Multifunctional integrated viscoelastic body anti-corrosion adhesive, adhesive tape and preparation method of multifunctional integrated viscoelastic body anti-corrosion adhesive

Abstract

The invention discloses a multifunctional integrated viscoelastic body anti-corrosion adhesive, an adhesive tape and a preparation method of the multifunctional integrated viscoelastic body anti-corrosion adhesive. The viscoelastic body anti-corrosion adhesive is prepared from the following components in parts by weight: 35 to 50 parts of a gradient molecular weight polyisobutene composite system, 5 to 10 parts of organic montmorillonite-nano hydroxyapatite composite filler, 12 to 20 parts of modified silicate, 10 to 15 parts of fluoro-acrylate and 3 to 5 parts of a silane coupling agent. The viscoelastic body anti-corrosion adhesive tape disclosed by the invention can realize oil bonding under the condition that the surface has slight greasy dirt, the greasy dirt and floating rust on the surface do not need to be thoroughly cleaned, and the application range of the viscoelastic body anti-corrosion adhesive tape is expanded, so that the viscoelastic body anti-corrosion adhesive tape can be applied for a long time within the temperature range of 70 DEG C below zero to 80 DEG C and can be applied to greasy dirt environments and chemical media for a long time; meanwhile, the anti-corrosion, sealing and anti-impact functions are achieved, multiple functions are integrated, the construction efficiency is improved, and the construction cost is reduced.

Description

A multifunctional integrated viscoelastic anti-corrosion adhesive, tape, and preparation method thereof Technical Field

[0001] This invention relates to the field of corrosion protection technology for humid environments and oily surfaces, and particularly to a multifunctional integrated viscoelastic anticorrosive adhesive, tape, and preparation method. Background Technology

[0002] Viscoelastics are flexible polymeric anti-corrosion materials. Their unique cold-flow characteristics give them excellent waterproof sealing properties and outstanding adhesion, effectively bonding to various substrates. They have been widely used in pipeline and steel structure anti-corrosion fields. However, existing technologies have obvious limitations in application scenarios: 1. Poor adaptability: Existing viscoelastic anti-corrosion materials all require the substrate to be thoroughly degreased; otherwise, the peel strength will drop significantly or even cause the viscoelastic material to dissolve. However, in scenarios such as offshore platforms and old pipelines, the substrate surface is prone to slight oil stains, making it difficult to meet the pretreatment requirements and preventing the viscoelastic material from bonding and sealing. 2. Low self-shear force: Due to the introduction of a large amount of medium molecular weight polyisobutylene into existing viscoelastic materials, the adhesive layer is relatively soft and has low self-shear force, making it prone to interlayer shear peeling under external force. Other solutions introduce high molecular weight polyisobutylene, which can improve its own shear strength, but will significantly reduce its compatibility with fillers, resulting in uneven mixing and reduced anti-corrosion performance; 3. Single function: Existing underwater anti-corrosion materials do not integrate impact resistance or have poor impact resistance. They are easily damaged and rendered ineffective by waves, marine organisms and offshore equipment construction, requiring additional impact resistance layers, which increases construction costs and process complexity. Summary of the Invention

[0003] To address the technical problems of existing viscoelastic anticorrosion materials, such as limited functionality, high requirements for substrate pretreatment, and poor impact resistance, this invention provides a multifunctional integrated viscoelastic anticorrosion adhesive, tape, and preparation method. This invention possesses synergistic functions of water absorption, water retention, impact resistance, and long-lasting anticorrosion, making it suitable for various scenarios including humid environments and oily pipelines.

[0004] In a first aspect, the present invention provides a multifunctional integrated viscoelastic anticorrosive adhesive, which is achieved by the following technical solution.

[0005] A multifunctional integrated viscoelastic anticorrosive adhesive comprises the following components in parts by weight: 35-50 parts of a gradient molecular weight polyisobutylene composite system, 5-10 parts of an organomontmorillonite-nanohydroxyapatite composite filler, 12-20 parts of modified silicate, 10-15 parts of fluoroacrylate, and 3-5 parts of silane coupling agent.

[0006] Furthermore, the gradient molecular weight polyisobutylene composite system includes dimolecular weight polyisobutylene and hydroxyl-terminated polyisobutylene, with a mass ratio of dimolecular weight polyisobutylene to hydroxyl-terminated polyisobutylene of (30~42):(5~8).

[0007] Furthermore, the dimolecular weight polyisobutylene includes medium molecular weight polyisobutylene with a molecular weight of 35,000 to 45,000 and high molecular weight polyisobutylene with a molecular weight of 85,000 to 95,000, with a mass ratio of (18 to 25): (12 to 17).

[0008] Furthermore, the molecular weight of hydroxyl-terminated modified polyisobutylene is 2000~5000.

[0009] Furthermore, the organic montmorillonite-nano hydroxyapatite composite filler is composed of modified sodium montmorillonite and nano hydroxyapatite with a particle size of 50~80nm, and the mass ratio of modified sodium montmorillonite to nano hydroxyapatite is (6~9):(4~6).

[0010] Furthermore, the modified silicate is composed of natural kaolin and modified nano silica sol, with a mass ratio of natural kaolin to modified nano silica sol of (8~14):(4~6).

[0011] Furthermore, the modified nano-silica sol is obtained by modifying nano-silica sol with γ-aminopropyltriethoxysilane.

[0012] Furthermore, the fluoroacrylate is a perfluoroalkyl ethyl acrylate.

[0013] Secondly, the present invention provides a multifunctional integrated viscoelastic anti-corrosion tape, which is achieved by the following technical solution.

[0014] A multifunctional integrated viscoelastic anticorrosive tape includes a flexible adhesive layer made of the aforementioned viscoelastic anticorrosive adhesive, and an anti-sticking release film and a fiber composite material respectively disposed on both sides of the flexible adhesive layer.

[0015] Furthermore, the thickness of the flexible adhesive layer is 3-5 mm; preferably 3 mm, 3.5 mm, 4 mm, 4.5 mm, or 5 mm, and more preferably, the thickness of the flexible adhesive layer is 3.5 mm.

[0016] Furthermore, the anti-stick release film is a PET release film or a PE release film; the thickness of the anti-stick release film is 0.5~1mm, preferably 0.5mm, 0.7mm, 0.8mm, 0.9mm, or 1mm. More preferably, the anti-stick release film is a 0.5mm PET release film.

[0017] Furthermore, the fiber composite material is a water-curing fiber composite material, which cures in a humid environment. Specifically, the water-curing fiber composite material is composed of any one of glass fiber cloth and non-woven fabric, combined with a water-curing epoxy adhesive or a polyurethane adhesive.

[0018] Thirdly, the present invention provides a method for preparing a multifunctional integrated viscoelastic anti-corrosion tape, which is achieved by the following technical solution.

[0019] A method for preparing the above-mentioned multifunctional integrated viscoelastic anticorrosion tape includes the following steps: S1. Melting the polyisobutylene composite system: Medium and high molecular weight polyisobutylene and hydroxyl-terminated modified polyisobutylene are melted and stirred at 90~95℃ for 30 minutes; S2. Pre-treatment of fillers: Organomontmorillonite-nanohydroxyapatite composite filler and modified silicate are dried and dispersed; S3. Mixing and dispersing: Organomontmorillonite-nanohydroxyapatite composite filler and modified silicate are added to the melt system of step S1 and mixed at 110~125℃ for 2.5~3.5 hours; S4. Adding fluoroacrylate and silane coupling agent: Cooling to 70~80℃, adding fluoroacrylate and silane coupling agent, and stirring evenly; S5. Molding and extruding into sheets: The anti-sticking release film and fiber composite material are respectively coated on both sides of the adhesive layer to form a multifunctional integrated viscoelastic anticorrosion tape.

[0020] S6. Packaging: After the anti-corrosion tape is rolled up, it is placed in an aluminum foil bag and sealed to prevent the fiber composite material from curing before use.

[0021] Fourthly, the present invention provides a method for using a multifunctional integrated viscoelastic anti-corrosion tape, which is achieved by the following technical solution.

[0022] A method for using a multifunctional integrated viscoelastic anti-corrosion tape includes the following steps: (1) Grinding the surface of the steel substrate to remove loose rust, loose impurities and oxide scale; (2) Unpacking the aluminum foil tape containing the multifunctional integrated viscoelastic anti-corrosion tape, soaking it thoroughly with water, taking out the tape, peeling off the anti-sticking release film on the inner surface, wrapping it once in place, and then spirally wrapping the tape with a 50% overlap. After it is fully cured, it can achieve integrated anti-corrosion and impact resistance.

[0023] The present application has the following beneficial effects: 1. The multifunctional integrated viscoelastic anticorrosion adhesive and tape of the present invention can quickly react with the water adsorbed by the organomontmorillonite by introducing nano-hydroxyapatite to form a hydroxyapatite-aluminosilicate composite gel, which has higher shear strength and higher peel strength, and fully resists the longitudinal slippage of the anticorrosion layer caused by ice cones falling in winter; 2. The multifunctional integrated viscoelastic anticorrosion adhesive and tape of the present invention can improve the initial tack through the combined action of hydroxyl-terminated modified low molecular weight polyisobutylene and silane coupling agent, so that it can achieve good adhesion even on slightly oily substrates. Furthermore, the gradient molecular weight polyisobutylene used ensures that the material does not become brittle at -70℃ and does not flow or drip at 80℃. Simultaneously, the introduction of nano-silica sol improves the compatibility between polyisobutylene and the powder, solving the problem of insufficient mixing of high molecular weight polyisobutylene and powder. 3. This invention's multifunctional integrated viscoelastic anticorrosion adhesive and tape introduces fluorine-containing groups for the first time, enhancing the anticorrosion material's resistance to oil, solvents, and seawater erosion, solving the problem that viscoelastic anticorrosion materials cannot be used in oil and solvent environments. 4. This invention's multifunctional integrated viscoelastic anticorrosion tape integrates water-curing reinforcing fiber composite materials and is sealed in packaging. After unpacking, it can be wrapped to achieve complete coverage. The reinforcing fiber composite material on the outer surface can be cured by water or water molecules in the air, achieving multiple functions in one, including anticorrosion, sealing, oil resistance, and external protection, eliminating the need for secondary construction of the outer protective layer and achieving cost reduction and efficiency improvement. Detailed Implementation

[0024] The present patent application will be further described below with reference to the embodiments. Unless otherwise specified, the materials used in the preparation process in the following embodiments have not undergone further processing and have been commercially available.

[0025] The commercially available information of the raw materials used in the following embodiments of this application is as follows: medium molecular weight polyisobutylene (manufacturer: Shandong Hongrui New Material Technology Co., Ltd., model: HRD350, viscosity-average molecular weight 35,000~45,000); high molecular weight polyisobutylene (manufacturer: Shandong Hongrui New Material Technology Co., Ltd., model: HRD850, viscosity-average molecular weight 85,000~95,000); hydroxyl-terminated modified polyisobutylene (manufacturer: Xi'an Ruixi Biotechnology Co., Ltd., model: PIB-2OH, viscosity-average molecular weight 2,000~5,000); perfluoroalkyl ethyl acrylate (manufacturer: Shanghai Freon Chemical Co., Ltd., model: FR-EHA); nano hydroxyapatite (manufacturer: Nanjing Epuri Nanomaterials Co., Ltd., model: EP-HAP-50, particle size 50~80nm); modified sodium montmorillonite (manufacturer: Zhejiang Fenghong New Material Co., Ltd., model: DK-4); natural kaolin (manufacturer: Suzhou Zhongfei Kaolin) (The following text appears to be a list of chemical products and their components, possibly related to a chemical company and its products: SK-1, modified nano-silica sol; SN-30; modified nano-silica sol obtained by γ-aminopropyltriethoxysilane modification, specific modification methods are described in "Research Progress on Surface Modification and Application of Silica Sol. Li Jie, Chen Lianxi, Zhang Zhongming, Jiao Caibin. China Inorganic Salts (Special Issue). 2012 National Inorganic Silicon Compounds Industry Annual Meeting and Further Implementation of Industry "Adjustment of Structure, Transformation of Mode, and Stable Growth" Seminar. 2012, 166-168, 3 pages); Silane coupling agent (Nanjing Shuguang Chemical Group Co., Ltd., model: KH-550); PET release film (Chenying Packaging Technology (Shanghai Co., Ltd.), model: PET-05, thickness 0.5mm); Water molecule curing fiber composite material (Nanjing Shuangwei Technology New Material Co., Ltd., model: EWR330, thickness 1.0mm).)

[0026] Example 1 The multifunctional integrated viscoelastic anticorrosive adhesive of this example includes 18 kg of medium molecular weight polyisobutylene, 12 kg of high molecular weight polyisobutylene, 5 kg of hydroxyl-terminated modified polyisobutylene, 10 kg of organomontmorillonite-nanohydroxyapatite composite filler, 15 kg of modified silicate, 10 kg of fluoroacrylate, and 3 kg of silane coupling agent.

[0027] The tape preparation method of this embodiment includes the following steps: 1. Melting of the polyisobutylene composite system: 18 kg of medium molecular weight polyisobutylene, 12 kg of high molecular weight polyisobutylene and 5 kg of hydroxyl-terminated modified polyisobutylene are added to a dual planetary mixer (model: HY-DLH5L, manufacturer: Guangzhou Hongyun Mixing Equipment Co., Ltd.), and melted and stirred at 95°C, 60 r / min, and 2000 r / min for 30 minutes; 2. Filler pretreatment: 6 kg of modified sodium montmorillonite and 4 kg of nano hydroxyapatite are combined to form a composite material. The composite filler and 15 kg of modified silicate (11 kg of natural kaolin and 4 kg of modified nano silica sol) were placed in a 105℃ constant temperature drying oven (model: TH-01-250, manufacturer: Cypress Tianyu Test Equipment (Chengdu) Co., Ltd.) and dried for 4 hours. Then, they were dispersed for 15 minutes at 2000 r / min using a high-speed disperser (model: CLSFS-1.1, manufacturer: Chiler (Shanghai) Machinery Technology Co., Ltd.). 3. Mixing and dispersion: The pretreated composite filler and modified silicate were added to the above-mentioned melt. The system was heated to 120℃, rotated at 60 rpm, and dispersed at 3000 rpm; then mixed in a mixer for 3 hours. 4. Fluoroacrylate and silane coupling agent were added: the temperature was lowered to 75℃, 10 kg of perfluoroalkyl ethyl acrylate and 3 g of silane coupling agent were added, and the mixture was stirred in a dual planetary mixer at 60 rpm and 2000 rpm for 30 minutes until homogeneous. 5. Molding: the mixture was extruded into sheets using a twin-screw extruder (model: SHJ-35, manufacturer: Nanjing Keerte Machinery Manufacturing Co., Ltd.). (Thickness 2.5mm), screw speed 30r / min, barrel temperature zone 1 80℃, zone 2 90℃, zone 3 100℃, die head temperature 110℃; the coating production line (model: RTB-2J-350, manufacturer: Xuteng Machinery Co., Ltd., Ruian City, Zhejiang Province, China) coats 0.5mm thick PET anti-stick release film and 1.0mm thick water molecule curing fiber composite material on both sides of the adhesive layer to produce a multi-functional integrated viscoelastic anti-corrosion tape with a flexible adhesive layer thickness of 3.5mm; the die head temperature setting parameters of the coating machine are all 80℃.

[0028] Example 2: The multifunctional integrated viscoelastic anticorrosive adhesive of this example includes 25 kg of medium molecular weight polyisobutylene, 17 kg of high molecular weight polyisobutylene, 8 kg of hydroxyl-terminated modified polyisobutylene, 10 kg of organomontmorillonite-nanohydroxyapatite composite filler (5 kg of modified sodium montmorillonite and 5 kg of nanohydroxyapatite), 15 kg of modified silicate (11 kg of natural kaolin and 4 kg of modified nano silica sol), 20 kg of fluoroacrylate, and 5 kg of silane coupling agent.

[0029] The tape preparation method in this embodiment is the same as that in Example 1.

[0030] Example 3: The multifunctional integrated viscoelastic anticorrosive adhesive of this example includes 20 kg of medium molecular weight polyisobutylene, 15 kg of high molecular weight polyisobutylene, 6 kg of hydroxyl-terminated modified polyisobutylene, 8 kg of organomontmorillonite-nanohydroxyapatite composite filler (4 kg of modified sodium montmorillonite and 4 kg of nanohydroxyapatite), 15 kg of modified silicate (11 kg of natural kaolin and 4 kg of modified nano silica sol), 10 kg of fluoroacrylate, and 5 kg of silane coupling agent.

[0031] The tape preparation method in this embodiment is the same as that in Example 1.

[0032] Comparative Example 1: The formulation of the multifunctional integrated viscoelastic anticorrosive adhesive in this comparative example is the same as that in Example 1, except that hydroxyl-terminated modified polyisobutylene and silane coupling agent are not added.

[0033] The tape preparation method in this comparative example is the same as that in Example 1.

[0034] Comparative Example 2: The formulation of the multifunctional integrated viscoelastic anticorrosive adhesive in this comparative example is the same as that in Example 1, except that nano-hydroxyapatite is not added.

[0035] The tape preparation method in this comparative example is the same as that in Example 1.

[0036] Comparative Example 3: The formulation of the multifunctional integrated viscoelastic anticorrosive adhesive in Comparative Example 3 is the same as that in Example 1, except that fluoroacrylate is not added.

[0037] The tape preparation method of this comparative example is the same as that of Example 1, except that the surface layer is not covered with fiber composite material.

[0038] The tapes prepared in Examples 1-3 and Comparative Examples 1-3 were wrapped with the tapes in a state where the surface contained water and oil, and tested after 48 hours. The specific test results are as follows: The results above show that the flexible adhesive layer prepared by Examples 1-3 has the ability to directly bond to oily and damp surfaces, can be used for a long time in oily and chemical media environments, and has an impact resistance of up to 25J without damage.

[0039] The embodiments described herein are preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Therefore, all equivalent changes made in accordance with the structure, shape, and principle of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A multifunctional integrated viscoelastic anti-corrosion adhesive, characterized in that: The product comprises the following components in parts by weight: 35-50 parts of gradient molecular weight polyisobutylene composite system, 5-10 parts of organomontmorillonite-nanohydroxyapatite composite filler, 12-20 parts of modified silicate, 10-15 parts of fluoroacrylate, and 3-5 parts of silane coupling agent.

2. The multifunctional integrated viscoelastic anti-corrosion adhesive according to claim 1, characterized in that: The gradient molecular weight polyisobutylene composite system includes dimolecular weight polyisobutylene and hydroxyl-terminated polyisobutylene, with a mass ratio of dimolecular weight polyisobutylene to hydroxyl-terminated polyisobutylene of (30~42):(5~8).

3. The multifunctional integrated viscoelastic anti-corrosion adhesive according to claim 2, characterized in that: The dimolecular weight polyisobutylene includes medium molecular weight polyisobutylene with a molecular weight of 35,000 to 45,000 and high molecular weight polyisobutylene with a molecular weight of 85,000 to 95,000, with a mass ratio of (18 to 25): (12 to 17).

4. The multifunctional integrated viscoelastic anti-corrosion adhesive according to claim 2, characterized in that: The molecular weight of hydroxyl-terminated modified polyisobutylene is 2000~5000.

5. The multifunctional integrated viscoelastic anti-corrosion adhesive according to claim 1, characterized in that: The organic montmorillonite-nano hydroxyapatite composite filler is composed of modified sodium montmorillonite and nano hydroxyapatite with a particle size of 50~80nm. The mass ratio of modified sodium montmorillonite to nano hydroxyapatite is (6~9):(4~6).

6. The multifunctional integrated viscoelastic anti-corrosion adhesive according to claim 1, characterized in that: The modified silicate is composed of natural kaolin and modified nano silica sol, with a mass ratio of natural kaolin to modified nano silica sol of (8~14):(4~6).

7. The multifunctional integrated viscoelastic anti-corrosion adhesive according to claim 1, characterized in that: Fluoroacrylates are perfluoroalkyl ethyl acrylates.

8. A multifunctional integrated viscoelastic anti-corrosion tape, characterized in that, It includes a flexible adhesive layer made of any of the viscoelastic anticorrosive adhesives described in claims 1-7, and an anti-sticking release film and a fiber composite material respectively disposed on both sides of the flexible adhesive layer.

9. The multifunctional integrated viscoelastic anti-corrosion tape according to claim 8, characterized in that, The thickness of the flexible adhesive layer is 3-5 mm; the anti-sticking release film is a PET release film or a PE release film; the fiber composite material is a water molecule curing fiber composite material.

10. A method for preparing the multifunctional integrated viscoelastic anti-corrosion tape according to claim 8 or 9, characterized in that: Includes the following steps: S1. Melting the polyisobutylene composite system: Melt and stir medium and high molecular weight polyisobutylene and hydroxyl-terminated modified polyisobutylene at 90~95℃ for 30 minutes; S2. Pretreatment of fillers: Dry and disperse the organomontmorillonite-nanohydroxyapatite composite filler and modified silicate; S3. Mixing and dispersing: Add the organomontmorillonite-nanohydroxyapatite composite filler and modified silicate to the melt system of step S1, and mix at 110~125℃ for 2.5~3.5 hours; S4. Adding fluoroacrylate and silane coupling agent: Cool to 70~80℃, add fluoroacrylate and silane coupling agent, and stir evenly; S5. Molding and extruding into sheets: Cover the anti-sticking release film and fiber composite material on both sides of the adhesive layer to make a multifunctional integrated viscoelastic anti-corrosion tape.

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