137] High-temperature strength retention rate: The compressive strength of the test specimen at 25℃ and 120℃ is measured, and the retention rate is calculated.

[0138] Interface evaluation after thermal cycling: The bonded sample was cycled 10 times between -20℃ (2h) and 120℃ (2h). After cooling to room temperature, the interface was observed and recorded to see if bulging, cracking or peeling occurred.

[0139] The test results are shown in Table 1.

[0140]

[0141] As shown in Table 1, the epoxy resin lining adhesives of Examples 1-5 are generally superior to those of Comparative Examples 1-4 in terms of various performance indicators. This indicates that the present invention can effectively improve the performance of epoxy resin lining adhesives by rationally adding toughening particles, aramid pulp fibers, alumina ceramic balls, and using tertiary amine accelerators. Toughening particles can enhance the toughness and tensile shear strength of the adhesive, aramid pulp fibers help improve wear resistance and high-temperature strength retention, glass microspheres can improve the overall performance of the adhesive, and tertiary amine accelerators also have a positive effect on performance improvement during the curing process.

[0142] Regarding tensile shear strength, the values ​​of the embodiments were generally higher than those of the comparative examples, indicating that the reasonable addition of each component enhanced the bonding force between the adhesive and the substrate. In terms of abrasion resistance, the volumetric wear of the embodiments was mostly less than that of the comparative examples, indicating that the combination of these components improved the abrasion resistance of the adhesive. Regarding high-temperature strength retention, most embodiments also performed better, demonstrating the improvement of the adhesive's performance stability under high-temperature conditions due to component addition. In the post-thermal cycling interface evaluation, the embodiments remained intact, while some comparative examples showed micro-cracks at the edges and corners, and obvious bulging, further proving the rationality and effectiveness of the component addition in this invention.

[0143] In Comparative Example 1, without the addition of toughening particles, their mass was increased by an equal amount into micron-sized rigid microspheres, resulting in a decrease in tensile shear strength. This may be because the toughening particles possess a unique core-shell structure, where the different properties of the core and shell layers work synergistically to effectively disperse stress and enhance the adhesive's toughness and bonding to the substrate. In contrast, the micron-sized rigid microspheres primarily function as fillers and supports, unable to optimize and improve the adhesive's structure at the microscopic level like the toughening particles. They cannot effectively disperse and absorb stress, making the adhesive more prone to crack propagation and failure under tensile shear forces, thus leading to a decrease in tensile shear strength.

[0144] In Comparative Example 2, without the addition of aramid pulp fibers, but with an equal mass added to the SiC filler, the wear resistance decreased and microcracks appeared at the edges and corners. Aramid fibers possess high strength, high modulus, and good wear resistance. They can form a reinforcing network structure in the adhesive, effectively resisting the impact and friction of abrasive particles and reducing adhesive wear. When SiC filler replaces aramid fibers, although SiC itself has a certain degree of hardness, it cannot form a reinforcing network similar to aramid fibers, and therefore cannot effectively disperse stress and resist wear, leading to an increase in volumetric wear. Simultaneously, during thermal cycling, due to the lack of reinforcement from aramid fibers, the bonding force between the adhesive and the liner matrix cannot be well maintained with temperature changes, making stress concentration more likely at the edges and corners, thus causing microcracks.

[0145] In Comparative Example 3, without the addition of alumina ceramic balls, an equal mass of alumina ceramic balls was added to the glass microspheres, resulting in significant bulging and increased volumetric wear. This is likely because alumina ceramic balls possess excellent hardness, wear resistance, and dispersibility, allowing them to distribute evenly in the adhesive, providing support and reinforcement, and effectively preventing localized stress concentration and deformation during curing. While glass microspheres also provide some filling, their hardness and wear resistance are relatively inferior to alumina ceramic balls, and their dispersion in the adhesive may not be as uniform. During thermal cycling, the glass microspheres cannot effectively resist the thermal stress caused by temperature changes, leading to uneven expansion and contraction within the adhesive layer, resulting in noticeable bulging. Simultaneously, the lack of support and reinforcement from alumina ceramic balls also affects the wear resistance of the adhesive layer, further increasing volumetric wear.

[0146] Comparative Example 4, without using tertiary amine accelerators, added an equal mass of them to the modified alicyclic amine curing agent. This resulted in a lower high-temperature strength retention rate and overall lower strength. Tertiary amine accelerators synergistically work with the modified alicyclic amine curing agent during curing to form a denser and more stable cross-linked structure. This cross-linked structure exhibits better stability at high temperatures, effectively maintaining the strength of the adhesive. Without tertiary amine accelerators, the cross-linked structure formed solely by the modified alicyclic amine curing agent is relatively loose, making it prone to molecular chain breakage and structural damage at high temperatures, leading to a lower high-temperature strength retention rate and affecting overall strength.

[0147] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. An epoxy resin lining adhesive, characterized in that, The epoxy resin lining adhesive is a two-component system, comprising component A and component B, wherein the mixing mass ratio of component A to component B is (1.5-2.5):1; wherein: Component A comprises epoxy resin, liquid toughening agent, toughening particles, microspheres, reinforcing fibers, and a first wear-resistant filler; Component B comprises a curing agent, a curing accelerator, and a second wear-resistant filler; The toughening particles and the microspheres synergistically form a biphase composite reinforcement in component A; The toughening particles have an average particle size of 50-500 nm and are made of MBS resin; the microspheres have an average particle size of 50-500 μm and are surface-treated glass microspheres or ceramic microspheres; the surface treatment uses a silane coupling agent compound solution, wherein the silane coupling agent is a compound of vinyltriisopropoxysilane and 3-(trimethoxysilyl)propyl methacrylate in a volume ratio of 1:1-1.2; The first and second wear-resistant fillers comprise silicon carbide and alumina ceramic balls; the silicon carbide has at least three different particle sizes, including a first silicon carbide with an average particle size of 5-15 μm, a second silicon carbide with an average particle size of 40-100 μm, and a third silicon carbide with an average particle size of 0.5-2 μm; the alumina ceramic balls have an average particle size of 150-500 μm; Based on the total mass of component A, component A comprises: 15-22 wt.% epoxy resin, 5-12 wt.% liquid toughening agent, 5-12 wt.% toughening particles, 35-45 wt.% microspheres, 2-5 wt.% reinforcing fibers, and 15-25 wt.% first wear-resistant filler; Based on the total mass of component B, component B comprises: 18-28 wt.% curing agent, 2-6 wt.% curing accelerator, and 60-75 wt.% secondary wear-resistant filler; The preparation method of the epoxy resin lining adhesive includes preparing component A and preparing component B; wherein preparing component A includes the following steps: S1a: Mix epoxy resin with liquid toughening agent to obtain matrix mixture; S2a: Add a coupling agent and the first wear-resistant filler of component A to the matrix mixture, and perform a first mixing and dispersion under heating, vacuum and first shear conditions to obtain a primary mixture; S3a: Add toughening particles to the primary mixture and perform a second mixing and dispersion under a second shear condition lower than the first shear condition; S4a: Add reinforcing fibers for third dispersion; S5a: Add microspheres and mix at a speed of 15-40 rpm, avoiding high-speed shearing. S6a: Add the first thixotropic agent, perform final mixing and degassing to obtain component A.

2. The epoxy resin lining adhesive according to claim 1, characterized in that, The reinforcing fiber includes at least one of aramid pulp fiber and polyimide pulp fiber, with a fiber length of 0.3-1.2 mm; The liquid toughening agent is liquid-terminated carboxyl-terminated butadiene-acrylonitrile rubber.

3. The epoxy resin lining adhesive according to claim 1, characterized in that, Component A further comprises a coupling agent and a first thixotropic agent; component B further comprises a second thixotropic agent; the first thixotropic agent is oleophilic silica; and the second thixotropic agent is hydrophilic silica.

4. The epoxy resin lining adhesive according to claim 1, characterized in that, The curing accelerator is a tertiary amine accelerator; The curing agent is at least one of modified alicyclic amine curing agents or aromatic amine curing agents.

5. A method for preparing an epoxy resin lining adhesive, characterized in that, The preparation of the epoxy resin lining adhesive according to any one of claims 1-4 includes the preparation of component A and the preparation of component B; The preparation of component A includes the following steps: S1a: Mix epoxy resin with liquid toughening agent to obtain matrix mixture; S2a: Add a coupling agent and the first wear-resistant filler of component A to the matrix mixture, and perform a first mixing and dispersion under heating, vacuum and first shear conditions to obtain a primary mixture; S3a: Add toughening particles to the primary mixture and perform a second mixing and dispersion under a second shear condition lower than the first shear condition; S4a: Add reinforcing fibers for third dispersion; S5a: Add microspheres and mix them under conditions lower than the first shear condition; S6a: Add the first thixotropic agent, perform final mixing and degassing to obtain component A; The preparation of component B includes the following steps: S1b: Mix the curing agent and the curing accelerator to obtain a curing agent mixture; S2b: The second wear-resistant filler of component B is added to the curing agent mixture and mixed and dispersed under vacuum and shear conditions; S3b: Add the second thixotropic agent, mix well, and obtain component B.

6. The method for preparing epoxy resin lining adhesive according to claim 5, characterized in that, In step S2a, the first shearing conditions include dispersion using a dispersion disk with a rotation speed of 1000-1600 rpm, a vacuum degree of -0.08 ~ -0.1 MPa, and a temperature of 50-60℃; In step S3a, the second shearing condition includes dispersion using a dispersion disc with a rotation speed of 600-1000 rpm; In step S5a, after adding the microspheres, stir at a speed of 15-40 rpm and avoid using high-speed shearing.

7. The method for preparing epoxy resin lining adhesive according to claim 5, characterized in that, In step S1b, the mixing temperature is 25-35℃ and the mixing time is 10-20 minutes; In step S2b, the mixing temperature is controlled at 25-35℃ and the vacuum degree is -0.08 ~ -0.095 MPa.

8. An application of the epoxy resin lining adhesive as described in any one of claims 1-4, characterized in that, The epoxy resin liner adhesive is used for liner bonding. The method for bonding the liner includes the following steps: (1) Surface treatment of the liner substrate; (2) Mix component A and component B evenly at a mass ratio of (1.5-2.5):1 to obtain the construction colloid; (3) Apply the construction adhesive to the surface of the treated lining substrate to form an adhesive layer; (4) Curing the coated liner: cure at 20-30℃ for 24-48 hours to complete the curing process.

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