Modified solid waste rock wool reinforced underwater epoxy adhesive and preparation method thereof

Abstract

The invention discloses a modified solid waste rock wool reinforced underwater epoxy adhesive and a preparation method thereof. The adhesive is composed of a component A and a component B, the component A comprises epoxy resin, a reactive diluent, a flexibilizer, a coupling agent and modified rock wool; the component B comprises a phenolic aldehyde amine curing agent, an accelerant and talcum powder. The mass fraction ratio of the component A to the component B is (1-4.5): 1. The preparation method of the underwater curing epoxy adhesive comprises the following steps: 1) adding a reactive diluent, a flexibilizer, a coupling agent and modified rock wool fibers into epoxy resin to prepare an epoxy mixed liquid component A; 2) mixing a phenolic aldehyde amine curing agent, an accelerant and talcum powder to prepare a mixed solution component B; the modified solid waste rock wool reinforced underwater epoxy adhesive has the advantages of high underwater bonding strength and wide underwater application range, and can be applied to steel surface and concrete bonding; in addition, the rock wool fibers are stable in chemical property and high in corrosion resistance, and the newly developed underwater epoxy adhesive is more environmentally friendly.

Description

Technical Field

[0001] The present invention relates to the technical field of epoxy resin adhesives, and in particular to a modified solid waste rock wool reinforced underwater epoxy adhesive and a preparation method thereof. Background Art

[0002] Adhesives are widely used in daily life and industrial development. However, with the continuous development of engineering practice, an increasing number of underwater structures and equipment, such as dams, underwater bridges, ports, and underwater island facilities, may suffer structural damage or destruction during long-term use, requiring in-situ bonding, repair, reinforcement, or restoration underwater. Epoxy resins offer strong adhesion and a wide operating temperature range, making the development of underwater adhesives with rapid curing and high bond strength essential.

[0003] Basalt rock wool is a fiber material made from natural basalt rock, which is melted and centrifuged at high speed to form cotton-like fibers. Basalt rock wool fibers possess excellent mechanical properties, exhibiting high tensile strength and stiffness. By adding binders such as phenolic resin, rock wool boards are made into rock wool boards, which exhibit excellent chemical stability, thermal insulation, and waterproof properties. Due to their excellent properties, rock wool boards are widely used in the insulation field. However, once used, rock wool boards are discarded, resulting in energy waste and environmental pollution.

[0004] Chinese patent CN 108865034 discloses an adhesive for underwater repair of steel structures and its preparation method. The adhesive is composed of nano-silica, epoxy resin, acetone as a diluent, silica powder, a wetting and leveling agent, an underwater curing agent, light calcium powder, and a talcum powder adhesion promoter. The adhesive can be constructed underwater and has excellent underwater curing performance. However, the use of acetone as a diluent in the adhesive is environmentally polluting and not conducive to environmental protection.

[0005] After the above analysis, solid waste rock wool is processed into modified rock wool fiber and added to underwater epoxy resin, which not only solves the recycling problem of solid waste rock wool boards, but also reduces the impact of solid waste rock wool on energy waste and environmental pollution; at the same time, it can prepare environmentally friendly underwater epoxy adhesives and improve the bonding strength and water resistance stability of epoxy adhesives underwater. Summary of the Invention

[0006] The present invention provides a modified solid waste rock wool-reinforced underwater epoxy adhesive and a method for preparing the same. The modified solid waste rock wool-reinforced underwater epoxy adhesive exhibits rapid underwater curing, high bonding strength, and stable chemical properties. Furthermore, the newly developed underwater epoxy adhesive is more environmentally friendly. Furthermore, the method for preparing the recycled rock wool-reinforced underwater curing epoxy adhesive utilizes readily available, low-cost raw materials and a simple preparation process.

[0007] In order to achieve the above solution, the present invention provides a method for preparing a modified solid waste rock wool reinforced underwater epoxy adhesive; The modified solid waste rock wool reinforced underwater epoxy adhesive consists of component A and component B, wherein component A includes: 1) Adding active diluent and toughening agent to epoxy resin to prepare epoxy mixed solution a1; 2) Mix the mixed solution a1 with the modified rock wool and coupling agent to prepare the epoxy mixed solution component A, which is then sealed and stored for future use; Among them, component B includes: 3) Mix the phenalkamine curing agent, talcum powder and accelerator to form a mixed liquid component B.

[0008] In the above technical scheme, the modified rock wool treatment method is to stir and clean the solid waste rock wool in water and dry it in a vacuum oven; use a ball mill at a ball milling speed of 200 rpm and a ball milling time of 12 hours to obtain rock wool fibers; prepare anhydrous ethanol and distilled water into a solution in a volume ratio of 9:1, add a silane coupling agent and rock wool fibers to the ethanol-water solution, and react in a water bath at 40-60°C for 6-8 hours to obtain modified rock wool fibers; the particle size of the modified rock wool fibers is 30-80um.

[0009] The present invention also provides a modified solid waste rock wool reinforced underwater epoxy adhesive, which is obtained by the above-mentioned preparation method. The mass ratio of component A to component B is 1-4.5:1, and the proportions of the respective substances are as follows: Component A and its proportions: 100 parts of epoxy resin, 0-20 parts of active diluent, 2-10 parts of toughening agent, 1-5 parts of coupling agent, and 0-10 parts of modified rock wool; Component B materials and proportions: 40-70 parts of amine curing agent, 0-7 parts of accelerator, and 5-35 parts of water-absorbing filler.

[0010] The modified solid waste rock wool reinforced underwater epoxy adhesive prepared by the above steps and proportions of the present invention is prepared by mixing component A and component B evenly when in use. It is suitable for interface bonding of concrete facilities and steel facilities in underwater environments, and has an underwater steel-steel shear strength of more than 10 MPa and a carbon fiber-carbon fiber shear strength of more than 12 MPa. Summary of the Invention

[0011] Figure 1 This is a flow chart for the preparation of modified solid waste rock wool reinforced underwater epoxy adhesive.

[0012] Figure 2 This is an infrared image of modified solid waste rock wool.

[0013] Figure 3Micromorphology of solid waste rock wool before and after treatment and modification, where (a) is the micromorphology of solid waste rock wool, (b) is the micromorphology of rock wool fiber, and (c) is the micromorphology of modified rock wool fiber. Specific implementation cases

[0014] The following is a detailed description of the specific embodiments of the present invention. The present invention provides a method for preparing an underwater curing epoxy adhesive reinforced with waste recycled rock wool. The preparation process of the modified solid waste rock wool reinforced underwater epoxy adhesive is as follows: Figure 1 As shown; the waste recycled rock wool reinforced underwater epoxy adhesive consists of component A and component B, wherein component A includes: 1) Adding active diluent and toughening agent to epoxy resin to prepare epoxy mixed solution a1; 2) Mix the mixed solution a1 with the modified rock wool and coupling agent to prepare the epoxy mixed solution component A, which is then sealed and stored for future use; Among them, component B includes: 3) Mix the phenalkamine curing agent, talcum powder and accelerator to form a mixed liquid component B.

[0015] In step 1) of the present invention, in order to make the prepared epoxy adhesive have better underwater bonding performance, the heating and mixing conditions are preferably a heating temperature of 40° C. and a mixing time of 20-40 minutes.

[0016] In step 1) of the present invention, in order to make the prepared epoxy adhesive have better underwater bonding performance, the epoxy resin is preferably one of bisphenol A epoxy resin E51 or bisphenol A epoxy resin E44.

[0017] In step 1) of the present invention, in order to make the prepared epoxy adhesive have better underwater bonding performance, the reactive diluent is preferably one of butyl glycidyl ether or phenyl glycidyl ether.

[0018] In step 1) of the present invention, in order to make the prepared epoxy adhesive have better underwater bonding performance, the toughening agent is preferably carboxyl liquid nitrile rubber (CTBN).

[0019] In step 2) of the present invention, in order to make the prepared epoxy adhesive have better underwater bonding performance, the coupling agent is one of 3-aminopropyltriethoxysilane (KH550) or γ-(2,3-epoxypropyloxy)propyltrimethoxysilane (KH560).

[0020] In step 2) of the present invention, the solid waste rock wool treatment method is to mix rock wool and clean water in a weight ratio of 1:10, place the rock wool fibers in the clean water and stir for 10 minutes, remove dust and impurities in the rock wool, and vacuum dry the rock wool; then use a ball mill at a ball milling speed of 200 rpm for 12 hours to prepare rock wool fibers.

[0021] In step 2) of the present invention, the method for modifying solid waste rock wool is as follows: first, anhydrous ethanol and distilled water are prepared into a solution in a volume ratio of 9:1, and a silane coupling agent 3-aminopropyltriethoxysilane and rock wool fiber are added to the ethanol aqueous solution, wherein the amount of the silane coupling agent is 1-6% by mass of the ethanol aqueous solution, and the amount of the rock wool fiber is 1-5% by mass of the ethanol aqueous solution; after the above-mentioned mixed solution is ultrasonically dispersed and mechanically stirred for 30 minutes, it is reacted in a water bath at 40-60°C for 6-8 hours, filtered, and vacuum dried at 80°C to obtain modified rock wool fiber; the modified rock wool fiber has a particle size of 30-80 μm.

[0022] In step 3) of the present invention, in order to make the prepared epoxy adhesive have better underwater bonding performance, the curing agent is selected as a phenalkamine curing agent, and the water-absorbing filler is one or both of talc powder and quicklime. The talc powder and quicklime are preferably 800 mesh or 1200 mesh. The water-absorbing filler is dried in an oven before use.

[0023] In step 3) of the present invention, in order to make the prepared epoxy adhesive have better underwater bonding performance, the accelerator is preferably 2,4,6-tris(dimethylaminomethyl)phenol (DMP30).

[0024] In the present invention, various substances can be appropriately selected from a wide range; however, in order to make the prepared epoxy adhesive have more excellent underwater bonding performance, the mass ratio of component A to component B is preferably 1-4.5:1, and the amount ratio of each substance is as follows: Component A and its proportions: 100 parts of epoxy resin, 0-20 parts of active diluent, 2-10 parts of toughening agent, 1-5 parts of coupling agent, and 0-10 parts of modified rock wool; Component B materials and proportions: 40-70 parts of amine curing agent, 0-7 parts of accelerator, and 5-35 parts of water-absorbing filler.

[0025] The improved effects of this invention are as follows: by adding modified rock wool fibers to the adhesive system, the interfacial wettability between the underwater substrate and the epoxy resin adhesive is improved, which facilitates the formation of hydrogen bonds and other bonding between the epoxy resin and the substrate, thereby increasing the adhesion between the adhesive and the substrate. At the same time, the modified rock wool fibers and the adhesive form a network structure, enhancing the cohesive strength of the adhesive. The silane coupling agent can improve the dispersion of the rock wool fibers in the epoxy resin, promote the bonding between the epoxy resin matrix and the rock wool, and increase the toughness and strength of the epoxy resin.

[0026] The recycling and reuse of rock wool reduces its impact on energy waste and environmental pollution. The modified rock wool fiber composite epoxy resin adhesive can not only improve the adhesive's underwater bonding strength and water resistance stability, but the new adhesive is also more environmentally friendly.

[0027] The tensile shear strength of the adhesive was tested according to the method described in ASTM D1002 "Test Method for Apparent Shear Strength of Single-Lap Adhesive-Jointed Metal Specimens by Tensile Loading (Metal to Metal)". Each test was performed 5 times, and the average of the 5 results was taken.

[0028] The following specific examples illustrate the preparation and advantages of the underwater curing epoxy adhesive reinforced with waste recycled rock wool of the present invention.

[0029] Example 1 Rock wool and clean water are mixed in a weight ratio of 1:10, the rock wool fibers are placed in the clean water and stirred for 10 minutes, and the rock wool is vacuum dried; then a ball mill is used at a ball milling speed of 200 rpm and a ball milling time of 12 hours to prepare rock wool fibers. Figure 3 (a) and (b) are the microscopic morphologies of solid waste rock wool before and after treatment, respectively. (a) is the microscopic morphology of solid waste rock wool. Rock wool has a large aspect ratio, and the fiber length is above 300um and cannot be directly used as a reinforcing agent for epoxy resin; Figure (b) is the microscopic morphology of rock wool fibers after grinding. The rock wool is cut into shorter rock wool fibers with a fiber particle size of 30-80um.

[0030] Example 2 Anhydrous ethanol and distilled water were prepared into a solution in a volume ratio of 9:1, and a silane coupling agent 3-aminopropyltriethoxysilane and rock wool fiber were added to the ethanol aqueous solution. The amount of silane coupling agent was 5% by mass of the ethanol aqueous solution, and the amount of rock wool fiber was 1% by mass of the ethanol aqueous solution. The above mixture was ultrasonically dispersed and mechanically stirred for 30 minutes, reacted in a 50°C water bath for 6 hours, filtered, and vacuum dried at 80°C to obtain modified rock wool fiber.

[0031] like Figure 2 The infrared images of rock wool fiber and modified rock wool fiber are shown. For rock wool fiber, there are only two infrared characteristic peaks, which are located at 900 cm -1 Si-O bonds and 700 cm -1 Al-O bond; for modified rock wool fibers, at 950-1000 cm -1 Other peaks appeared nearby, which can be attributed to the Si-O bond in KH550. Since the other end of O in KH550 is connected to an ethyl group, and the other end of Si is connected to other groups, these other groups cause the chemical shift of Si-O. Therefore, the infrared characteristic peak of the Si-O bond of the modified rock wool fiber is different from that of the rock wool fiber. In addition, at 1500 cm-1 Several characteristic peaks near 3500-2800 cm are derived from the stretching vibration of CH in methyl and methylene groups in KH550. -1 In the range of 1:1, a broad vibration peak appears, which is related to the vibration of the NH bond in the amino group and the hydrogen bond formed between the rock wool fiber and KH550. Figure 3 (c) is the microscopic morphology of the modified rock wool fiber. Compared with the smooth surface of the rock wool fiber, the surface of the modified rock wool fiber coated with silane coupling agent appears rough. The results of infrared testing and microscopic images of rock wool fibers before and after modification show that the modified rock wool fiber was successfully prepared.

[0032] Example 3 The ingredients and dosage of component A are as follows: 100 parts of E51 epoxy resin, 20 parts of reactive diluent, 2 parts of carboxyl liquid nitrile rubber, 1 part of 3-aminopropyltriethoxysilane, and 2 parts of modified rock wool fiber; the ingredients and dosage of component B are as follows: 50 parts of amine curing agent, 7 parts of 2,4,6-tris(dimethylaminomethyl)phenol, and 5 parts of talc; the substances in component A are mixed at 40°C for 30 minutes to prepare epoxy mixed liquid component A, and the curing agent, accelerator and talc are mixed evenly to form mixed liquid component B; components A and B are stirred evenly in water to prepare steel-steel and carbon fiber-carbon fiber single lap shear specimens.

[0033] Example 4 The ingredients and dosage of component A are as follows: 100 parts of E51 epoxy resin, 15 parts of reactive diluent, 4 parts of carboxyl liquid nitrile rubber, 2 parts of 3-aminopropyltriethoxysilane, and 4 parts of modified rock wool fiber; the ingredients and dosage of component B are as follows: 50 parts of amine curing agent, 5 parts of 2,4,6-tris(dimethylaminomethyl)phenol, and 15 parts of talc; the substances in component A are mixed at 40°C for 30 minutes to prepare epoxy mixed liquid component A, and the curing agent, accelerator and talc are mixed evenly to form mixed liquid component B; components A and B are stirred evenly in water to prepare steel-steel and carbon fiber-carbon fiber single lap shear specimens.

[0034] Example 5 The ingredients and dosage of component A are as follows: 100 parts of E51 epoxy resin, 10 parts of reactive diluent, 6 parts of carboxyl liquid nitrile rubber, 3 parts of 3-aminopropyltriethoxysilane, and 6 parts of modified rock wool fiber; the ingredients and dosage of component B are as follows: 50 parts of amine curing agent, 3 parts of 2,4,6-tris(dimethylaminomethyl)phenol, and 25 parts of talc; the substances in component A are mixed at 40°C for 30 minutes to prepare epoxy mixed liquid component A, and the curing agent, accelerator and talc are mixed evenly to form mixed liquid component B; components A and B are stirred evenly in water to prepare steel-steel and carbon fiber-carbon fiber single lap shear specimens.

[0035] Example 6 The ingredients and dosage of component A are as follows: 100 parts of E51 epoxy resin, 5 parts of reactive diluent, 8 parts of carboxyl liquid nitrile rubber, 4 parts of 3-aminopropyltriethoxysilane, and 8 parts of modified rock wool fiber; the ingredients and dosage of component B are as follows: 50 parts of amine curing agent, 5 parts of 2,4,6-tris(dimethylaminomethyl)phenol, and 35 parts of talc; the substances in component A are mixed at 40°C for 30 minutes to prepare epoxy mixed liquid component A, and the curing agent, accelerator and talc are mixed evenly to form mixed liquid component B; components A and B are stirred evenly in water to prepare steel-steel and carbon fiber-carbon fiber single lap shear specimens.

[0036] Example 7 The ingredients and dosage of component A are: 100 parts of E51 epoxy resin, 10 parts of carboxyl liquid nitrile rubber, 5 parts of 3-aminopropyltriethoxysilane, and 10 parts of modified rock wool fiber; the ingredients and dosage of component B are: 50 parts of amine curing agent, and 35 parts of talcum powder. The substances in component A are mixed at 40°C for 30 minutes to prepare epoxy mixed liquid component A, and the curing agent, accelerator and talcum powder are mixed evenly to form mixed liquid component B. Components A and B are stirred evenly in water to prepare steel-steel and carbon fiber-carbon fiber single lap shear specimens.

[0037] Example 8 The ingredients and dosage of component A are as follows: 100 parts of E44 epoxy resin, 15 parts of reactive diluent, 6 parts of carboxyl liquid nitrile rubber, 3 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, and 6 parts of modified rock wool fiber; the ingredients and dosage of component B are as follows: 40 parts of amine curing agent, 7 parts of 2,4,6-tris(dimethylaminomethyl)phenol, and 35 parts of talc; the substances in component A are mixed at 40°C for 20 minutes to prepare epoxy mixed liquid component A, and the curing agent, accelerator and talc are mixed evenly to form mixed liquid component B; components A and B are stirred evenly in water to prepare steel-steel and carbon fiber-carbon fiber single lap shear specimens.

[0038] Example 9 The ingredients and dosage of component A are as follows: 100 parts of E44 epoxy resin, 15 parts of reactive diluent, 6 parts of carboxyl liquid nitrile rubber, 4 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, and 4 parts of modified rock wool fiber; the ingredients and dosage of component B are as follows: 60 parts of amine curing agent, 5 parts of 2,4,6-tris(dimethylaminomethyl)phenol, and 35 parts of talc; the substances in component A are mixed at 40°C for 30 minutes to prepare epoxy mixed liquid component A, and the curing agent, accelerator and talc are mixed evenly to form mixed liquid component B; components A and B are stirred evenly in water to prepare steel-steel and carbon fiber-carbon fiber single lap shear specimens.

[0039] Example 10 The ingredients and dosage of component A are as follows: 100 parts of E44 epoxy resin, 15 parts of reactive diluent, 6 parts of carboxyl liquid nitrile rubber, 5 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, and 4 parts of modified rock wool fiber; the ingredients and dosage of component B are as follows: 70 parts of amine curing agent, 3 parts of 2,4,6-tris(dimethylaminomethyl)phenol, and 35 parts of talc; the substances in component A are mixed at 40°C for 40 minutes to prepare epoxy mixed liquid component A, and the curing agent, accelerator and talc are mixed evenly to form mixed liquid component B; components A and B are stirred evenly in water to prepare steel-steel and carbon fiber-carbon fiber single lap shear specimens.

[0040] Comparative Example The ingredients and dosage of component A are: 100 parts of E51 epoxy resin, 15 parts of reactive diluent, 6 parts of carboxyl liquid nitrile rubber, and 3 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane; the ingredients and dosage of component B are: 50 parts of amine curing agent, 5 parts of 2,4,6-tris(dimethylaminomethyl)phenol, and 35 parts of talc. The substances in component A were mixed at 40°C for 30 minutes to prepare epoxy mixed liquid component A, and the curing agent, accelerator and talc were mixed evenly to form mixed liquid component B. Components A and B were stirred evenly in water to prepare steel-steel and carbon fiber-carbon fiber single lap shear specimens.

[0041] The following table shows the single lap shear test results of the underwater bonding adhesives in Examples 1-8 after curing in water for 7 days: Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example Steel-steel shear strength (MPa) 6.36 7.84 10.91 8.75 6.62 8.48 9.94 8.58 5.97 Carbon fiber board-carbon fiber shear strength (MPa) 8.65 10.29 12.36 10.97 9.75 10.63 11.52 10.84 8.25 The experimental test results in Table 1 show the following conclusions: the modified solid waste rock wool reinforced underwater epoxy adhesive disclosed in the present invention has excellent underwater bonding performance. The underwater steel-steel single lap shear test strength exceeds 10 MPa, and the underwater carbon fiber-carbon fiber single lap shear test strength exceeds 12 MPa. The modified rock wool fiber and filler system in the present invention improve the underwater bonding performance of the adhesive system.

Claims

1. A modified solid waste rock wool reinforced underwater epoxy adhesive and a preparation method thereof, characterized in that: It is composed of two components, component A and component B. Among them, component A includes: 1) Adding active diluent and toughening agent to epoxy resin to prepare epoxy mixed solution a1; 2) Mix the mixed solution a1 with the modified rock wool and coupling agent to prepare the epoxy mixed solution component A, which is then sealed and stored for future use; Among them, component B includes: 3) Mix the phenalkamine curing agent, talc powder and accelerator to form a mixed liquid component B.

2. The preparation method according to claim 1, characterized in that In step 1) and step 2), the epoxy resin mixing temperature is 40°C and the mixing time is 20-40 minutes; The epoxy resin is selected from epoxy resin E44 and epoxy resin E51.

3. The preparation method according to claim 1, characterized in that In step 1), the reactive diluent is one of butyl glycidyl ether and phenyl glycidyl ether, and the toughening agent is liquid nitrile rubber.

4. The preparation method according to claim 1, characterized in that The modified rock wool treatment method comprises the following steps: stirring and cleaning solid waste rock wool in water, and drying in a vacuum oven; using a ball mill at a ball milling speed of 200 revolutions and a ball milling time of 12 hours to obtain rock wool fibers; preparing anhydrous ethanol and distilled water into a solution in a volume ratio of 9:1, adding a silane coupling agent and rock wool fibers to the ethanol-water solution, and reacting in a water bath at 40-60° C. for 6-8 hours to obtain modified rock wool fibers; the particle size of the modified rock wool fibers is 30-80 μm.

5. The preparation method according to claim 1, characterized in that In step 2), modified rock wool and a coupling agent are added to the epoxy mixture a1. The coupling agent is any one of 3-aminopropyltriethoxysilane and γ-(2,3-epoxypropyloxy)propyltrimethoxysilane.

6. The preparation method according to claim 1, characterized in that In step 3), the water-absorbing filler is one or both of talc and quicklime, and the filler particle size is 800 mesh or 1200 mesh; and the accelerator is 2, 4, 6-tris(dimethylaminomethyl)phenol (DMP-30).

7. The preparation method according to any one of claims 1 to 6, characterized in that The mass ratio of component A to component B is 1-4.5:1, and the dosage ratio of each substance is as follows: Component A and its proportions: 100 parts of epoxy resin, 0-20 parts of active diluent, 2-10 parts of toughening agent, 1-5 parts of coupling agent, and 0-10 parts of modified rock wool; Component B materials and proportions: 40-70 parts of amine curing agent, 0-7 parts of accelerator, and 5-35 parts of water-absorbing filler.

8. The preparation method according to any one of claims 1 to 7, characterized in that The modified solid waste rock wool reinforced underwater epoxy adhesive is obtained. When in use, component A and component B are mixed and stirred evenly and then used immediately. The adhesive is suitable for interface bonding of concrete facilities and steel facilities in underwater environments. The underwater bonding steel-steel shear strength is 10MPa, and the carbon fiber-carbon fiber shear strength is above 12MPa.

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