Adhesive for underwater repair of pipeline under pressure and preparation method of adhesive

Abstract

The invention discloses an adhesive for underwater repair of an under-pressure pipeline and a preparation method of the adhesive, and relates to the technical field of underwater pipeline repair and adhesives, the adhesive is composed of a component A and a component B, the component A is prepared from organic-inorganic hybrid epoxy ceramic resin, gamma-aminopropyltrimethoxysilane, a core-shell toughening agent, a reactive diluent and a first filler; the component B is composed of a curing agent, di (gamma-trimethoxysilyl propyl) amine and a second filler; the organic-inorganic hybrid epoxy ceramic resin is obtained by carrying out hydrolysis and dehydration condensation reaction on phenyltriethoxysilane, tetraethyl silicate and KH-567; the adhesive for underwater repair of the pipeline under pressure has the characteristics of good bonding performance, good underwater constructability, high curing speed, high bonding strength, excellent sealing performance and corrosion resistance and good durability, and is particularly suitable for emergency repair and permanent repair of the underwater pipeline under pressure.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of underwater pipeline repair and adhesive technology, in particular to an adhesive for underwater repair of pipelines under pressure and a preparation method thereof. BACKGROUND

[0002] As a key infrastructure for marine oil and gas transportation, municipal water supply and drainage, and energy transmission, the structural integrity and safe operation of underwater pipelines are of great significance to the national economy and environmental protection. However, due to the harsh environment in which underwater pipelines are subjected to for a long time, they are easily affected by factors such as seawater corrosion, wave impact, seabed geological activity, and accidental impact, resulting in defects such as corrosion perforation, crack cracking, and mechanical damage. If these defects are not repaired in time, they may lead to oil and gas leakage, production interruption, environmental pollution, and even major safety accidents, causing immeasurable economic losses and ecological disasters.

[0003] Traditional underwater pipeline repair techniques mainly include on-water welding repair, mechanical clamp repair, and replacement of pipe sections. However, these traditional methods have limitations such as high construction difficulty, long repair period, high safety risk, and poor economic efficiency. Especially for deep-sea pipelines, welding repair requires creating a dry environment or using expensive underwater welding equipment, and the quality is difficult to guarantee; mechanical clamps may not match the shape of the pipeline, resulting in poor sealing and unsatisfactory repair results.

[0004] With the rapid development of composite material technology, underwater pipeline repair technology based on composite materials has emerged. This technology uses high-performance fiber-reinforced composite materials and special resin matrices to form a reinforced protective layer at the defect site of the pipeline through a unique molding process, restoring or even improving the pressure-bearing capacity and sealing performance of the pipeline. Preformed repair of pipelines uses unsaturated polyester and glass fiber to pre-manufacture a composite sleeve in the factory according to the pipe diameter of the pipeline with defects, and then bonds the composite sleeve to the pipeline surface through strong adhesive at the repair site, thereby restoring the strength of the pipeline. However, there are two major drawbacks: first, the composite sleeve itself has high stiffness and is difficult to deform, requiring high requirements for the adhesive during repair; second, the composite sleeve needs to go through a series of production processes such as extrusion, drying, heat treatment, and curing during processing. Existing adhesives cannot be used for underwater construction, or they cannot achieve the required mechanical strength when cured underwater.

[0005] Therefore, to solve the above technical problems, it is desirable to develop an adhesive for wet winding method composite materials with excellent mechanical properties, which can be used for underwater construction and underwater curing. SUMMARY

[0006] To solve the above problems, the purpose of the present application is to provide an adhesive for underwater repair of pipelines under pressure and a preparation method thereof.

[0007] The adhesive for underwater repair of pipelines under pressure is composed of component A and component B in a mass ratio of 100:60-80. The adhesive for underwater repair of pipelines under pressure is composed of component A and component B in a mass ratio of 100:60-80. The organic-inorganic hybrid epoxy ceramic resin is obtained through hydrolysis and dehydration condensation reaction of phenyltriethoxysilane, tetraethyl silicate and KH-567.

[0008] Preferably, the organic-inorganic hybrid epoxy ceramic resin is prepared according to the following steps: In weight parts, 145-155 parts of anhydrous ethanol, 20-25 parts of phenyltriethoxysilane and 20-25 parts of tetraethyl silicate are added to a reaction kettle, stirring is started, and stirring is carried out for 10-20 minutes, 5-10 parts of deionized water is added to the reaction kettle under stirring, hydrochloric acid aqueous solution is used to adjust pH to 2-4, stirring is carried out at 55-65 DEG C for 10-12 hours, 25-30 parts of KH-567 is added to the reaction kettle in 5-8 times, then 6-7 parts of deionized water is added to the reaction kettle, hydrochloric acid aqueous solution is used to adjust pH to 2-4, and stirring is carried out at 55-65 DEG C for 10-12 hours to obtain a reaction liquid; the obtained reaction liquid is distilled under reduced pressure to remove excess ethanol, water and reaction by-products to obtain the organic-inorganic hybrid epoxy ceramic resin.

[0009] Preferably, the core-shell toughening agent is one or two of MX-153, MX-154 or EPX-125.

[0010] Preferably, the active diluent is one or two of butyl glycidyl ether, benzyl glycidyl ether or ethylene glycol diglycidyl ether.

[0011] Preferably, the curing agent is one or two of T-31, LSW-523, SF-SX-3326A or SF-SX-5253.

[0012] Preferably, the first filler is one or two of hollow glass microbeads, cement, talcum powder, cerium oxide or graphene oxide; and the second filler is one or two of hollow glass microbeads, cement, talcum powder, cerium oxide or graphene oxide.

[0013] Preferably, the cerium oxide has a particle size of 30-100 μm, and the surface is treated with silane coupling agent UM-08. The treated rare earth material is added as an additive to the polyurethane material, which can significantly improve the heat resistance of the material, increase the heat resistance temperature from 70℃ to 95℃, and greatly improve the tensile strength, thereby effectively improving the comprehensive performance of the material; on the other hand, the silane modification can greatly improve the bonding performance of the adhesive.

[0014] The present application also includes a preparation method of the adhesive for underwater repair of pressurized pipelines, comprising the following steps: ①Preparation of component A: 70-90 parts by weight of organic-inorganic hybrid epoxy ceramic resin, 1-3 parts of γ-aminopropyltrimethoxysilane, 10-15 parts of core-shell toughening agent, 1-5 parts of active diluent and 10-20 parts of first filler are added to a planetary stirrer, stirred for 5-10 minutes, vacuum stirred for 30-60 minutes, and discharged to obtain component A; ②Preparation of component B: 20-80 parts of curing agent, 0.5-1 parts of di(γ-trimethoxysilylpropyl)amine and 20-40 parts of second filler are added to a planetary stirrer, stirred for 5-10 minutes, vacuum stirred for 30-60 minutes, and discharged to obtain component B; ③Gluing: when used, components A and B are mixed uniformly at a mass ratio of 100:60-80 to obtain the adhesive for underwater repair of pressurized pipelines.

[0015] Compared with the prior art, the present application has the following advantages: The adhesive for underwater repair of pressurized pipelines is a two-component solvent-free environmentally friendly adhesive, which has good bonding performance, good underwater workability, fast curing speed, high bonding strength, excellent sealing performance, excellent corrosion resistance and good durability, and is particularly suitable for emergency repair and permanent repair of underwater pipelines under pressure.

[0016] The adhesive for underwater repair of pressurized pipelines of the present application uses organic-inorganic hybrid epoxy resin and curing agent and other components to react to form a crosslinked structure, thereby improving the strength and bonding performance of the adhesive layer, so that the adhesive can be cured in an underwater environment and has excellent corrosion resistance. Firstly, the organic-inorganic hybrid epoxy resin of the present application has an epoxy value of 0.2-0.4 mol / 100g, and the moderate content of epoxy value can react with the amine group in component B to form a crosslinked structure, thereby improving the strength and toughness of the adhesive, and making the adhesive have corrosion resistance.

[0017] Secondly, the present application combines the high cross-linking degree rigid skeleton Si-O-Si three-dimensional network structure with the organic structure together; after hydrolysis and condensation of phenyltriethoxysilane (PhTES), the bulky phenyl group is suspended on the siloxane skeleton as a side group. These phenyl groups have a steric hindrance effect on the one hand, which can prevent the inorganic phase from excessive aggregation; on the other hand, its organic characteristics form a flexible interface layer between the inorganic phase and the organic phase. The rigid inorganic skeleton is easy to produce cracks when impacted, and the flexible phenyl phase dispersed therein can effectively induce silver lines, terminate crack propagation, and absorb a large amount of energy through its own deformation, thereby achieving a perfect balance of rigidity enhancement and toughness improvement, overcoming the brittleness of traditional epoxy resins. The non-polar phenyl group reduces the surface energy of the material, making it have better hydrophobicity, thereby improving the moisture resistance and corrosion resistance of the material. DETAILED DESCRIPTION

[0018] The purpose of the present application is to provide an adhesive for underwater repair of a pressurized pipeline and a preparation method thereof, which is realized by the following technical scheme: The CAS number of di (gamma-trimethoxysilyl propyl) amine is 82985-35-1.

[0019] The T-31 curing agent in the embodiment of the present application is provided by Suzhou Hengsiter Industry Co., Ltd., the LSW-523 curing agent is provided by Dalian Liansheng New Material Co., Ltd., the SF-SX-3326A curing agent is provided by Changzhou Shanfeng Chemical Co., Ltd., and the SF-SX-5253 curing agent is provided by Changzhou Shanfeng Chemical Co., Ltd.

[0020] The core-shell toughening agent MX-153 is provided by Zhongyuan Chemical Industry Co., Ltd., the core-shell toughening agent MX-154 is provided by Zhongyuan Chemical Industry Co., Ltd., and the core-shell toughening agent EPX-125 is provided by Complex High New Material (Shanghai) Co., Ltd.

[0021] The silane coupling agent UM-08 is provided by Wuhan Anruike Material Co., Ltd., and is a long-chain siloxane oligomer.

[0022] The cerium oxide with a particle size of 30-100 mu m treated by the silane coupling agent UM-08 is prepared according to the following steps: a. An ethanol aqueous solution with a mass concentration of 70-80% is prepared; b. The silane coupling agent UM-08 is added to the ethanol aqueous solution to obtain a silane coupling agent solution with a mass concentration of 0.1-0.3%; c. Add cerium oxide to the above silane coupling agent solution in 5 to 8 portions, start stirring, and after the addition is complete, ultrasonically disperse for 0.5 to 1 hour, then place it in an oven and dry it at 105 to 115°C to obtain silane-modified cerium oxide; the mass ratio of the silane coupling agent solution to cerium oxide is 2 to 4:1.

[0023] In the embodiments of the present invention, the mass concentration of the hydrochloric acid aqueous solution used is 0.1~0.5 mol / L.

[0024] The γ-aminopropyltrimethoxysilane of this invention, used as an underwater wetting modifier, has a methoxy group in its structure that hydrolyzes to generate silanol groups. These silanol groups can dehydrate and condense with hydroxyl groups on the metal surface to form stable Si-OM (M represents metal) chemical bonds. Organic end connection: The amino group at the other end can react with the epoxy groups of the epoxy resin, thereby firmly "bridging" the epoxy resin and the metal substrate together through chemical bonds.

[0025] The present invention will be further described below with reference to specific embodiments. Example

[0026] An adhesive for underwater repair of pressurized pipelines, wherein component A is composed of the following raw materials: 7 kg of organic-inorganic hybrid epoxy ceramic resin, 0.1 kg of γ-aminopropyltrimethoxysilane, 1 kg of core-shell toughening agent MX-153, 0.1 kg of reactive diluent butyl glycidyl ether, and 1 kg of hollow glass microspheres; and component B is composed of the following raw materials: 2 kg of curing agent T-31, 0.05 kg of di(γ-trimethoxysilylpropyl)amine, and 2 kg of cement; Take 6 kg of component A and 3.6 kg of component B to form an adhesive for underwater repair of pressurized pipelines; The organic-inorganic hybrid epoxy ceramic resin is obtained from phenyltriethoxysilane, tetraethyl silicate, and KH-567 through hydrolysis and dehydration condensation reactions; the specific steps are as follows: 21.75 kg of anhydrous ethanol, 3 kg of phenyltriethoxysilane, and 3 kg of tetraethyl silicate were added to a reaction vessel, and stirring was started. After stirring for 10 minutes, 0.75 kg of deionized water was added to the reaction vessel while stirring, and the pH was adjusted to 2 with hydrochloric acid aqueous solution. The mixture was stirred at 55°C for 12 hours. 3.75 kg of KH-567 was added to the reaction vessel in 5 portions, followed by 0.9 kg of deionized water. The pH was adjusted to 2 with hydrochloric acid aqueous solution, and the mixture was stirred at 55°C for 12 hours to obtain the reaction solution. The resulting reaction solution was distilled under reduced pressure to remove excess ethanol, water, and reaction byproducts to obtain an organic-inorganic hybrid epoxy ceramic resin. Example

[0027] An adhesive for underwater repair of pressurized pipelines, wherein component A is composed of the following raw materials: 9 kg of organic-inorganic hybrid epoxy ceramic resin, 0.3 kg of γ-aminopropyltrimethoxysilane, 1.5 kg of core-shell toughening agent MX-154, 0.5 kg of reactive diluent benzyl glycidyl ether, and 2 kg of talc; and component B is composed of the following raw materials: 8 kg of curing agent LSW-523, 0.1 kg of di(γ-trimethoxysilylpropyl)amine, and 4 kg of graphene oxide. Take 13 kg of component A and 10.4 kg of component B to form an adhesive for underwater repair of pressurized pipelines; The organic-inorganic hybrid epoxy ceramic resin is obtained from phenyltriethoxysilane, tetraethyl silicate, and KH-567 through hydrolysis and dehydration condensation reactions; the specific steps are as follows: 23.25 kg of anhydrous ethanol, 3.75 kg of phenyltriethoxysilane, and 3.75 kg of tetraethyl silicate were added to a reaction vessel, and stirring was started. The mixture was stirred for 20 minutes. While stirring, 1.5 kg of deionized water was added to the reaction vessel, and the pH was adjusted to 4 with hydrochloric acid aqueous solution. The mixture was stirred at 65°C for 10 hours. 4.5 kg of KH-567 was added to the reaction vessel in 8 portions, followed by 1.05 kg of deionized water. The pH was adjusted to 4 with hydrochloric acid aqueous solution, and the mixture was stirred at 65°C for 10 hours to obtain the reaction solution. The resulting reaction solution was distilled under reduced pressure to remove excess ethanol, water, and reaction byproducts, yielding an organic-inorganic hybrid epoxy ceramic resin. Example

[0028] An adhesive for underwater repair of pressurized pipelines comprises component A and component B in a mass ratio of 100:70. Component A consists of the following raw materials: 7.5 kg of organic-inorganic hybrid epoxy ceramic resin, 0.15 kg of γ-aminopropyltrimethoxysilane, 1.2 kg of core-shell toughening agent EPX-125, 0.2 kg of reactive diluent ethylene glycol diglycidyl ether, and 1.2 kg of cerium oxide. Component B consists of the following raw materials: 2.5 kg of curing agent SF-SX-3326A, 0.06 kg of di(γ-trimethoxysilylpropyl)amine, and 2.5 kg of talc. Take 7 kg of component A and 4.9 kg of component B to form an adhesive for underwater repair of pressurized pipelines; The organic-inorganic hybrid epoxy ceramic resin is obtained from phenyltriethoxysilane, tetraethyl silicate, and KH-567 through hydrolysis and dehydration condensation reactions; the specific steps are as follows: 22.2 kg of anhydrous ethanol, 3.3 kg of phenyltriethoxysilane, and 3.3 kg of tetraethyl silicate were added to a reaction vessel, and stirring was started. The mixture was stirred for 12 minutes. While stirring, 0.9 kg of deionized water was added to the reaction vessel, and the pH was adjusted to 2.5 with hydrochloric acid aqueous solution. The mixture was stirred at 58°C for 11 hours. 3.9 kg of KH-567 was added to the reaction vessel in 6 portions. Then, 0.95 kg of deionized water was added to the reaction vessel, and the pH was adjusted to 3 with hydrochloric acid aqueous solution. The mixture was stirred at 58°C for 11 hours to obtain the reaction solution. The resulting reaction solution was distilled under reduced pressure to remove excess ethanol, water, and reaction byproducts to obtain an organic-inorganic hybrid epoxy ceramic resin. Example

[0029] An adhesive for underwater repair of pressurized pipelines comprises component A and component B in a mass ratio of 100:65. Component A consists of the following raw materials: 8.5 kg of organic-inorganic hybrid epoxy ceramic resin, 0.25 kg of γ-aminopropyltrimethoxysilane, 1 kg of core-shell toughening agent MX-153, 0.4 kg of core-shell toughening agent MX-154, 0.3 kg of reactive diluent butyl glycidyl ether, 0.1 kg of benzyl glycidyl ether, 0.7 kg of hollow glass microspheres, and 0.7 kg of cement. Component B consists of the following raw materials: 5 kg of curing agent T-31, 2 kg of curing agent LSW-523, 0.09 kg of di(γ-trimethoxysilylpropyl)amine, 2 kg of talc, and 1.6 kg of cerium oxide. The adhesive for underwater repair of pressurized pipelines is prepared by combining 11 kg of component A and 7.15 kg of component B. The cerium oxide has a particle size of 30~100μm and its surface is treated with silane coupling agent UM-08; The organic-inorganic hybrid epoxy ceramic resin is obtained from phenyltriethoxysilane, tetraethyl silicate, and KH-567 through hydrolysis and dehydration condensation reactions; the specific steps are as follows: 22.8 kg of anhydrous ethanol, 3.6 kg of phenyltriethoxysilane, and 3.6 kg of tetraethyl silicate were added to a reaction vessel, and stirring was started. The mixture was stirred for 18 minutes. While stirring, 1.35 kg of deionized water was added to the reaction vessel, and the pH was adjusted to 3.5 with hydrochloric acid aqueous solution. The mixture was stirred at 62°C for 10.5 hours. 4.2 kg of KH-567 was added to the reaction vessel in 6 portions. Then, 1 kg of deionized water was added to the reaction vessel, and the pH was adjusted to 2.5 with hydrochloric acid aqueous solution. The mixture was stirred at 62°C for 11.5 hours to obtain the reaction solution. The resulting reaction solution was distilled under reduced pressure to remove excess ethanol, water, and reaction byproducts to obtain an organic-inorganic hybrid epoxy ceramic resin. Example

[0030] An adhesive for underwater repair of pressurized pipelines, wherein component A is composed of the following raw materials: 7.8 kg of organic-inorganic hybrid epoxy ceramic resin, 0.18 kg of γ-aminopropyltrimethoxysilane, 0.6 kg of core-shell toughening agent MX-154, 0.7 kg of core-shell toughening agent EPX-125, 0.2 kg of reactive diluent benzyl glycidyl ether, 0.1 kg of ethylene glycol diglycidyl ether, 0.8 kg of talc, and 0.6 kg of cerium oxide; component B is composed of the following raw materials: 3 kg of curing agent SF-SX-5253, 0.07 kg of di(γ-trimethoxysilylpropyl)amine, and 2.5 kg of hollow glass microspheres; 8 kg of component A and 6 kg of component B are used to form the adhesive for underwater repair of pressurized pipelines. The cerium oxide has a particle size of 30~100μm and its surface is treated with silane coupling agent UM-08; The organic-inorganic hybrid epoxy ceramic resin is obtained from phenyltriethoxysilane, tetraethyl silicate, and KH-567 through hydrolysis and dehydration condensation reactions; the specific steps are as follows: 17.76 kg of anhydrous ethanol, 2.64 kg of phenyltriethoxysilane, and 2.88 kg of tetraethyl silicate were added to a reaction vessel, and stirring was started. The mixture was stirred for 18 minutes. While stirring, 0.84 kg of deionized water was added to the reaction vessel, and the pH was adjusted to 2.5 with hydrochloric acid aqueous solution. The mixture was stirred at 60 °C for 11 hours. 3.12 kg of KH-567 was added to the reaction vessel in 6 portions, followed by 0.78 kg of deionized water. The pH was adjusted to 3 with hydrochloric acid aqueous solution, and the mixture was stirred at 62 °C for 10.5 hours to obtain the reaction solution. The resulting reaction solution was distilled under reduced pressure to remove excess ethanol, water, and reaction byproducts, yielding an organic-inorganic hybrid epoxy ceramic resin. Example

[0031] An adhesive for underwater repair of pressurized pipelines, wherein component A is composed of the following raw materials: 8 kg of organic-inorganic hybrid epoxy ceramic resin, 0.2 kg of γ-aminopropyltrimethoxysilane, 0.7 kg of core-shell toughening agent MX-153, 0.7 kg of core-shell toughening agent EPX-125, 0.2 kg of reactive diluent ethylene glycol diglycidyl ether, 1 kg of hollow glass microspheres, and 0.5 kg of talc; and component B is composed of the following raw materials: 3 kg of curing agent LSW-523, 2 kg of curing agent SF-SX-3326A, 0.08 kg of di(γ-trimethoxysilylpropyl)amine, and 3 kg of graphene oxide; 11 kg of component A and 7.7 kg of component B are used to form the adhesive for underwater repair of pressurized pipelines. The organic-inorganic hybrid epoxy ceramic resin is obtained from phenyltriethoxysilane, tetraethyl silicate, and KH-567 through hydrolysis and dehydration condensation reactions; the specific steps are as follows: 21 kg of anhydrous ethanol, 3.36 kg of phenyltriethoxysilane, and 3.08 kg of tetraethyl silicate were added to a reaction vessel, and stirring was started. After stirring for 15 minutes, 0.84 kg of deionized water was added to the reaction vessel while stirring, and the pH was adjusted to 3 with hydrochloric acid aqueous solution. The mixture was stirred at 60°C for 11 hours. 3.64 kg of KH-567 was added to the reaction vessel in 8 portions, followed by 0.9 kg of deionized water. The pH was adjusted to 3 with hydrochloric acid aqueous solution, and the mixture was stirred at 60°C for 11 hours to obtain the reaction solution. The resulting reaction solution was distilled under reduced pressure to remove excess ethanol, water, and reaction byproducts to obtain an organic-inorganic hybrid epoxy ceramic resin. Example

[0032] The preparation method of the adhesive for underwater repair of pressurized pipelines as described in Example 1 includes the following steps: ① Preparation of component A: 7 kg of organic-inorganic hybrid epoxy ceramic resin, 0.1 kg of γ-aminopropyltrimethoxysilane, 1 kg of core-shell toughening agent MX-153, 0.1 kg of reactive diluent butyl glycidyl ether and 1 kg of hollow glass microspheres were added to a planetary stirrer and stirred for 5 minutes to mix evenly. The mixture was then stirred under vacuum for 30 minutes and discharged to obtain component A. ② Preparation of component B: Add 2 kg of curing agent T-31, 0.05 kg of bis(γ-trimethoxysilylpropyl)amine and 2 kg of cement to a planetary mixer, mix for 5 minutes to mix evenly, vacuum mix for 30 minutes, and discharge to obtain component B; ③ Adhesive preparation: When using, mix 6 kg of component A and 3.6 kg of component B evenly to obtain an adhesive for underwater repair of pressurized pipelines. Example

[0033] The preparation method of the adhesive for underwater repair of pressurized pipelines described in Example 2 includes the following steps: ① Preparation of component A: 9 kg of organic-inorganic hybrid epoxy ceramic resin, 0.3 kg of γ-aminopropyltrimethoxysilane, 1.5 kg of core-shell toughening agent MX-154, 0.5 kg of reactive diluent benzyl glycidyl ether, and 2 kg of talc powder were added to a planetary mixer and stirred for 10 minutes to mix evenly. The mixture was then stirred under vacuum for 60 minutes and discharged to obtain component A. ② Preparation of component B: Add 8 kg of curing agent LSW-523, 0.1 kg of bis(γ-trimethoxysilylpropyl)amine and 4 kg of graphene oxide to a planetary mixer, stir for 10 minutes to mix evenly, vacuum stir for 60 minutes, and discharge to obtain component B; ③ Adhesive preparation: When using, take 13 kg of component A and 10.4 kg of component B and mix them evenly to obtain an adhesive for underwater repair of pressurized pipelines. Example

[0034] The preparation method of the adhesive for underwater repair of pressurized pipelines described in Example 3 includes the following steps: ① Preparation of component A: 7.5 kg of organic-inorganic hybrid epoxy ceramic resin, 0.15 kg of γ-aminopropyltrimethoxysilane, 1.2 kg of core-shell toughening agent EPX-125, 0.2 kg of reactive diluent ethylene glycol diglycidyl ether, and 1.2 kg of cerium oxide were added to a planetary stirrer and stirred for 6 minutes to mix evenly. The mixture was then stirred under vacuum for 40 minutes and discharged to obtain component A. ② Preparation of component B: Add 2.5 kg of curing agent SF-SX-3326A, 0.06 kg of di(γ-trimethoxysilylpropyl)amine and 2.5 kg of talc to a planetary mixer, stir for 8 minutes to mix evenly, vacuum stir for 50 minutes, and discharge to obtain component B; ③ Adhesive preparation: When using, take 7 kg of component A and 4.9 kg of component B and mix them evenly to obtain an adhesive for underwater repair of pressurized pipelines. Example

[0035] The preparation method of the adhesive for underwater repair of pressurized pipelines described in Example 4 includes the following steps: ① Preparation of Component A: 8.5 kg of organic-inorganic hybrid epoxy ceramic resin, 0.25 kg of γ-aminopropyltrimethoxysilane, 1 kg of core-shell toughening agent MX-153, 0.4 kg of core-shell toughening agent MX-154, 0.3 kg of reactive diluent butyl glycidyl ether, 0.1 kg of benzyl glycidyl ether, 0.7 kg of hollow glass microspheres, and 0.7 kg of cement were added to a planetary mixer and stirred for 8 minutes to mix evenly. The mixture was then vacuum stirred for 45 minutes, and the material was discharged to obtain Component A. ② Preparation of component B: Add 5 kg of curing agent T-31, 2 kg of curing agent LSW-523, 0.09 kg of bis(γ-trimethoxysilylpropyl)amine, 2 kg of talc powder and 1.6 kg of cerium oxide into a planetary mixer, stir for 6 minutes to mix evenly, vacuum stir for 50 minutes, and discharge to obtain component B; ③ Adhesive preparation: When using, take 11 kg of component A and 7.15 kg of component B and mix them evenly to obtain an adhesive for underwater repair of pressurized pipelines. Example

[0036] The preparation method of the adhesive for underwater repair of pressurized pipelines as described in Example 5 includes the following steps: ① Preparation of Component A: 7.8 kg of organic-inorganic hybrid epoxy ceramic resin, 0.18 kg of γ-aminopropyltrimethoxysilane, 0.6 kg of core-shell toughening agent MX-154, 0.7 kg of core-shell toughening agent EPX-125, 0.2 kg of reactive diluent benzyl glycidyl ether, 0.1 kg of ethylene glycol diglycidyl ether, 0.8 kg of talc, and 0.6 kg of cerium oxide were added to a planetary mixer and stirred for 7 minutes to mix evenly. The mixture was then stirred under vacuum for 40 minutes, and the material was discharged to obtain Component A. ② Preparation of component B: Add 3 kg of curing agent SF-SX-5253, 0.07 kg of bis(γ-trimethoxysilylpropyl)amine and 2.5 kg of hollow glass microspheres to a planetary stirrer, stir for 8 minutes to mix evenly, vacuum stir for 40 minutes, and discharge to obtain component B; ③ Adhesive preparation: When using, take 8 kg of component A and 6 kg of component B and mix them evenly to obtain an adhesive for underwater repair of pressurized pipelines. Example

[0037] The preparation method of the adhesive for underwater repair of pressurized pipelines as described in Example 6 includes the following steps: ① Preparation of Component A: 8 kg of organic-inorganic hybrid epoxy ceramic resin, 0.2 kg of γ-aminopropyltrimethoxysilane, 0.7 kg of core-shell toughening agent MX-153, 0.7 kg of core-shell toughening agent EPX-125, 0.2 kg of reactive diluent ethylene glycol diglycidyl ether, 1 kg of hollow glass microspheres, and 0.5 kg of talc powder were added to a planetary mixer and stirred for 8 minutes to mix evenly. The mixture was then vacuum stirred for 50 minutes, and the material was discharged to obtain Component A. ② Preparation of component B: Add 3 kg of curing agent LSW-523, 2 kg of curing agent SF-SX-3326A, 0.08 kg of bis(γ-trimethoxysilylpropyl)amine and 3 kg of graphene oxide to a planetary mixer, stir for 8 minutes to mix evenly, then vacuum stir for 50 minutes, and discharge to obtain component B; ③ Adhesive preparation: When using, take 11 kg of component A and 7.7 kg of component B and mix them evenly to obtain an adhesive for underwater repair of pressurized pipelines.

[0038] The performance of the adhesives for underwater repair of pressurized pipelines obtained in Examples 7-12 was tested. Underwater metal adhesion and lap shear strength were tested according to GB / T 7124; 24h Shore hardness was tested according to GB / T 531.1; tensile strength was tested according to ISO 527; heat distortion temperature was tested according to GB / T 3354; compressive strength was tested according to ASTM D695; non-volatile content was tested according to GB / T 2793; chemical resistance (10% NaOH / 10% HCl / 3.5% NaCl, 168h) was tested according to Q / SY GD 0215.1; and short-term survival test or similar pressure test was conducted according to ASME PCC-2-2018. The results are shown in Table 1.

[0039] Table 1 Performance test results of the adhesives for underwater repair of pressurized pipelines obtained in Examples 7-12

[0040] As can be seen from the results in Table 1, the adhesive for underwater repair of pressurized pipelines of the present invention is a two-component solvent-free environmentally friendly adhesive with good adhesion, good underwater workability, fast curing speed, high bonding strength, excellent sealing performance, corrosion resistance and good durability. It is particularly suitable for emergency repair and permanent repair of underwater pipelines under pressurized conditions.

Claims

1. An adhesive for underwater repair of pressurized pipelines, characterized in that: The product is composed of component A and component B in a mass ratio of 100:60~80. By weight, component A consists of the following raw materials: 70~90 parts of organic-inorganic hybrid epoxy ceramic resin, 1~3 parts of γ-aminopropyltrimethoxysilane, 10~15 parts of core-shell toughening agent, 1~5 parts of reactive diluent, and 10~20 parts of first filler. Component B consists of the following raw materials: 20~80 parts of curing agent, 0.5~1 parts of di(γ-trimethoxysilylpropyl)amine, and 20~40 parts of second filler. The organic-inorganic hybrid epoxy ceramic resin is obtained by hydrolysis and dehydration condensation reaction of phenyltriethoxysilane, tetraethyl silicate and KH-567.

2. The adhesive for underwater repair of pressurized pipelines according to claim 1, characterized in that: The organic-inorganic hybrid epoxy ceramic resin was prepared according to the following steps: By weight, 145-155 parts of anhydrous ethanol, 20-25 parts of phenyltriethoxysilane, and 20-25 parts of tetraethyl silicate were added to a reaction vessel. The vessel was stirred for 10-20 minutes. While stirring, 5-10 parts of deionized water were added to the reaction vessel, and the pH was adjusted to 2-4 with hydrochloric acid aqueous solution. The mixture was stirred at 55-65°C for 10-12 hours. 25-30 parts of KH-567 were added to the reaction vessel in 5-8 portions. Then, 6-7 parts of deionized water were added to the reaction vessel, and the pH was adjusted to 2-4 with hydrochloric acid aqueous solution. The mixture was stirred at 55-65°C for 10-12 hours to obtain a reaction solution. The resulting reaction solution was distilled under reduced pressure to remove excess ethanol, water, and reaction byproducts to obtain an organic-inorganic hybrid epoxy ceramic resin.

3. The adhesive for underwater repair of pressurized pipelines according to claim 1, characterized in that: The core-shell toughening agent is one or two of MX-153, MX-154 or EPX-125.

4. The adhesive for underwater repair of pressurized pipelines according to claim 1, characterized in that: The active diluent is one or two of butyl glycidyl ether, benzyl glycidyl ether, or ethylene glycol diglycidyl ether.

5. The adhesive for underwater repair of pressurized pipelines according to claim 1, characterized in that: The curing agent is one or two of T-31, LSW-523, SF-SX-3326A or SF-SX-5253.

6. The adhesive for underwater repair of pressurized pipelines according to claim 1, characterized in that: The first filler is one or two of hollow glass microspheres, cement, talc, cerium oxide, or graphene oxide; the second filler is one or two of hollow glass microspheres, cement, talc, cerium oxide, or graphene oxide.

7. The adhesive for underwater repair of pressurized pipelines according to claim 1, characterized in that: The cerium oxide has a particle size of 30~100μm and its surface is treated with silane coupling agent UM-08.

8. The method for preparing an adhesive for underwater repair of pressurized pipelines as described in claim 1, characterized in that: Includes the following steps: ① Preparation of component A: By weight, 70-90 parts of organic-inorganic hybrid epoxy ceramic resin, 1-3 parts of γ-aminopropyltrimethoxysilane, 10-15 parts of core-shell toughening agent, 1-5 parts of reactive diluent and 10-20 parts of first filler are added to a planetary stirrer and stirred for 5-10 minutes to mix evenly. The mixture is then stirred under vacuum for 30-60 minutes, and the material is discharged to obtain component A. ② Preparation of component B: Add 20-80 parts of curing agent, 0.5-1 parts of di(γ-trimethoxysilylpropyl)amine and 20-40 parts of second filler to a planetary mixer, stir for 5-10 minutes to mix evenly, vacuum stir for 30-60 minutes, and discharge to obtain component B; ③ Adhesive preparation: When using, mix component A and component B evenly at a mass ratio of 100:60~80 to obtain an adhesive for underwater repair of pressurized pipelines.

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