Composite flexible asphalt-based anticorrosion patch and preparation method thereof

Abstract

The present application relates to a kind of composite flexible asphalt-based anticorrosion paste and its preparation method, the composite flexible asphalt-based anticorrosion paste of the present application is divided into four layers, respectively, hydrophobic barrier layer, high-temperature resistant anticorrosion cloth, low-temperature flexible anticorrosion adhesive layer and release film, hydrophobic barrier layer includes barrier layer A, barrier layer B, barrier layer C, barrier layer D and barrier layer E connected in sequence.Release film is the adhesive layer protection film before construction, when construction, tear off, low-temperature flexible anticorrosion adhesive layer is pasted with traffic barrier wall.The product of the present application has high adhesive force, can low-temperature construction, high and low temperature resistance, not afraid of freeze-thaw, aging resistance, salt resistance, ultraviolet resistance, acid and alkali corrosion resistance, waterproof and multiple performance, effectively prevent the penetration of chloride ion and salt water, prevent the corrosion of snow-melting agent to cement concrete crash barrier, make crash barrier anticorrosion maintenance interval extend to 3-5 years or more.In low temperature state, the product can be well adhered to crash barrier, and the apparent color of material does not change after snow-melting agent corrosion.

Description

Technical Field

[0001] This invention belongs to the field of highway maintenance technology, and in particular relates to a composite flexible asphalt-based anti-corrosion patch and its preparation method. Background Technology

[0002] Cement concrete crash barriers on highways and municipal road bridges often suffer from defects such as peeling, flaking, exposed aggregate, grooves, exposed reinforcement, and damage. Over the years, maintenance units have tried various repair solutions using different materials and processes. However, these solutions are time-consuming, labor-intensive, and costly, and cannot be applied in low-temperature winter conditions. Some materials have solved the problem of corrosion from de-icing agents, such as the applicant's previous invention patent application, "A Salt-Resistant Anti-Corrosion Adhesive for Highway Cement Crane Barriers and Its Manufacturing and Construction Method" (application number 202311273909X). This patent discloses an anti-corrosion adhesive with a modified asphalt material in the middle layer. This material has good adhesion, can stick to the surface of the cement crash barrier, is salt-resistant, UV-resistant, and heat-resistant, and can effectively prevent the cement crash barrier from being corroded by de-icing agents in winter. However, it still suffers from reduced flexibility and insufficient adhesion in low-temperature winter conditions, making it impossible to apply. Furthermore, under the corrosive effects of de-icing agents in winter and the high temperatures and sunlight in summer, the material's appearance is prone to discoloration and a large color difference from the cement wall surface, resulting in mottled colors on the cement wall. Summary of the Invention

[0003] In response to the above problems, especially the low winter temperatures, large temperature differences between winter and summer, and the extensive use of de-icing agents in recent years, the applicant, based on its previous technology and leveraging the technical advantages of asphalt-based self-adhesive materials, as well as the research and development concepts of energy conservation, environmental protection, convenient construction, cost reduction, and aesthetic durability, has abandoned the rigid material anti-corrosion approach and provided a composite flexible asphalt-based anti-corrosion sticker with a color close to that of a cement crash barrier. This solves the problems of anti-corrosion materials being susceptible to aging, cracking, peeling, and delamination in winter, while also addressing the issues of color difference between the material's surface and the cement crash barrier, color discoloration after prolonged exposure, and the inability to apply the material in winter. Furthermore, it further improves the adhesion between the material and the cement substrate.

[0004] A composite flexible bitumen-based anti-corrosion patch comprises, in sequence, a hydrophobic barrier layer, a high-temperature resistant anti-corrosion cloth, a low-temperature flexible anti-corrosion adhesive layer, and a release film connected to each other.

[0005] The hydrophobic barrier layer includes barrier layer A, barrier layer B, barrier layer C, barrier layer D and barrier layer E connected in sequence. The total thickness of the hydrophobic barrier layer is 0.3mm-0.8mm, preferably 0.5mm. The thickness of the hydrophobic barrier layer is not limited to 0.3mm-0.8mm, and can also be other thicknesses.

[0006] The barrier layer A is obtained by spraying the following hot-melt material onto the high-temperature resistant anti-corrosion cloth and then curing it: 45%-60% hydroxyl polyester resin, 5%-10% organic solvent, 20%-30% chlorinated rubber, 2%-4% methyltrimethoxysilane, and 15%-20% isocyanate adduct, without the thickness of the high-temperature resistant anti-corrosion cloth. The thickness of the barrier layer A is 0.05mm-0.15mm. It mainly serves to prevent corrosion, oil, petroleum solvents, and petroleum products, while preventing the black material of the anti-corrosion adhesive layer from penetrating the high-temperature resistant anti-corrosion cloth and preventing the black color from showing.

[0007] The barrier layer B is a ceramic micro powder layer adhered to the barrier layer A, with a thickness of 0.07mm-0.2mm. It mainly serves to prevent corrosion, oil, petroleum solvents and petroleum products, while preventing the black material of the anti-corrosion bonding layer from penetrating the high-temperature anti-corrosion cloth and preventing the black color from showing.

[0008] The barrier layer C is obtained by spraying the following hot-melt material onto the barrier layer B and then curing it: 65%-80% chlorinated polyethylene resin, 5%-10% organic solvent, 2%-4% methyltrimethoxysilane, 0.5%-1% mineral pigment, 2%-6% hydrogenated SBS, and 5%-12% additives. The additives consist of the following components in parts by weight: heat stabilizer: plasticizer: antioxidant = 15:20:50, with a thickness of 0.1mm-0.25mm. They enhance the material's resistance to acid, alkali, and salt corrosion, as well as its resistance to extreme cold, high temperatures, and aging. They also adjust the material's color to closely resemble that of a cement crash barrier, resulting in a more aesthetically pleasing finish after construction.

[0009] The barrier layer D is a TPE film containing 2%-6% epoxy powder, which is laminated onto the barrier layer C by hot pressing. The thickness is 0.08mm-0.2mm, which enhances the tensile strength and elongation at break of this anti-corrosion patch, while also giving the material wear resistance, oil resistance and resistance to ozone and radiation.

[0010] The barrier layer E is an epoxy resin composite material layer sprayed onto the surface of the barrier layer D, with a thickness of 0.05mm-0.1mm, which enhances the chemical corrosion resistance of the material and improves its resistance to acid, alkali and salt corrosion, hydrophobicity and resistance to petroleum solvents.

[0011] The high-temperature resistant and corrosion-resistant fabric is woven from polyurethane thermoplastic elastomer (TPU) yarn, with a weight of 65g or 80g per square meter. The thickness of the 65g fabric is 0.05mm ± 0.01mm, and the thickness of the 80g fabric is 0.06mm ± 0.01mm.

[0012] The low-temperature flexible anti-corrosion adhesive layer is composed of the following materials and their weight percentages:

[0013] Petroleum asphalt 40%-60%, polyurethane 10%-18%, linear silicone oil 0.1%-0.5%, rubber oil 1%-3%, SBS 2%-5%, radial tire powder 12%-25%, high clay 1%-5%, kaolin 1%-3%, naphthenic oil 0.5%-2%, aromatic oil 1%-3%, silane coupling agent 0.5%-2%, pour point depressant 1%-3%, glass fiber 3%-7%.

[0014] The total thickness of the hydrophobic barrier layer is 0.3mm-0.8mm, preferably 0.5mm, wherein the thickness of barrier layer A is 0.05mm-0.15mm; the thickness of barrier layer B is 0.07mm-0.2mm; the thickness of barrier layer C is 0.1mm-0.25mm; the thickness of barrier layer D is 0.08mm-0.2mm; and the thickness of barrier layer E is 0.05mm-0.1mm.

[0015] The thickness of the anti-corrosion adhesive layer is 1.0mm-2mm.

[0016] The release film is a low-tack PE protective film with a thickness of 0.03mm ± 0.003mm and a peel strength of 10-20g / cm.

[0017] The material in the epoxy resin composite coating layer is Amo 370 (AP370PLC).

[0018] The ceramic micro powder layer contains ceramic micro powder particles with a size of 1000 mesh or larger.

[0019] The mineral pigments are composed of three types of mineral pigments: black, white, and gray, with a weight ratio of black:white:gray = 1-1.1:5-6:2-3. In application, colorists will make fine adjustments during the production process based on the color of the crash barrier provided by the customer to achieve a color closer to the customer's cement crash barrier.

[0020] The heat stabilizer is a calcium-zinc composite stabilizer; the plasticizer is dibutyl phthalate; and the antioxidant is BASF antioxidant 1330.

[0021] The isocyanate adduct is an aliphatic isocyanate adduct.

[0022] The organic solvent is an alcohol-based organic solvent. Methanol, ethanol, or isopropanol are preferred.

[0023] TPE film containing 2%-6% epoxy powder.

[0024] The polyurethane is a polyurea-type polyurethane.

[0025] The linear silicone oil is a low-viscosity dimethyl silicone oil with a viscosity of 130±10 mPa·s.

[0026] The radial tire powder is radial tire powder with a mesh size of 1000 or higher.

[0027] The high-clay and kaolin are high-clay and kaolin powders with a mesh size of 800 or higher.

[0028] The silane coupling agent is silane coupling agent KH550 (3-aminopropyltriethoxysilane).

[0029] The glass fiber is alkali-resistant glass fiber.

[0030] The preparation method of the above-mentioned composite flexible bitumen-based anticorrosion patch includes the following steps:

[0031] 1) Preparation of the hydrophobic barrier layer:

[0032] After the barrier layer A material is hot-melted, mixed, ground, and then sprayed onto the high-temperature resistant and anti-corrosion cloth, ceramic micro powder is adhered to the barrier layer A through an isolation circulation box before curing. Unadhered powder is then blown off to form barrier layer B, which is then cured in a curing box. The barrier layer C material is hot-melted and sprayed onto barrier layer B to form a new barrier layer C. After barrier layer C is cured, a TPE film containing epoxy powder is laminated onto barrier layer C by hot pressing to form a new barrier layer D. Finally, Amo 370 (AP370PLC) is sprayed onto barrier layer D to form a new barrier layer E.

[0033] 2) Preparation of low-temperature flexible anti-corrosion adhesive layer:

[0034] The prepared material is applied and rolled onto the side opposite to the high-temperature resistant and anti-corrosion cloth and the barrier layer A. At the same time, the release film is applied to the other side of the adhesive layer.

[0035] The preparation method of barrier layer A and barrier layer B is as follows: 45%-60% of hydroxyl polyester resin is melted and stirred, and 5%-10% of organic solvent is added. At a constant temperature of 60℃-80℃, 20%-30% of chlorinated rubber, 2%-4% of methyltrimethoxysilane, and 15%-20% of isocyanate adduct are added successively. After mixing and grinding, the mixture is sprayed onto a high-temperature resistant and anti-corrosion cloth to form barrier layer A. Before barrier layer A is cured, ceramic micro powder is adhered to barrier layer A in an isolation circulation box, and the unadhered powder is blown off to form barrier layer B. Then, it is placed in a curing box for curing.

[0036] The dry film thickness of the barrier layer A is ≥0.05mm, and the spraying amount is 0.03-0.12kg / ㎡.

[0037] The amount of ceramic micro powder used in the barrier layer B is 0.05-0.15 kg / m², and it is blown off as an adhesive powder before the barrier layer A is cured.

[0038] The barrier layer C is prepared as follows: 65%-80% chlorinated polyethylene resin is melted and then 5%-10% organic solvent is added. The temperature is kept constant below 60°C. Then, 2%-4% methyltrimethoxysilane D20, 0.5%-1% mineral pigment, 2%-6% hydrogenated SBS, and 5%-12% additives (stabilizer:plasticizer:antioxidant = 15:20:50) are added sequentially and sprayed onto the barrier layer B that adheres to the ceramic powder. The dry film thickness is ≥0.1mm, the spraying amount is 0.1-0.2kg / m², the surface drying time is 30min at 25°C, and the actual drying time is 1-2h, forming a new barrier layer C.

[0039] Amo 370 (AP370PLC) is sprayed onto barrier layer D to form a new barrier layer E. The dry film thickness is ≥0.05mm, the spraying amount is 0.03-0.12kg / ㎡, the surface drying time is 30min at 25℃, and the complete drying time is 1-2h.

[0040] The preparation method of the low-temperature flexible anti-corrosion adhesive layer is as follows: First, the petroleum asphalt is instantly heated to 190°C through a high-temperature heat exchanger and then put into a premixing tank and uniformly mixed with radial tire powder, high clay, kaolin, glass fiber and SBS. After mixing, the temperature is 160°C-180°C, and then pumped into a reaction vessel. The reaction is carried out in the reaction vessel for 40min-60min, while the mixture in the reaction vessel is ground 3-5 times through a colloid mill.

[0041] After mixing evenly, gradually reduce the temperature of the mixture to 60℃-80℃, and add aromatic oil, rubber oil, linear silicone oil, silane coupling agent KH, polyurethane, naphthenic oil, and pour point depressant in sequence. Stir at a constant temperature for 60 minutes, and after mixing evenly, pump it into the coating molding equipment and coat and press it onto the surface of the high temperature resistant and anti-corrosion cloth.

[0042] This invention discloses a composite flexible asphalt-based anti-corrosion patch with multiple properties, including high adhesion, low-temperature application capability, resistance to high and low temperatures, freeze-thaw resistance, aging resistance, salt resistance, UV protection, acid and alkali corrosion resistance, and waterproofing. It effectively prevents the penetration of chloride ions and salt water, inhibits the corrosion of cement concrete crash barriers by de-icing agents, and extends the anti-corrosion maintenance interval of the crash barriers to 3-5 years or more. Even at low temperatures, this product adheres well to the crash barrier, and its surface color remains unchanged after corrosion by de-icing agents.

[0043] A composite flexible asphalt-based anti-corrosion patch can maintain flexibility and certain adhesion properties even at low ambient temperatures of 40 degrees Celsius (-40℃), and can also be applied normally at ambient temperatures below 0 degrees Celsius.

[0044] A composite flexible asphalt-based anti-corrosion patch consists of four layers and can be stored in rolls. The four layers are a hydrophobic barrier layer, a high-temperature resistant anti-corrosion fabric, a low-temperature flexible anti-corrosion adhesive layer, and a release film. The release film serves as a protective film for the adhesive layer before construction; it is removed during construction, and the low-temperature flexible anti-corrosion adhesive layer is then adhered to the cement crash barrier. Because the other three layers are flexible, they possess excellent adhesion, aging resistance, high and low temperature resistance, and the ability to prevent acid, alkali, and salt corrosion.

[0045] The high-temperature resistant and anti-corrosion cloth is a woven fabric, mainly made of modified polyurethane thermoplastic elastomer (TPU) yarns. Reinforcing threads are added in both the warp and weft directions, with a spacing of 2mm-10mm between the reinforcing threads. The high-temperature resistant and anti-corrosion cloth has excellent oil resistance and cold resistance, and sufficient resistance to ozone, oxygen, and radiation. It also has excellent ozone resistance, heat aging resistance, UV aging resistance, and good low-temperature performance.

[0046] The hydrophobic barrier layer is further divided into barrier layer A, barrier layer B, barrier layer C, barrier layer D, and barrier layer E, which are connected in sequence.

[0047] The main functions of barrier layer A and barrier layer B (ceramic micro powder) are to provide corrosion protection, oil resistance, and resistance to petroleum solvents and petroleum products, while preventing the black material of the anti-corrosion bonding layer from penetrating the high-temperature anti-corrosion cloth and preventing the black material from showing.

[0048] Barrier layer C enhances the material's resistance to acid, alkali, and salt corrosion, as well as its resistance to extreme cold, high temperatures, and aging. It also allows for adjustment of the material's color to closely resemble that of a cement crash barrier, resulting in a more aesthetically pleasing finish after construction.

[0049] The composite of barrier layer D enhances the tensile strength and elongation at break of this anti-corrosion patch, while also giving the material wear resistance, oil resistance, and resistance to ozone and radiation.

[0050] The composite of barrier layer E enhances the material's resistance to chemical corrosion, and improves its resistance to acid, alkali, and salt corrosion, as well as its hydrophobic and petroleum solvent resistance.

[0051] The hydrophobic barrier layer is attached to the high-temperature resistant and anti-corrosion fabric. It is composed of multiple layers with a total thickness of 0.3mm-0.8mm. Each layer has excellent performance. After the multiple layers are combined, the performance of each layer is enhanced and complement each other. This makes the material block the penetration of ultraviolet rays, oils, acids, alkalis, salts, and common chemicals. It has better resistance to ultraviolet rays, high and low temperatures, and moisture. The composite material is hydrophobic and does not stick to rainwater.

[0052] The hydrophobic barrier layer is mainly composed of epoxy powder, amoxicillin 370 (AP370PLC), ceramic micro powder of 1000 mesh or higher, mineral pigments, isocyanate adducts, chlorinated polyethylene resin, hydroxyl-containing polyester resin, chlorinated rubber, hydrogenated SBS, additives, organic solvents, methyltrimethoxysilane D20, TPE film, etc., and is compounded in multiple ways. It has good chemical resistance, water resistance, acid and alkali resistance, mineral oil resistance, petroleum solvent resistance, acid, alkali and salt corrosion resistance, strong adhesion, and toughness.

[0053] The epoxy powder is a thermosetting, non-toxic coating that, after curing, forms a high-molecular-weight cross-linked coating with excellent chemical corrosion resistance and high mechanical properties, especially superior wear resistance and adhesion.

[0054] The aforementioned Amo 370 (AP370PLC) consists of two components, A (white) and B (black), which cure to a light gray color. After spraying, Amo 370 (AP370PLC) forms a long-term chemical barrier, blocking most chemicals, including caustic soda, dilute acids, salt solutions, water, and petroleum solvents. It also provides UV protection. This material has been successfully applied to the corrosion protection of concrete and metal pipes.

[0055] The additives include heat stabilizers, plasticizers, and antioxidants. Heat stabilizers help improve the high-temperature stability of chlorinated polyethylene during processing; calcium-zinc composite stabilizers are commonly used. Plasticizers help reduce intermolecular forces, improve plasticity and softness, and reduce the difficulty of spraying; dibutyl phthalate is commonly used. Antioxidants help inhibit and delay the oxidation and degradation of materials; BASF antioxidant 1330 is commonly used. In this invention, the preferred ratio of the three materials is: stabilizer: plasticizer: antioxidant = 15:20:50.

[0056] The ceramic micro powder with a mesh size of 1000 or higher is a lightweight non-metallic multifunctional material. Its main components are SiO2 and Al2O3. It has low density, good dispersibility, and strong adsorption. It has good weather resistance, durability, corrosion resistance, and high temperature resistance. Importantly, it has high hiding power, which can reduce film permeability, prevent the black seepage of the anti-corrosion adhesive layer, and prevent the material from yellowing.

[0057] The mineral pigments are composed of black, white, and gray mineral pigments. The mineral pigments have stable chemical properties and can maintain color stability for a long time. The weight ratio of black:white:gray is 1-1.1:5-6:2-3. In application, colorists will make fine adjustments to the color of the crash barrier provided by the customer during the production process to achieve a color closer to the customer's cement crash barrier.

[0058] The isocyanate adducts are classified into aromatic isocyanates, aliphatic isocyanates, and alicyclic isocyanates, with aliphatic isocyanate adducts being preferred. These include, but are not limited to, trimethylhexamethylene diisocyanate (TMDI), a colorless to pale yellow transparent liquid with the molecular formula C11H18N2O2, catalog number CD115118, a relative density of 1.17, and an NCO content of 12.5%–13.5%. In this application, it is used as a curing agent and adhesive. The isocyanate adducts polymerized with hydroxyl-containing polyester resins are used in cement products, exhibiting good chemical resistance, water resistance, acid and alkali resistance, and resistance to petroleum solvents and petroleum products.

[0059] The chlorinated polyethylene resin maintains good physical properties within a temperature range of -30℃ to 120℃. It exhibits good oil and chemical resistance, high thermal stability and cold resistance, and good resistance to most chemicals such as acids, alkalis, salts, and oils, particularly demonstrating outstanding resistance to mineral oils and fuel oils.

[0060] The hydroxyl polyester resin, also known as saturated hydroxylated polyester resin, has the molecular formula VOK-2776-TS and model number VOK-2776-TS. Its superior performance is attributed to specific functional groups in its molecular structure, with the hydroxyl group (-OH) being a key component. Raw materials for introducing hydroxyl groups include polyols and hydroxy acids. The hydroxyl polyester resin incorporates hydroxyl groups into the polyester resin molecular chain through an esterification reaction. The hydroxyl groups used are primarily glycolic acid, a type of hydroxy acid. The introduction of hydroxyl groups significantly improves the polyester resin's chemical resistance, UV resistance, and adhesion.

[0061] The chlorinated rubber is a mixture of trichloride and tetrachloride with a chlorine content of 65%, formed by chlorinating natural rubber. Its general structural formula is [C10H11Cl7]N. The introduction of chlorinated rubber can improve toughness, adhesion, solvent resistance, acid and alkali resistance, water resistance, salt spray resistance, and abrasion resistance, as well as increase the film's drying rate and reduce dust adhesion.

[0062] The hydrogenated SBS, SBS (Styrene-Butadiene-Styrene), is a styrene-butadiene-styrene block copolymer and a commonly used additive in modified asphalt. Modified asphalt with added SBS exhibits better crack resistance, abrasion resistance, and high-temperature stability, thus extending the service life of the asphalt. Moderate directional hydrogenation of SBS in the presence of a catalyst can improve the material's temperature resistance, with its embrittlement temperature reaching below -60°C. The good solubility, miscibility, and oil-extending properties of hydrogenated SBS enhance its stability and aging resistance when mixed with other materials. SBS is produced by hydrogenating the double bonds to saturate them, thus hydrogenating the polybutadiene segments into polyethylene (E) and polybutene (B) segments, abbreviated as SEBS. Many domestic manufacturers produce SEBS.

[0063] The additives include heat stabilizers, plasticizers, and antioxidants. Heat stabilizers help improve the high-temperature stability of chlorinated polyethylene during processing; calcium-zinc composite stabilizers are commonly used. Plasticizers help reduce intermolecular forces, improve plasticity and softness, and reduce the difficulty of spraying; dibutyl phthalate is commonly used. Antioxidants help inhibit and delay the oxidation and degradation of materials; BASF antioxidant 1330 is commonly used. In this invention, the preferred ratio of the three materials is stabilizer:plasticizer:antioxidant = 15:20:50.

[0064] The organic solvent is preferably an alcohol compound such as methanol, ethanol, and isopropanol. Isopropanol is more preferred. Isopropanol has the molecular formula C3H8O, is a colorless and transparent liquid with an odor similar to a mixture of ethanol and acetone, a melting point of -89.5℃, a boiling point of 82.5℃, and a relative density of 0.786 g / mL. It is soluble in organic solvents such as water, ethanol, ether, acetone, and benzene, and can participate in various chemical reactions, such as esterification, etherification, and oxidation. It can be oxidized to acetone and can also be used to produce isopropene through a dehydration reaction.

[0065] The methyltrimethoxysilane D20, a colorless liquid, is a trifunctional organosilane coupling agent. The conventional addition amount is 0.5% to 4%, and the preferred amount in this application is 2% to 4%. It is used to improve the heat distortion temperature of the product and enhance its mechanical, electrical, and processing properties. Methyltrimethoxysilane D20 is used as a conditioning agent to reinforce plastic laminates to improve the mechanical strength, heat resistance, and moisture resistance of the product.

[0066] The TPE film described above incorporates epoxy powder. TPE films exhibit excellent wear resistance, oil resistance, and cold resistance, and possess sufficient resistance to ozone, oxygen, and radiation. Furthermore, as an elastomer, they possess high tensile strength and elongation at break. This invention utilizes a TPE film incorporating thermosetting epoxy powder, meaning that epoxy powder is added during the TPE film production process. This further enhances the TPE film's corrosion resistance, weather resistance, and acid and alkali resistance. Additionally, the material with the added TPE film does not easily yellow after prolonged exposure to sunlight and strong ultraviolet radiation.

[0067] The flexible anti-corrosion adhesive layer is 1mm-2mm thick. It has the characteristics of not flowing at high temperatures above 100℃ and not becoming brittle at low temperatures of -40℃. Even at -40℃, it still has good flexibility and adhesion, can resist the oxidation and thermal aging caused by environmental temperature, can adapt to the thermal expansion and contraction of cement crash barriers, and can offset the damage of the high-temperature anti-corrosion cloth and hydrophobic barrier layer caused by the tensile stress of cement crash barriers.

[0068] The material composition of the flexible anti-corrosion bonding layer is as follows: petroleum asphalt 40%-60%, polyurethane 10%-18%, linear silicone oil 0.1%-0.5%, rubber oil 1%-3%, SBS 2%-5%, radial tire powder 15%-25%, high clay 1%-5%, kaolin 1%-3%, naphthenic oil 0.5%-2%, aromatic oil 1%-3%, silane coupling agent KH 0.5%-2%, pour point depressant 1%-3%, and glass fiber 3%-7%.

[0069] The petroleum asphalt mentioned is conventional heavy-duty road petroleum asphalt, generally 70#, but 90#, 120# or other types of asphalt can be selected according to different specifications.

[0070] The polyurethane, a single-component polyurethane, is a macromolecule containing repeating urethane groups (-NHCOO) on its main chain. There are many types of polyurethane; this application uses a polyurea-type polyurethane, obtained through silicone modification. Silicone-modified polyurethane adhesives not only improve flexibility but also avoid the foaming problems common in traditional polyurethane adhesives during curing. They also possess advantages such as thermal stability, water resistance, weather resistance, corrosion resistance, non-toxicity, odorlessness, and biocompatibility.

[0071] The linear silicone oil is a colorless, odorless, and transparent oily liquid. As an additive, linear silicone oil has high temperature resistance and weather resistance. In this application, a low-viscosity dimethyl silicone oil with a viscosity of 130±10 mPa·s is used, which mainly serves to reduce surface tension. Other types of silicone oil can also be tried.

[0072] The rubber oil is preferably KN4010 rubber oil, which has a good softening and dispersing effect, making the mixture soft and smooth, and improving the material's cold resistance, scorching prevention and slowing properties.

[0073] SBS (Styrene-Butadiene-Styrene) is a styrene-butadiene-styrene block copolymer, which is a commonly used additive in modified asphalt. Modified asphalt with added SBS has better crack resistance, wear resistance and high temperature stability, thereby extending the service life of asphalt.

[0074] The radial tire powder with a mesh size of 1000 or higher is a tire rubber powder, preferably made from the tread of waste large truck tires through a freeze-grinding process. Rubber powder made from other parts of tires or other types of tires can also be used, but the application effect will be lower.

[0075] The high-clay and kaolin are white powders made from non-metallic minerals. Their main component is silicon dioxide (SiO2), which has strong adsorption and bonding force, excellent suspension properties, and good corrosion resistance. High-clay and kaolin powders with a mesh size of 800 or higher are preferred. The larger the mesh size, the better the application effect, but the higher the cost.

[0076] The naphthenic oil is a petroleum fraction with naphthenes as the main component. It is used as a filler oil. Naphthenic oil is inexpensive and has high solubility, excellent low-temperature performance, good compatibility with resins and polymers, and good plasticizing and miscibility with rubber. In this application, it can improve the low-temperature performance of materials, improve the flexibility of materials at low temperatures, and also improve the plasticity and elasticity of raw materials such as polyurethane and radial tire powder.

[0077] The aromatic oil, also known as aromatic hydrocarbon or aromatic hydrocarbon, is a hydrocarbon compound containing a benzene ring structure in its molecular structure. It exhibits good compatibility with radial tire powder, providing light oil components that aid in the mixing and dispersion of fillers in the rubber compound. This improves the material's resistance to weathering, oxidation, abrasion, and aging. Aromatic oils possess excellent rubber compatibility, high-temperature resistance, and low volatility, significantly improving the processing performance of rubber and enhancing the resistance of rubber products to weathering, oxidation, friction, and aging. This application preferably uses high-viscosity aromatic oils with a low aniline point. These types of aromatic oils can adjust asphalt viscosity, improve the tensile strength and elongation at break of the material, and exhibit good compatibility with radial tire powder, thus improving the processability of the material used in this application.

[0078] The silane coupling agent KH is a bonding promoter, preferably 3-aminopropyltriethoxysilane. In this application, it can improve the dispersibility of polyurethane materials and their adhesion to glass fibers, cement materials, stone, etc. KH550 is preferred in this application, which can greatly improve the flexural strength, tensile strength and shear strength of the mixture in this application.

[0079] The pour point depressant, also known as low-temperature flow improver PPD, is mainly used to slow down the hardening speed of asphalt. By reacting with the high molecular weight compounds in petroleum asphalt, it effectively reduces the viscosity and pour point of petroleum asphalt and improves its fluidity.

[0080] The glass fiber is an inorganic non-metallic material with good insulation, strong heat resistance, good corrosion resistance, and high mechanical strength. This application preferably uses AR glass fiber, also known as alkali-resistant glass fiber, which can effectively resist the erosion of cement concrete and high-alkali substances in the environment. It has strong adhesion, extremely high impact, tensile, and flexural strength, strong resistance to freezing, temperature and humidity changes, and excellent crack resistance and impermeability.

[0081] The release film is a low-adhesion PE protective film with a thickness of (0.03mm ± 0.003mm), a substrate (PE), a peel strength of (10-20g / cm), a temperature resistance of (60°C), and an elongation of (>400). Advantages: stable adhesion, good adhesion, excellent re-peeling performance, and no adhesive residue.

[0082] Preparation method:

[0083] Barrier Layer A: During the application process, 45%-60% hydroxyl polyester resin is melted and stirred, then 5%-10% organic solvent is added. At a constant temperature of 60℃-80℃, 20%-30% chlorinated rubber, 2%-4% methyltrimethoxysilane D20, and 15%-20% isocyanate adduct are added sequentially. After mixing and grinding, the mixture is sprayed onto the high-temperature resistant and corrosion-resistant fabric. This coating is referred to as Barrier Layer A. Barrier Layer A, once formed, is tough and possesses excellent weather resistance, chemical resistance, acid and alkali corrosion resistance, resistance to petroleum solvents and petroleum products, and good impact resistance. The dry film thickness is ≥0.05mm, and the spraying amount is 0.03-0.12kg / ㎡.

[0084] Before curing, ceramic micropowder of 1000 mesh or finer is adhered to barrier layer A in a certain proportion in an isolation circulation chamber, and the unadhered powder is blown off to form barrier layer B. Then, it enters the curing chamber, and after barrier layer A has cured, it proceeds to the next stage. The ceramic micropowder layer protects the surface from contact with strong chemicals, preventing chemical corrosion, and also has a certain temperature buffering effect, preventing sudden cooling and heating of the material.

[0085] After the ceramic micropowder of barrier layer A (barrier layer B) has been adhered and cured, 65%-80% chlorinated polyethylene resin is melted and then 5%-10% organic solvent is added. The temperature is kept constant below 60℃, and then 2%-4% methyltrimethoxysilane D20, 0.5%-1% mineral pigment, 2%-6% hydrogenated SBS, and 5%-12% additives are added sequentially and sprayed onto the barrier layer B with the adhered ceramic powder. The dry film thickness is ≥0.1mm, the spraying amount is 0.18-0.3kg / ㎡, the surface drying time is 30min at 25℃, and the actual drying time is 1-2h, forming a new barrier layer, referred to as barrier layer C.

[0086] The sprayed barrier layer C has strong adhesion, good resistance to acid, alkali and salt corrosion, resistance to severe cold, high temperature and ultraviolet radiation, and excellent anti-aging properties. At the same time, it has good long-lasting resistance to the complex physical and chemical environment of cement anti-collision walls and outstanding resistance to alternating dry and wet conditions.

[0087] After the barrier layer C has cured, a TPE film containing 2%-6% epoxy powder is laminated onto the barrier layer C by hot pressing. The hot pressing temperature is not higher than 70℃, forming a new barrier layer, referred to as barrier layer D.

[0088] Finally, Amo 370 (AP370PLC) is sprayed onto barrier layer D, with a dry film thickness ≥0.05mm, a spraying amount of 0.02-0.12kg / ㎡, a surface drying time of 30min at 25℃, and a complete drying time of 1-2h, forming a new barrier layer, referred to as barrier layer E.

[0089] The flexible anti-corrosion adhesive layer is made by applying and rolling the prepared material onto the side opposite to the high-temperature anti-corrosion cloth and the barrier layer A. The application temperature is not higher than 60℃. At the same time as the application, the release film is laminated onto the other side of the adhesive layer.

[0090] In the production process of the flexible anti-corrosion bonding layer, the petroleum asphalt is first heated to 190°C instantaneously through a high-temperature heat exchanger and then put into a premixing tank. It is then uniformly added and mixed with radial tire powder, high clay, kaolin, glass fiber, and SBS. After mixing, the temperature does not exceed 180°C. After premixing, it is pumped into a reaction vessel and reacted in the reaction vessel for no less than 40 minutes. At the same time, the mixture in the reaction vessel is ground through a colloid mill no less than 3 times.

[0091] After stirring evenly, continue stirring to lower the temperature of the mixture to 60℃-80℃. Once the mixture in the reactor reaches this temperature range, add aromatic oil, rubber oil, linear silicone oil, silane coupling agent, polyurethane, naphthenic oil, and retarder in sequence. Stir at a constant temperature for 60 minutes, and after stirring evenly, pump it into the coating molding equipment.

[0092] After being processed by the coating and molding equipment, the main functional layer of a composite flexible asphalt-based anticorrosion film with a specified width and thickness is produced. After cooling to room temperature, it is rolled up, then heat-sealed with a film and stored for later use.

[0093] The release film is attached to the anti-corrosion adhesive layer and can be peeled off during construction. It is not easy to fall off and is easy to separate from the high-strength adhesive layer. It is not easy to break. It is usually made of materials such as PE film with a thickness of micron.

[0094] How to use:

[0095] 1) Use a wire brush to remove debris from the corner where the wall base meets the road surface, and then use a shoulder-mounted hair dryer to clean the wall surface and the base of the wall.

[0096] 2) The grooves in the wall need to be treated with quick-drying cement mortar to level the base layer. Peeling areas need to be cleaned with a wire brush to remove dust and dirt.

[0097] 3) Based on the width and length of the anti-corrosion sticker, flexibly adjust the number of personnel on the construction site, and place one employee at a distance of 1.5-2.0 meters. Each employee should carry the anti-corrosion sticker release film that has been removed beforehand to avoid losses caused by the high-adhesion anti-corrosion stickers accidentally sticking together after the release film is removed.

[0098] 4) Before applying the adhesive tape, peel off one-third of the release liner on a level surface. Then, at 1.5-meter intervals, each person holds the side with the release liner removed and applies the tape along the pre-marked baseline on the crash barrier.

[0099] 5) The order of pasting the anti-corrosion sticker on the wall: Starting from one end, gradually paste and press the sticker parallel to the other end along the marked baseline. After the top part is firmly pasted, slowly peel off two-thirds of the release film. One person peels the film while the other person uses their palm to push and press the anti-corrosion sticker from top to bottom on the wall to ensure that the anti-corrosion sticker is flat and there are no bulges or wrinkles. After that, check carefully again. If there are any areas that are not properly adhered or if there are any curled edges, use a roller or rubber mallet to press them firmly.

[0100] 6) Applying sealant: Apply sealant to both sides of the seams and edges of the anti-corrosion film, ensuring the sealant is parallel to the seams or edges of the anti-corrosion film.

[0101] 7) After the grout is pasted, apply sealant between the grout sheets to seal the edges, and use a special tool to smooth it out. After smoothing, a set thickness of sealant will be left.

[0102] 8) After smoothing, wait about 10 minutes before completely removing the grout.

[0103] 9) The base of the crash barrier and the road surface are also sealed with sealant. This can be done by pasting anti-corrosion tape on one side of the wall and not on the side of the road. In order to prevent salt water from seeping into the bottom of the crash barrier along the road surface gaps, a little more sealant needs to be injected at the inside corner. The width of the sealant should be about 5 cm. The construction should be flexible depending on the condition of the road surface and the corner. Attached Figure Description

[0104] Figure 1 The effect of the product of this invention in snow melting agent and brine soaking (soaking for 60 days). Detailed Implementation

[0105] To make the objectives, technical solutions, and advantages of this invention clearer, the following detailed embodiments further illustrate this invention.

[0106] Customization: The high-temperature resistant and corrosion-resistant fabric is woven from polyurethane thermoplastic elastomer (TPU) threads, weighing 65g per square meter. The width and length can be cut to size as needed.

[0107] The following materials are preferred commercially available materials.

[0108] Additive formulation (stabilizer: plasticizer: antioxidant = 15:20:50)

[0109] Hydroxy-coated polyester resin: Hydroxy-coated polyester resin is also called saturated hydroxylated polyester resin, with the molecular formula VOK-2776-TS and model number VOK-2776-TS.

[0110] Chlorinated rubber: a mixture of trichloride and tetrachloride with a chlorine content of 65%, with the general structural formula [C10H11Cl7]N.

[0111] Methyltrimethoxysilane D20, a colorless liquid, is a trifunctional organosilane coupling agent.

[0112] Isocyanate adduct: Trimethylhexamethylene diisocyanate (TMDI), colorless to pale yellow transparent liquid, molecular formula C11H18N2O2, catalog number: CD115118.

[0113] The mineral pigments are composed of three types of mineral pigments: black, white, and gray, with a weight ratio of black:white:gray = 1-1.1:5-6:2-3. In application, colorists will make fine adjustments during the production process based on the color of the crash barrier provided by the customer to achieve a color closer to the customer's cement crash barrier.

[0114] The epoxy resin composite material is Amo 370 (AP370PLC).

[0115] Petroleum asphalt: Conventional heavy-duty road petroleum asphalt, 70#.

[0116] Polyurethane: Polyurea-Urethane (PUU for short).

[0117] Linear silicone oil: Dimethyl silicone oil with a viscosity of 130±10 mPa.s is used.

[0118] Rubber oil: KN4010 rubber oil.

[0119] High clay and kaolin: High clay and kaolin powder with a mesh size of 800 or higher.

[0120] Naphthenic oil: A dark liquid with an aggressive odor, density 0.89–0.95. A petroleum fraction mainly composed of cycloalkanes.

[0121] Aromatic oil: Model 0012320123, is a brown, viscous liquid.

[0122] Silane coupling agent: Silane coupling agent KH550.

[0123] Pour point depressant: also known as low-temperature flow improver PPD (Pour Point Depressant), model PPD-1216.

[0124] The release film is a low-tack PE protective film with a thickness of (0.03mm±0.003), a substrate of PE, a peel strength of (10-20g / cm), a temperature resistance of (60°C), and an elongation of (>400).

[0125] Isopropanol was chosen as the organic solvent.

[0126] Example 1

[0127] Prepare a 1m wide high-temperature resistant anti-corrosion cloth as described in this application (the width can be adjusted according to the equipment if it is greater than 1m, and can be cut to the actual required width if it is less than 1m). Then, complete the composite of hydrophobic barrier layer and low-temperature flexible anti-corrosion adhesive layer on both sides of the anti-corrosion cloth.

[0128] Composite of hydrophobic barrier layers:

[0129] Barrier Layer A: During the application process, 54% hydroxyl polyester resin is melted and stirred, then 7% organic solvent is added. At a constant temperature of 75℃, 22% chlorinated rubber, 2% methyltrimethoxysilane D20, and 15% isocyanate adduct are added sequentially. After mixing and grinding, the mixture is sprayed onto the high-temperature resistant and corrosion-resistant fabric. This coating is referred to as Barrier Layer A. Barrier Layer A, once formed, is tough and possesses excellent weather resistance, chemical resistance, acid and alkali corrosion resistance, resistance to petroleum solvents and petroleum products, and good impact resistance. The dry film thickness is 0.09 mm, and the spraying amount is 0.09 kg / m².

[0130] Before curing, 1000-mesh ceramic powder is adhered to barrier layer A at a rate of 0.09 kg / m² in an isolation circulation chamber. Unadhered powder is then blown away to form barrier layer B. The layer is then placed in a curing chamber for 45 minutes. After barrier layer A has cured, the process proceeds to the next stage. The ceramic powder layer protects the surface from strong chemicals, preventing chemical corrosion and providing a temperature buffer to prevent sudden temperature changes. Barrier layer B has a thickness of 0.12 mm.

[0131] After the barrier layer A and the ceramic micro powder (barrier layer B) are adhered and cured, 71% chlorinated polyethylene resin is melted and 8% organic solvent is added. The mixture is kept at a constant temperature below 58℃, and then 4% methyltrimethoxysilane D20, 0.5% mineral pigment, 5.5% hydrogenated SBS, and 11% additive (stabilizer:plasticizer:antioxidant = 15:20:50) are added sequentially and sprayed onto the barrier layer B with the adhered ceramic powder. The spraying amount is 0.2 kg / m², the dry film thickness is 0.12 mm, and it is placed in an environment of 25℃ for 45 min to cure, forming a new barrier layer, referred to as barrier layer C.

[0132] The sprayed barrier layer C has strong adhesion, is cement gray in color, and has good resistance to acid, alkali and salt corrosion. It is also resistant to severe cold, high temperature and ultraviolet rays, and has excellent anti-aging properties. At the same time, it has good long-lasting resistance to the complex physical and chemical environment of cement anti-collision walls and outstanding resistance to alternating dry and wet conditions.

[0133] After the barrier layer C is cured, a TPE film containing 5% epoxy powder is laminated onto the barrier layer B by hot pressing at a temperature of 65°C to form a new barrier layer, referred to as barrier layer D. The thickness of barrier layer D after compression is 0.11 mm.

[0134] Finally, Amo 370 (AP370PLC) is sprayed onto barrier layer D with a coating amount of 0.05 kg / m² and a dry film thickness of 0.06 mm to form a new barrier layer, referred to as barrier layer E.

[0135] The total thickness of the hydrophobic barrier layer is 0.5 mm.

[0136] Composite of low-temperature flexible anti-corrosion adhesive layer:

[0137] The flexible anti-corrosion adhesive layer is formed by applying and rolling the prepared material onto the side opposite to the high-temperature anti-corrosion cloth and the barrier layer 1. The application temperature is 55℃. At the same time, the release film is laminated onto the other side of the adhesive layer.

[0138] During the production process, 46.8% petroleum asphalt is first heated to 190°C instantaneously through a high-temperature heat exchanger and then added to a premixing tank along with 21% radial tire powder, 3% high clay, 1% kaolin, 4% glass fiber, and 3% SBS. After mixing, the temperature is 178°C. The premixed mixture is then pumped into a reaction vessel and reacted for 40 minutes. Simultaneously, the mixture in the reaction vessel is ground three times through a colloid mill.

[0139] After stirring evenly, continue stirring to lower the temperature of the mixture to 78℃. Once the mixture in the reactor reaches this temperature range, add 1% aromatic oil, 1% rubber oil, 0.2% linear silicone oil, 0.5% silane coupling agent KH, 16% polyurethane, 0.5% naphthenic oil, and 2% pour point depressant in sequence. Stir at a constant temperature for 60 minutes. After stirring evenly, pump the mixture into a coating and molding equipment. After coating and rolling, the thickness is 1mm.

[0140] After being applied using a coating molding device, a cement-gray composite flexible asphalt-based anti-corrosion film is produced under low-temperature conditions. It is 1.5mm thick, 1m wide, and 10m long. After cooling to room temperature, it is rolled up, then heat-sealed with a film and stored for later use.

[0141] Example 2

[0142] Prepare a 1m wide high-temperature resistant and corrosion-resistant fabric as described in this application, and then apply a hydrophobic barrier layer and a low-temperature flexible corrosion-resistant adhesive layer to both sides of the fabric.

[0143] Composite of hydrophobic barrier layers:

[0144] Barrier Layer A: During the application process, 51% hydroxyl polyester resin is melted and stirred, then 6% organic solvent is added. At a constant temperature of 78℃, 23% chlorinated rubber, 3% methyltrimethoxysilane D20, and 17% isocyanate adduct are added sequentially. After mixing and grinding, the mixture is sprayed onto the high-temperature resistant and corrosion-resistant fabric. This coating is referred to as Barrier Layer A. Barrier Layer A, once formed, is tough and possesses excellent weather resistance, chemical resistance, acid and alkali corrosion resistance, resistance to petroleum solvents and petroleum products, and good impact resistance. The dry film thickness is 0.12 mm, and the coating amount is 0.1 kg / m².

[0145] Before curing, 1000-mesh ceramic powder is applied at a rate of 0.11 kg / m² to barrier layer A in an isolation circulation chamber. Unattached powder is then blown away to form barrier layer B. The chamber is then placed in a curing chamber and cured for 45 minutes. After barrier layer A has cured, the next step is performed. The cured barrier layer B has a thickness of 0.16 mm. The ceramic powder layer (barrier layer B) protects the surface from strong chemicals, preventing chemical corrosion, and provides a certain temperature buffer to prevent sudden temperature changes.

[0146] After the barrier layer A and ceramic micropowder (barrier layer B) are adhered and cured, 74% chlorinated polyethylene resin is melted and then 7% organic solvent is added. The mixture is kept at a constant temperature of 57°C. Then, 3% methyltrimethoxysilane D20, 0.6% mineral pigment prepared to be close to cement color, 5.4% hydrogenated SBS, and 10% additives are added sequentially and mixed. The mixture is then sprayed onto the barrier layer B with the adhered ceramic powder at a dosage of 0.15 kg / m². After curing for 45 minutes, a new barrier layer, referred to as barrier layer C, is formed with a thickness of 0.2 mm.

[0147] The sprayed barrier layer C has strong adhesion, good resistance to acid, alkali and salt corrosion, resistance to severe cold, high temperature and ultraviolet radiation, and excellent anti-aging properties. At the same time, it has good long-lasting resistance to the complex physical and chemical environment of cement anti-collision walls and outstanding resistance to alternating dry and wet conditions.

[0148] After the barrier layer C is cured, a TPE film containing 5% epoxy powder is laminated onto the barrier layer 2 by hot pressing at a temperature of 68°C to form a new barrier layer, referred to as barrier layer D, with a thickness of 0.1 mm after hot pressing.

[0149] Finally, Amo 370 (AP370PLC) was sprayed onto barrier layer D at a rate of 0.09 kg / m², cured for 45 minutes, and the cured layer was 0.08 mm thick, forming a new barrier layer, referred to as barrier layer E.

[0150] After lamination, the total thickness of the hydrophobic barrier layer is 0.66 mm.

[0151] Composite of low-temperature flexible anti-corrosion adhesive layer:

[0152] The flexible anti-corrosion adhesive layer is made by applying and rolling the prepared material onto the side opposite to the high-temperature anti-corrosion cloth and the barrier layer A. The application temperature is 50℃. At the same time, the release film is laminated onto the other side of the adhesive layer.

[0153] During the production process, 50.4% petroleum asphalt is first heated to 190°C instantaneously through a high-temperature heat exchanger and then introduced into a premixing tank. It is then uniformly mixed with 18% radial tire powder, 3% high clay, 1% kaolin, 5% glass fiber, and 2% SBS. After mixing, the temperature is 170°C. The premixed mixture is then pumped into a reaction vessel and reacted in the reaction vessel for 50 minutes. At the same time, the mixture in the reaction vessel is ground three times through a colloid mill.

[0154] After stirring evenly, continue stirring to lower the temperature of the mixture to 70℃. Once the mixture in the reactor reaches this temperature range, add 2% aromatic oil, 2% rubber oil, 0.3% linear silicone oil, 1.3% silane coupling agent KH, 11% polyurethane, 1% naphthenic oil, and 3% pour point depressant in sequence. Stir at a constant temperature for 60 minutes. After stirring evenly, pump the mixture into a coating and molding equipment. After coating and rolling, the thickness is 1.2mm.

[0155] After being applied using a coating molding device, a cement-gray composite flexible asphalt-based anti-corrosion film is produced under low-temperature conditions. It is 1m wide, 1.86mm thick, and 10m long. After cooling to room temperature, it is rolled up, then heat-sealed with a film and stored for later use.

[0156] Example 3

[0157] Prepare a 1m wide high-temperature resistant and corrosion-resistant fabric as described in this application, and then apply a hydrophobic barrier layer and a low-temperature flexible corrosion-resistant adhesive layer to both sides of the fabric.

[0158] Composite of hydrophobic barrier layers:

[0159] Barrier Layer A: During the application process, 55% hydroxyl polyester resin is melted and stirred, then 5% organic solvent is added. At a constant temperature of 74℃, 21% chlorinated rubber, 4% methyltrimethoxysilane D20, and 15% isocyanate adduct are added sequentially. After mixing and grinding, the mixture is sprayed onto the high-temperature resistant and corrosion-resistant fabric. This coating is referred to as Barrier Layer 1. Barrier Layer 1, after film formation, is tough and possesses good weather resistance, chemical resistance, acid and alkali corrosion resistance, resistance to petroleum solvents and petroleum products, and good impact resistance. The dry film thickness is 0.05 mm, and the spraying amount is 0.06 kg / m².

[0160] Before curing, 1400-mesh ceramic powder was applied to barrier layer A at a rate of 0.11 kg / m² in an isolation circulation chamber. Unattached powder was then blown away to form barrier layer B. The chamber was then placed in a curing chamber and cured for 45 minutes. After barrier layer A cured, the process proceeded to the next stage. Due to the smaller amount of barrier layer A and the relatively larger mesh size of the ceramic powder, adhesion was more uniform, and the amount used was less, resulting in a cured thickness of 0.07 mm. The ceramic powder layer (barrier layer B) protects the surface from contact with strong chemicals, preventing chemical corrosion, and also provides a certain temperature buffer to prevent sudden temperature changes.

[0161] After the barrier layer A and ceramic micro powder (barrier layer B) are adhered and cured, 78% chlorinated polyethylene resin is melted and 5% organic solvent is added. The mixture is kept at a constant temperature of 59°C, and then 2% methyltrimethoxysilane D20, 1% mineral pigment prepared to be close to cement color, 5% hydrogenated SBS, and 9% additives are added sequentially and mixed. The mixture is then sprayed onto the barrier layer B with the adhered ceramic powder at a dosage of 0.12 kg / m². It is cured at 25°C for 45 min to form a new barrier layer, referred to as barrier layer C, with a thickness of 0.1 mm.

[0162] The sprayed barrier layer C has strong adhesion, good resistance to acid, alkali and salt corrosion, resistance to severe cold, high temperature and ultraviolet radiation, and excellent anti-aging properties. At the same time, it has good long-lasting resistance to the complex physical and chemical environment of cement anti-collision walls and outstanding resistance to alternating dry and wet conditions.

[0163] After the barrier layer C has cured, a TPE film containing 5% epoxy powder is laminated onto the barrier layer C by hot pressing at a temperature of 69°C to form a new barrier layer, referred to as barrier layer D, with a thickness of 0.1 mm after hot pressing.

[0164] Finally, Amo 370 (AP370PLC) is sprayed onto barrier layer D at a rate of 0.03 kg / m², cured for 45 minutes, and cured to a thickness of 0.05 mm to form a new barrier layer, referred to as barrier layer E.

[0165] The total thickness of the hydrophobic barrier layer is 0.37 mm.

[0166] Composite of low-temperature flexible anti-corrosion adhesive layer:

[0167] The flexible anti-corrosion adhesive layer is applied by rolling the prepared material onto the side opposite to the high-temperature anti-corrosion cloth and the barrier layer 1. The application temperature is 53℃. At the same time, the release film is applied to the other side of the adhesive layer.

[0168] During the production process, 55% petroleum asphalt is first heated to 190°C instantaneously through a high-temperature heat exchanger and then added to a premixing tank along with 13% radial tire powder, 2% high clay, 1% kaolin, 6% glass fiber, and 4% SBS. After mixing, the temperature is 175°C. The premixed mixture is then pumped into a reaction vessel and reacted for 45 minutes. Simultaneously, the mixture in the reaction vessel is ground three times through a colloid mill.

[0169] After stirring evenly, continue stirring to lower the temperature of the mixture to 75℃. Once the mixture in the reactor reaches this temperature range, add 1.5% aromatic oil, 1.5% rubber oil, 0.5% linear silicone oil, 1% silane coupling agent KH, 11.5% polyurethane, 2% naphthenic oil, and 1% pour point depressant in sequence. Stir at a constant temperature for 60 minutes. After stirring evenly, pump the mixture into a coating and molding equipment. After coating and compression molding, the thickness is 1mm.

[0170] After being applied using a coating molding device, a cement-gray composite flexible asphalt-based anti-corrosion film is produced under low-temperature conditions. It is 1m wide, 1.37mm thick, and 10m long. After cooling to room temperature, it is rolled up, then heat-sealed with a film and stored for later use.

[0171] Comparative Example 1

[0172] Comparative Patent 1: A Salt-Resistant Anti-Corrosion Adhesive for Highway Cement Anti-Collision Walls and Its Manufacturing and Construction Method, Publication (Announcement) No.: CN117304834A.

[0173] The composition includes 50 parts heavy-duty road petroleum asphalt, 25 parts waste tire rubber powder, 3 parts styrene-butadiene-styrene thermoplastic elastomer, 0.1 parts polyoxypropylene glycerol ether, 0.2 parts thickener, 0.05 parts carbon fiber, 0.3 parts ethoxylated aliphatic alkylamine, 0.5 parts graphite powder, 25 parts PPET multilayer aluminized carbon composite film, and 25 parts PE film. The PE film is a protective film with a thickness of 0.008 mm. Silicone oil is applied to the contact surface with the intermediate layer, allowing it to adhere and be easily peeled off. This serves as a barrier and provides protection during storage and transportation. During construction, after peeling off the intermediate layer, the self-adhesive salt-resistant anti-corrosion tape is exposed. The self-adhesive salt-resistant anti-corrosion tape is L-shaped, with one side longer than the other. The shorter side of the intermediate layer is thicker, at least 1 mm thick and over 10 cm wide, for adhesion to the road surface, effectively preventing snowmelt from seeping into the cement crash barrier and its surroundings. The middle layer along the long side is relatively thin, with a thickness of 3mm. It can be thickened for special needs, with a height of 50cm, and is used for bonding to the facade of the cement anti-collision wall.

[0174] Comparative Example 2

[0175] Prepare a 1m wide high-temperature resistant and corrosion-resistant fabric as described in this application, and then apply a hydrophobic barrier layer and a low-temperature flexible corrosion-resistant adhesive layer to both sides of the fabric.

[0176] Composite of hydrophobic barrier layers:

[0177] Barrier Layer 1: During the application process, 54% hydroxyl polyester resin is melted and stirred, then 7% organic solvent is added. At a constant temperature of 75℃, 22% chlorinated rubber, 2% methyltrimethoxysilane D20, and 15% isocyanate adduct are added sequentially. After mixing and grinding, the mixture is sprayed onto the high-temperature resistant and corrosion-resistant fabric. This coating is referred to as Barrier Layer 1. Barrier Layer 1, after film formation, is tough and possesses good weather resistance, chemical resistance, acid and alkali corrosion resistance, resistance to petroleum solvents and petroleum products, and good impact resistance. The dry film thickness is ≥0.05mm, and the spraying rate is kg / m².

[0178] After curing, 71% chlorinated polyethylene resin is melted and 8% organic solvent is added. The temperature is kept constant below 58°C. Then, 4% methyltrimethoxysilane D20, 0.5% mineral pigment prepared to be close to cement color, 5.5% hydrogenated SBS, and 11% additives are added in sequence and sprayed onto the barrier layer 1 that adheres to the ceramic powder to form a new barrier layer, referred to as barrier layer 2.

[0179] The sprayed barrier layer 2 has strong adhesion, good resistance to acid, alkali and salt corrosion, resistance to severe cold, high temperature and ultraviolet radiation, and excellent anti-aging properties. At the same time, it has good long-lasting resistance to the complex physical and chemical environment of cement anti-collision walls and outstanding resistance to alternating dry and wet conditions.

[0180] After the barrier layer 2 has cured, a TPE film containing 5% epoxy powder is laminated onto the barrier layer 2 by hot pressing at a temperature of 65°C to form a new barrier layer, referred to as barrier layer 3.

[0181] Finally, Amo370 (AP370PLC) is sprayed onto barrier layer 3 with a thickness of 0.3mm to form a new barrier layer, referred to as barrier layer 4.

[0182] Composite of low-temperature flexible anti-corrosion adhesive layer:

[0183] The flexible anti-corrosion adhesive layer is formed by applying and rolling the prepared material onto the side opposite to the high-temperature anti-corrosion cloth and the barrier layer 1. The application temperature is 55℃. At the same time, the release film is laminated onto the other side of the adhesive layer.

[0184] During the production process, 36.9% petroleum asphalt is first heated to 190°C instantaneously through a high-temperature heat exchanger and then added to a premixing tank along with 30% radial tire powder, 3% high clay, 1% kaolin, 4% glass fiber, and 0.5% SBS. After mixing, the temperature is 178°C. The premixed mixture is then pumped into a reaction vessel and reacted for 40 minutes. Simultaneously, the mixture in the reaction vessel is ground three times through a colloid mill.

[0185] After stirring evenly, continue stirring to lower the temperature of the mixture to 78℃. Once the mixture in the reactor reaches this temperature range, add 1% aromatic oil, 0.5% rubber oil, 0.1% linear silicone oil, 0.5% silane coupling agent KH, 20% polyurethane, 0.5% naphthenic oil, and 2% retarder in sequence. Stir at a constant temperature for 60 minutes, and after stirring evenly, pump the mixture into the coating molding equipment.

[0186] After being applied using a coating molding device, cement-gray highway cement crash barrier anti-corrosion material with a specified width and thickness is produced under low-temperature conditions. After cooling to room temperature, it is rolled up, then heat-sealed with a thin film and stored for later use.

[0187] Comparative Example 3

[0188] Prepare a 1m wide high-temperature resistant and corrosion-resistant fabric as described in this application, and then apply a hydrophobic barrier layer and a low-temperature flexible corrosion-resistant adhesive layer to both sides of the fabric.

[0189] Composite of hydrophobic barrier layers:

[0190] Barrier Layer A: During the application process, 54% hydroxyl polyester resin is melted and stirred, then 7% organic solvent is added. At a constant temperature of 75℃, 22% chlorinated rubber, 2% methyltrimethoxysilane D20, and 15% isocyanate adduct are added sequentially. After mixing and grinding, the mixture is sprayed onto the high-temperature resistant and corrosion-resistant fabric. This coating is referred to as Barrier Layer A. Barrier Layer A, once formed, is tough and possesses excellent weather resistance, chemical resistance, acid and alkali corrosion resistance, resistance to petroleum solvents and petroleum products, and good impact resistance. The dry film thickness is 0.09 mm, and the spraying amount is 0.09 kg / m².

[0191] Before curing, 1000-mesh ceramic powder is applied at a rate of 0.09 kg / m² to barrier layer A in an isolation circulation chamber. Unattached powder is then blown away to form barrier layer B. The chamber then enters a curing chamber for 45 minutes. After barrier layer A has cured, the process proceeds to the next stage. The ceramic powder layer protects the surface from strong chemicals, preventing chemical corrosion, and provides a temperature buffer to prevent sudden temperature changes.

[0192] After barrier layer A has cured, a TPE film containing 5% epoxy powder is laminated onto barrier layer B by hot pressing at a temperature of 65°C to form a new barrier layer, referred to as barrier layer C, with a thickness of 0.1 mm after hot pressing.

[0193] The hydrophobic barrier layer is 0.19 mm thick.

[0194] Composite of low-temperature flexible anti-corrosion adhesive layer:

[0195] The flexible anti-corrosion adhesive layer is formed by applying and rolling the prepared material onto the side opposite to the high-temperature anti-corrosion cloth and the barrier layer 1. The application temperature is 55℃. At the same time, the release film is laminated onto the other side of the adhesive layer.

[0196] During the production process, 63.8% petroleum asphalt is first heated to 190°C instantaneously through a high-temperature heat exchanger and then added to a premixing tank along with 10% radial tire powder, 3% high clay, 1% kaolin, 4% glass fiber, and 7% SBS. After mixing, the temperature is 178°C. The premixed mixture is then pumped into a reaction vessel and reacted for 40 minutes. Simultaneously, the mixture in the reaction vessel is ground three times through a colloid mill.

[0197] After stirring evenly, continue stirring to lower the temperature of the mixture to 78℃. Once the mixture in the reactor reaches this temperature range, add 1% aromatic oil, 1% rubber oil, 0.2% linear silicone oil, 0.5% silane coupling agent KH, 6% polyurethane, 0.5% naphthenic oil, and 2% retarder in sequence. Stir at a constant temperature for 60 minutes. After stirring evenly, pump the mixture into a coating and molding equipment. After coating and rolling, the thickness is 1mm.

[0198] After being processed by the coating and molding equipment, the cement gray highway cement crash barrier anti-corrosion material, which is produced in a low-temperature state according to the complete structure, is completed. It is 1m wide, 1.19mm thick, and 10m long. After cooling to room temperature, it is rolled up, then heat-sealed with a film and stored for later use.

[0199] Performance verification:

[0200] The prepared material was divided into four portions. One portion was placed in an environment of -10℃ and irradiated with 200W ultraviolet light for 12 hours at 12-hour intervals. After the ultraviolet irradiation, the surface of the hydrophobic barrier layer was sprayed with a 30% sodium chloride solution for 2 hours. This cycle was repeated for 60 days, and the appearance color was observed to check the change in color difference with the cement crash barrier. One portion was placed in an environment of 25℃ and irradiated with 200W ultraviolet light for 12 hours at 12-hour intervals. After the ultraviolet irradiation, the surface of the hydrophobic barrier layer was sprayed with a 30% sodium chloride solution for 2 hours. This cycle was repeated for 60 days, and the appearance color was observed to check the change in color difference with the cement crash barrier. The low-temperature flexible anti-corrosion adhesive layer of one portion was scraped off and the tensile strength was tested at the same temperature. The low-temperature adhesive strength of the remaining portion was tested.

[0201] Table 1. Changes in appearance color (compared to cement color)

[0202]

[0203] By observing the appearance and color of the finished material, reducing the number of barrier layers and the thickness of the barrier layers will cause the low-temperature flexible anti-corrosion adhesive layer material to gradually penetrate into other layers, resulting in the material turning yellow or black.

[0204] Table 2. Tensile strength and bond strength at -10℃ under the same temperature.

[0205]

[0206]

[0207] Adjusting the proportions of materials such as petroleum asphalt, radial tire rubber powder, SBS, and polyurethane can affect the low-temperature flexibility and bond strength of the materials.

[0208] The inventors conducted anti-corrosion tests on the finished product. First, they verified the results through physical projects, including the Jilin Expressway, Beijing-Tibet Expressway, Xuanda Expressway, and Beijing-Lijiang Expressway. These projects and on-site environmental testing demonstrated that winter construction is entirely feasible. Second, they immersed the material in an outdoor iron basin containing de-icing agent and salt. After 60 days of observation, the iron basin rusted, but the material remained intact, showing no deformation or color change. Figure 1 Effects of de-icing agent and brine soaking (soaking for 60 days).

Claims

1. A composite flexible bitumen-based anticorrosion patch, comprising, in sequence, a hydrophobic barrier layer, a high-temperature resistant anticorrosion cloth, a low-temperature flexible anticorrosion adhesive layer, and a release film connected to each other; The hydrophobic barrier layer comprises barrier layer A, barrier layer B, barrier layer C, barrier layer D, and barrier layer E connected in sequence. The barrier layer A is obtained by spraying the following hot-melt material onto a high-temperature resistant and corrosion-resistant fabric and then curing it: 45%-60% hydroxyl polyester resin, 5%-10% organic solvent, 20%-30% chlorinated rubber, 2%-4% methyltrimethoxysilane, and 15%-20% trimethylhexamethylene diisocyanate. The barrier layer B is a ceramic micro powder layer adhered to the barrier layer A; The barrier layer C is obtained by spraying the following hot-melt material onto the barrier layer B and then curing it: 65%-80% chlorinated polyethylene resin, 5%-10% organic solvent, 2%-4% methyltrimethoxysilane, 0.5%-1% mineral pigment, 2%-6% hydrogenated SBS, and 5%-12% additives; the additives consist of the following components by weight. Composition: Heat stabilizer: Plasticizer: Antioxidant = 15:20:50; The barrier layer D is a TPE film containing 2%-6% epoxy powder, which is laminated onto the barrier layer C by hot pressing. The barrier layer E is an epoxy resin composite material layer sprayed onto the surface of the barrier layer D. The low-temperature flexible anti-corrosion adhesive layer is composed of the following materials and their weight percentages. composition: Petroleum asphalt 40%-60%, polyurethane 10%-18%, linear silicone oil 0.1%-0.5%, rubber oil 1%-3%, SBS 2%-5%, radial tire powder 12%-25%, high clay 1%-5%, kaolin 1%-3%, naphthenic oil 0.5%-2%, aromatic oil 1%-3%, silane coupling agent 0.5%-2%, pour point depressant 1%-3%, glass fiber 3%-7%.

2. The composite flexible asphalt-based anticorrosion patch according to claim 1, wherein the barrier layer A is obtained by spraying the following hot-melt material onto a high-temperature resistant anticorrosion cloth and then curing it: 50%-55% hydroxyl polyester resin, 5%-10% organic solvent, 20%-25% chlorinated rubber, 2%-4% methyltrimethoxysilane, and 15%-20% trimethylhexamethylene diisocyanate; and the barrier layer C is obtained by spraying the following hot-melt material onto the barrier layer B and then curing it: 70%-80% chlorinated polyethylene resin, 5%-10% organic solvent, 2%-4% methyltrimethoxysilane, 0.5%-1% mineral pigment, 5%-6% hydrogenated SBS, and 9%-12% additives.

3. The composite flexible bitumen-based anti-corrosion patch according to claim 1, wherein the low-temperature flexible anti-corrosion adhesive layer is composed of the following materials and their weight percentages: Petroleum asphalt 45%-55%, polyurethane 10%-16%, linear silicone oil 0.2%-0.5%, rubber oil 1%-2%, SBS 2%-4%, radial tire powder 13%-22%, high clay 2%-3%, kaolin 1%-2%, naphthenic oil 0.5%-2%, aromatic oil 1%-2%, silane coupling agent 0.5%-2%, pour point depressant 1%-3%, glass fiber 4%-6%.

4. The composite flexible bitumen-based anticorrosion patch according to claim 1, wherein the high-temperature resistant anticorrosion cloth is woven from polyurethane thermoplastic elastomer (TPU) yarn, with a weight of 65g or 80g per square meter; the total thickness of the hydrophobic barrier layer is 0.3mm-0.8mm, and the thickness of the anticorrosion adhesive layer is 1.0mm-2mm.

5. The composite flexible asphalt-based anticorrosion patch according to claim 4, wherein the thickness of barrier layer A is 0.05mm-0.15mm; the thickness of barrier layer B is 0.07mm-0.2mm; the thickness of barrier layer C is 0.1mm-0.25mm; the thickness of barrier layer D is 0.08mm-0.2mm; and the thickness of barrier layer E is 0.05mm-0.1mm.

6. The composite flexible asphalt-based anti-corrosion patch according to claim 1, wherein the epoxy resin composite coating layer contains amoxicillin 370, the organic solvent is an alcohol-based organic solvent, the heat stabilizer is a calcium-zinc composite stabilizer, the plasticizer is dibutyl phthalate, the antioxidant is BASF antioxidant 1330, the linear silicone oil is a low-viscosity dimethyl silicone oil of 130±10 mPa·s, and the mineral pigment is composed of black, white, and gray mineral pigments, wherein the weight ratio of black:white:gray is 1-1.1:5-6:2-3.

7. A method for preparing a composite flexible bitumen-based anticorrosion patch according to any one of claims 1-6, comprising the following steps: 1) Preparation of the hydrophobic barrier layer: After the barrier layer A material is hot-melted, mixed, ground, and then sprayed onto the high-temperature resistant and anti-corrosion cloth, ceramic micro powder is adhered to the barrier layer A through an isolation circulation box before curing. Unadhered powder is then blown off to form the barrier layer B, which is then cured in a curing box. The barrier layer C material is hot-melted and sprayed onto the barrier layer B to form a new barrier layer C. After the barrier layer C has cured, a TPE film containing 2%-6% epoxy powder is laminated onto the barrier layer C through hot pressing to form a new barrier layer D. Finally, an epoxy resin composite material is sprayed onto the barrier layer D to form a new barrier layer E. 2) Preparation of low-temperature flexible anti-corrosion adhesive layer: The prepared material is applied and rolled onto the side opposite to the high-temperature resistant and anti-corrosion cloth and the barrier layer A. At the same time, the release film is applied to the other side of the adhesive layer.

8. The preparation method according to claim 7, wherein the preparation method of the barrier layer A and the barrier layer B is as follows: 45%-60% of hydroxyl polyester resin is melted and stirred, then 5%-10% of organic solvent is added. At a constant temperature of 60℃-80℃, 20%-30% of chlorinated rubber, 2%-4% of methyltrimethoxysilane, and 15%-20% of trimethylhexamethylene diisocyanate are added sequentially. After mixing and grinding, the mixture is sprayed onto a high-temperature resistant anti-corrosion cloth to form barrier layer A. Before barrier layer A cures, ceramic micropowder is... In the isolation circulation chamber, the powder adheres to the barrier layer A and the unadhered powder is blown off to form the barrier layer B, which is then cured in the curing chamber. The barrier layer C is prepared by: hot-melting 65%-80% chlorinated polyethylene resin and adding 5%-10% organic solvent, keeping the temperature below 60°C, and then sequentially adding 2%-4% methyltrimethoxysilane, 0.5%-1% mineral pigment, 2%-6% hydrogenated SBS, and 5%-12% additives, which are then sprayed onto the barrier layer B that has adhered ceramic powder to form a new barrier layer C.

9. The preparation method according to claim 8, wherein the dry film thickness of barrier layer A is ≥0.05mm, and the spraying amount is 0.03-0.12kg / m²; the amount of ceramic micro powder used in barrier layer B is 0.05-0.15kg / m²; the dry film thickness of barrier layer C is ≥0.08mm, and the spraying amount is 0.18-0.3kg / m², with a surface drying time of 30min at 25℃ and a complete drying time of 1-2h; and the dry film thickness of barrier layer E is ≥0.05mm, and the spraying amount is 0.02-0.12kg / m², with a surface drying time of 30min at 25℃ and a complete drying time of 1-2h.

10. The preparation method according to claim 7, wherein the preparation method of the low-temperature flexible anti-corrosion adhesive layer is as follows: firstly, the petroleum asphalt is instantaneously heated to 190°C through a high-temperature heat exchanger and then introduced into a premixing tank and uniformly mixed with radial tire powder, high clay, kaolin, glass fiber, and SBS. After mixing, the temperature is 160°C-180°C, and the mixture is pumped into a reaction vessel. The reaction is carried out in the reaction vessel for 40-60 minutes, while the mixture in the reaction vessel is ground 3-5 times through a colloid mill. After mixing evenly, gradually reduce the temperature of the mixture to 60℃-80℃, and add aromatic oil, rubber oil, linear silicone oil, silane coupling agent, polyurethane, naphthenic oil, and pour point depressant in sequence. Stir at a constant temperature for 60-80 minutes. After mixing evenly, pump the mixture into a coating and molding equipment and coat and press it onto the surface of the high-temperature resistant and anti-corrosion cloth.

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