Polymer anti-permeation material with oil resistance and permeation resistance, preparation method and application thereof

Abstract

The application relates to the technical field of polyurethane impervious materials, and particularly discloses a high-molecular impervious material with oil resistance and imperviousness, a preparation method and application, which comprises the following components in parts by weight: 120 parts of polyurethane prepolymer, 20-45 parts of a diluent, 10-30 parts of an additive, 15-20 parts of micro-powder filling, 10-15 parts of carboxymethyl cellulose and 3-8 parts of a hydrogen phosphate di-salt; wherein the polyurethane prepolymer is prepared by reacting a diisocyanate compound with a polyether polyol; the micro-powder filling is a mixture of acrylic acid sodium hydrogel micro-powder and sodium alginate hydrogel micro-powder; and the hydrogen phosphate di-salt is a monovalent ion salt. The high-molecular impervious material has excellent imperviousness under an oil storage environment, has high adhesion, can be applied to grouting in a humid environment, and can better realize water resistance and oil resistance in a groundwater-sealed cave oil storage environment.

Description

Technical Field

[0001] This invention relates to the field of polyurethane waterproofing materials, specifically to polymer waterproofing materials that combine oil resistance and impermeability, as well as their preparation methods and applications. Background Technology

[0002] A water-sealed underground rock cavern oil depot (or simply cavern) consists of caverns excavated in rock below a stable groundwater level. A cavern consists of one or more interconnected caverns, functioning similarly to an oil tank on the surface. The cavern, along with construction tunnels, vertical shafts, water curtain openings, water curtain tunnels, and surface conveying and control facilities, constitutes an oil depot used to store crude oil and refined oil products.

[0003] Water-sealed oil and gas cavern engineering involves excavating underground caverns and utilizing the seepage pressure of groundwater into the cavern to suppress the outward leakage pressure of oil and gas, thereby achieving the storage purpose. The primary requirement for water-sealed oil and gas caverns is ensuring their hydraulic seal. When natural groundwater conditions are insufficient for a hydraulic seal, artificial water curtains are typically used to maintain the water seal. Due to the unique storage principle of water-sealed oil and gas caverns, groundwater will continuously seep into the cavern during construction and operation. Effectively controlling the seepage within design limits while ensuring the water seal is maintained is the key and challenging aspect of the design and construction of water-sealed oil and gas cavern engineering.

[0004] Polyurethane geomembranes are a common type of leak-sealing material. Existing polyurethane geomembranes primarily consider water as the seepage medium, as exemplified by CN110643017B – a hydrophilic and environmentally friendly polyurethane grouting material and its preparation method and application; and CN111777854A – a novel environmentally friendly flame-retardant polyurethane grouting material and its preparation method. However, for the special circumstances of oil depots, due to the use of water seals, the presence of petroleum and other oily substances in the stored medium, and the high humidity of the grouting location, not only are higher requirements placed on the water resistance of the geomembranes, but also on their oil resistance and adhesion in humid environments.

[0005] Therefore, it is necessary to design a seepage-proof material suitable for oil depots. Summary of the Invention

[0006] The purpose of this invention is to provide a polymeric anti-seepage material that combines oil resistance and impermeability. This polymeric anti-seepage material has excellent impermeability in oil storage environments and high adhesion, making it suitable for grouting in humid environments.

[0007] In addition, the present invention also provides a method for preparing the above-mentioned polymeric waterproofing material and its application.

[0008] This invention is achieved through the following technical solution:

[0009] A polymeric waterproofing material that combines oil resistance and impermeability, comprising the following components by weight:

[0010] 120 parts of polyurethane prepolymer, 20-45 parts of diluent, 10-30 parts of additives, 15-20 parts of micro powder filler, 10-15 parts of carboxymethyl cellulose and 3-8 parts of dihydrogen phosphate.

[0011] The polyurethane prepolymer is prepared by reacting a diisocyanate compound with a polyether polyol.

[0012] The micro powder filler is a mixture of sodium acrylate hydrogel micro powder and sodium alginate hydrogel micro powder.

[0013] Among them, dihydrogen phosphate is a monovalent ionic salt.

[0014] The polyurethane prepolymer, diluent, and additives used in this invention are all prior art. The concept of this invention is as follows:

[0015] By adding functional fillers to existing polyurethane waterproofing materials, the oil resistance, impermeability, and adhesion to humid environments of the polyurethane waterproofing materials can be improved, enabling the prepared polyurethane waterproofing materials to adapt to the environment of underground water-sealed rock cave oil depots.

[0016] The carboxymethyl cellulose in this invention contains pH-responsive groups, which enable the seepage-proof material to automatically increase its cross-linking density in an alkaline environment. The oil storage environment of the underground water-sealed rock cave oil depot of this invention is alkaline (the water storage environment of the underground water-sealed rock cave oil depot is mainly weakly alkaline (pH 7.5~9.1), because the cave depot is made of concrete sprayed anchor structure layer, and the concrete contains alkaline substances). That is, when the polymer seepage-proof material of this invention is used in the underground water-sealed rock cave oil depot in contact with the concrete sprayed anchor structure layer, it can improve the seepage resistance of the polymer seepage-proof material (resistance to water, crude oil and other media), so that the polymer seepage-proof material has excellent oil resistance and water resistance.

[0017] The polymeric seepage-proof material of this invention also contains dihydrogen phosphate, which is alkaline and provides an alkaline environment for carboxymethyl cellulose. Therefore, the seepage-proof material with both carboxymethyl cellulose and dihydrogen phosphate added simultaneously exhibits improved seepage-proofing performance. Compared to existing polyurethane seepage-proof materials, it also demonstrates enhanced resistance to water, crude oil, and other media, making it better suited to the water-sealed environment of underground water-sealed rock cavern oil depots. When the seepage-proof material with both carboxymethyl cellulose and dihydrogen phosphate is used in underground water-sealed rock cavern oil depots, compared to adding carboxymethyl cellulose alone, the dihydrogen phosphate and the oil depot itself provide an alkaline environment, further improving the seepage-proofing performance (resistance to water, crude oil, and other media).

[0018] Furthermore, the dihydrogen phosphate of the present invention is a monovalent ionic salt, which can avoid the reaction of high-valent ions with COO₂. -Complexation reduces the effect of carboxymethyl cellulose on automatically increasing crosslinking density in alkaline environments, for example: Mg 2+ AL 3+ I'll be meeting with the COO later. - Complexation.

[0019] The function of the micro-powder filler in this invention is to improve the adhesion of underwater seepage-proof materials in humid environments, thereby ensuring the durability of polymer seepage-proof materials in underground water-sealed rock cavern oil depots. The micro-powder filler of this invention is a mixture of sodium acrylate hydrogel micro-powder and sodium alginate hydrogel micro-powder. Both sodium acrylate and sodium alginate hydrogel micro-powders are existing technologies and can be prepared using existing methods. Sodium acrylate hydrogel micro-powder has higher strength and a certain advantage in water pressure resistance compared to sodium alginate hydrogel micro-powder; however, its adhesion is insufficient for use in humid environments. Sodium alginate hydrogel micro-powder has lower strength than sodium acrylate hydrogel micro-powder, but it has excellent adhesion properties. Combining sodium acrylate and sodium alginate hydrogel micro-powder allows the micro-powder filler to possess both excellent strength and adhesion properties in humid environments, thus enabling the polymer seepage-proof material with added micro-powder filler to exhibit excellent durability in underground water-sealed rock cavern oil depots.

[0020] In summary, the optimized polymer impermeable material of this invention has excellent impermeability (resistant to water, crude oil and other media) in oil storage environment, and has high adhesion, making it suitable for grouting in humid environments. It can better achieve water and oil resistance in underground water-sealed rock cavern oil depot environments.

[0021] In a preferred embodiment, the mass ratio of sodium acrylate hydrogel powder to sodium alginate hydrogel powder is 10:(1.0-2.0).

[0022] In a preferred embodiment, the mass ratio of sodium acrylate hydrogel powder to sodium alginate hydrogel powder is 10:(1.5-2.0).

[0023] The mass ratio of sodium acrylate hydrogel powder to sodium alginate hydrogel powder in the micro-powder filler of this invention affects the overall strength and adhesion to humid environments of the polymer waterproofing material. When the proportion of sodium alginate hydrogel powder is too large, although the adhesion to humid environments of the polymer waterproofing material is improved, its strength is reduced and it is not resistant to water pressure. When the proportion of sodium alginate hydrogel powder is too small, the adhesion to humid environments of the polymer waterproofing material is reduced.

[0024] In a preferred embodiment, the sodium acrylate hydrogel micropowder contains montmorillonite, which is added during the crosslinking process of preparing the sodium acrylate hydrogel micropowder.

[0025] Adding montmorillonite to sodium acrylate hydrogel micropowder can improve the adhesion of the sodium acrylate hydrogel micropowder. The synergistic effect of montmorillonite and sodium alginate hydrogel micropowder can improve the adhesion while ensuring the compressive strength of the polymer waterproofing material.

[0026] In a preferred embodiment, the preparation process of sodium acrylate hydrogel micropowder is as follows:

[0027] Acrylic acid and N-(3,4-dihydroxyphenylethyl)methacrylamide were added to an aqueous solution of sodium hydroxide under ice-water bath conditions to obtain solution A. An initiator and polyethylene glycol diacrylate were added to solution A under a nitrogen atmosphere. After ultraviolet irradiation, the solution was reacted in a water bath at 60-65℃ for 1-2 hours. After cooling, a hydrogel was obtained. The hydrogel was then prepared into powder to obtain sodium acrylate hydrogel micro powder.

[0028] When sodium acrylate hydrogel micropowder contains montmorillonite, the montmorillonite is dispersed in an aqueous sodium hydroxide solution.

[0029] In a preferred embodiment, the concentration of montmorillonite in the sodium hydroxide aqueous solution is 8-15 g / L.

[0030] Insufficient montmorillonite content does not significantly improve the adhesion of sodium acrylate hydrogel micropowder, while excessive content will affect the compressive strength of sodium acrylate hydrogel micropowder, and consequently affect the compressive strength of polymer waterproofing materials.

[0031] In a preferred embodiment, the sodium alginate hydrogel micropowder contains calcium carbonate and carbon nanotubes, which are added during the preparation of the sodium alginate hydrogel micropowder.

[0032] The presence of calcium carbonate and carbon nanotubes can improve the compressive strength of sodium alginate hydrogel micropowder. By adding sodium alginate hydrogel micropowder containing calcium carbonate and carbon nanotubes to polymeric waterproofing materials, the adhesion of the polymeric waterproofing materials can be improved while minimizing the impact of sodium alginate hydrogel micropowder on the compressive strength of the polymeric waterproofing materials.

[0033] Therefore, combining sodium alginate hydrogel powder containing calcium carbonate and carbon nanotubes with sodium acrylate hydrogel powder containing montmorillonite in a certain proportion can further improve the adhesion and compressive strength of polymer waterproofing materials.

[0034] In a preferred embodiment, the preparation process of sodium alginate hydrogel micropowder is as follows:

[0035] Acrylic acid was added to an aqueous solution of sodium alginate to adjust the pH to alkaline. Under nitrogen protection, N,N-methylenebisacrylamide, an initiator, and an aqueous solution of N,N,N',N'-tetramethylethylenediamine were added. After reacting for a period of time, calcium chloride was added, and the reaction was carried out for another period of time to obtain sodium alginate hydrogel. The hydrogel was then made into powder to obtain sodium alginate hydrogel micro powder.

[0036] When sodium alginate hydrogel micropowder contains calcium carbonate and carbon nanotubes, the pH value is adjusted to alkaline before adding calcium carbonate and carbon nanotubes.

[0037] In a preferred embodiment, the total amount of calcium carbonate and carbon nanotubes is 5%-8% based on the weight of sodium alginate hydrogel micropowder.

[0038] Insufficient calcium carbonate and carbon nanotube content does not significantly improve the strength of sodium alginate hydrogel micropowder, while excessive content will affect the adhesion of sodium alginate hydrogel micropowder.

[0039] In a preferred embodiment, the dihydrogen phosphate includes disodium hydrogen phosphate and dipotassium hydrogen phosphate.

[0040] Disodium hydrogen phosphate and dipotassium hydrogen phosphate can provide an alkaline environment and prevent cations from reacting with COO₂. - Complexation affects the crosslinking density of carboxymethyl cellulose auto-reinforcing waterproofing materials.

[0041] In a preferred embodiment, the content of dihydrogen phosphate is 25%-30% based on the weight of carboxymethyl cellulose.

[0042] In a preferred embodiment, the diisocyanate compound is an aromatic isocyanate or an aliphatic isocyanate.

[0043] In a preferred embodiment, the particle size of the sodium acrylate hydrogel microparticles is 40-70 μm; the particle size of the sodium alginate hydrogel microparticles is 20-30 μm.

[0044] In a preferred embodiment, the diluent is propylene glycol carbonate;

[0045] In a preferred embodiment, the additives include plasticizers, surfactants, and flame retardants.

[0046] The preparation method of the above-mentioned polymer waterproofing material includes the following steps:

[0047] S1. Prepare polyurethane prepolymer, mix sodium acrylate hydrogel powder and sodium alginate hydrogel powder to obtain micro powder filler, mix carboxymethyl cellulose and dihydrogen phosphate to obtain mixture.

[0048] S2. Mix the polyurethane prepolymer with diluent and additives in the specified proportions.

[0049] S3. Add micro powder filler and mixture, mix evenly to obtain a slurry-like polymer waterproof material.

[0050] Application of polymeric seepage-proof materials with both oil resistance and impermeability in underground water-sealed rock cavern oil depots.

[0051] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0052] This invention adds carboxymethyl cellulose and dihydrogen phosphate to existing polyurethane geomembranes. Under alkaline conditions, the pH-responsive groups of carboxymethyl cellulose ionize to release hydrogen ions, automatically increasing the crosslinking density of the geomembranes and improving their impermeability (resistance to water, crude oil, and other media). Furthermore, under the alkaline conditions of dihydrogen phosphate and the oil storage environment itself, the impermeability (resistance to water, crude oil, and other media) is further enhanced. By adding a micro-powder filler composed of sodium acrylate hydrogel powder and sodium alginate hydrogel powder, which combines strength and adhesion properties in humid environments, the invention improves the adhesion of the geomembranes in humid environments, thereby enhancing the durability of the polymer geomembranes in underground water-sealed rock cavern oil depots. Attached Figure Description

[0053] The accompanying drawings, which are included to provide a further understanding of embodiments of the invention and form part of this application, do not constitute a limitation thereof. In the drawings:

[0054] Figure 1 This is a schematic diagram of the sample block prepared in Example 1 before immersion;

[0055] Figure 2 This is a schematic diagram of the sample block prepared in Example 1 being immersed in water;

[0056] Figure 3 This is a schematic diagram of the sample block prepared in Example 1 after being immersed in water for 72 hours.

[0057] Figure 4 This is a schematic diagram of the sample block prepared in Example 1 after being immersed in water for 168 hours.

[0058] Figure 5 A schematic diagram of the sample block prepared in Example 1 being immersed in crude oil;

[0059] Figure 6 This is a schematic diagram of the sample block prepared in Example 1 after being immersed in crude oil for 72 hours.

[0060] Figure 7 A schematic diagram of the sample block prepared in Example 1 after being immersed in crude oil for 168 hours;

[0061] Figure 8This is a schematic diagram of the sample block prepared in Example 1 being immersed in gasoline;

[0062] Figure 9 A schematic diagram of the sample block prepared in Example 1 after being immersed in gasoline for 72 hours;

[0063] Figure 10 A schematic diagram of the sample block prepared in Example 1 after being immersed in gasoline for 168 hours;

[0064] Figure 11 This is a scanning electron microscope image of the sample block prepared in Example 1 at 30 μm.

[0065] Figure 12 The electron microscope scan image of the sample block prepared in Example 1 at 800 nm;

[0066] Figure 13 The electron microscope scan image of the sample block prepared for Comparative Example 8 at 30 μm;

[0067] Figure 14 The electron microscope scan image of the sample block prepared for Comparative Example 8 at 800 nm;

[0068] Figure 15 The image shows a scanning electron microscope (SEM) image of the sample block prepared in Example 7 at 20 μm, where the marked area represents the element Na.

[0069] Figure 16 The image shows a partial elemental energy spectrum of the sample block prepared in Example 7. In the image, the horizontal axis represents the characteristic X-ray energy of the excitation element, in keV; the vertical axis represents the count or signal intensity of the X-rays detected at that energy, in cps / eV; k represents the number 1000. Detailed Implementation

[0070] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. The illustrative embodiments and descriptions of this invention are for illustrative purposes only and are not intended to limit the invention. The embodiments described below are some, but not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0071] In the following description, numerous specific details are set forth to provide a thorough understanding of the invention. However, it will be apparent to those skilled in the art that these specific details are not necessary to practice the invention. In other embodiments, well-known structures, materials, or methods are not specifically described to avoid obscuring the invention. Unless otherwise specified, the materials, instruments, and reagents used in the following embodiments are commercially available. Unless otherwise specified, the techniques used in the embodiments are conventional methods well known to those skilled in the art.

[0072] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this application, "multiple" means two or more, unless otherwise explicitly specified.

[0073] Example:

[0074] This embodiment optimizes the formulation of existing polyurethane anti-seepage materials for the special environment of underground water-sealed rock cavern oil depots. Water-sealed rock cavern oil depots are caverns excavated in rock masses below the groundwater level and are used for storing oil and other materials using a water seal. This means that water-sealed rock cavern oil depots are not only in contact with water and have the characteristics of being humid, but are also subject to a certain pressure. In addition, the anti-seepage material also needs to be in contact with the concrete sprayed anchor structure layer of the oil depot. The concrete sprayed anchor structure layer is alkaline. Therefore, the anti-seepage material used for water-sealed rock cavern oil depots needs to consider not only the anti-seepage effect (water resistance and oil resistance) but also the durability under water pressure. This requires the anti-seepage material to not only be water-resistant and oil-resistant, but also have excellent adhesion performance in water pressure and humid environments.

[0075] Therefore, in order to adapt to the special environment of underground water-sealed rock cavern oil depots, this embodiment provides a polymeric seepage-proof material that combines oil resistance and impermeability, comprising the following components by weight:

[0076] 120 parts of polyurethane prepolymer, 20-45 parts of diluent, 10-30 parts of additives, 15-20 parts of micro powder filler, 10-15 parts of carboxymethyl cellulose and 3-8 parts of dihydrogen phosphate.

[0077] The polyurethane prepolymer is prepared by reacting a diisocyanate compound with a polyether polyol and a chain extender, wherein the chain extender is dimethylolpropionic acid. The diisocyanate compound is preferably an aromatic isocyanate or an aliphatic isocyanate, as aromatic and aliphatic isocyanates have better oil resistance. Specifically, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, etc. can be used.

[0078] The polyurethane prepolymer and its preparation process in this embodiment are existing technologies. Refer to CN111777854A - A novel environmentally friendly flame-retardant polyurethane grouting material and its preparation method for the preparation process. The specific steps are as follows:

[0079] (1) Dehydration of polyether polyols

[0080] The polyether polyol was heated and stirred, and then vacuum dehydrated. After cooling, the dehydrated raw material was obtained. The polyether polyol compound mixture was added to a vacuum bottle and heated to 100-110℃. The vacuum degree inside the bottle was gradually increased to -95kPa. The temperature and vacuum degree were maintained for 1-3 hours until the polyether polyol in the bottle was clear and transparent without large bubbles. The mixture was then cooled. The polyether polyol compound mixture was a mixture of N220, N230 and N310 in a mass ratio of 1:0.8:0.3.

[0081] (2) Hydrophilic modification of isophorone diisocyanate

[0082] Isophorone diisocyanate and PEG-200 were mixed in a molar ratio of 2:1. Dibutyltin dilaurate (0.04% molar percentage of isophorone diisocyanate) was added. Under an inert atmosphere, the temperature of the mixture was raised to 60-80℃ and stirred for 2-4 hours. The mixture was then cooled to room temperature to obtain hydrophilic modified isophorone diisocyanate.

[0083] (3) Polyurethane prepolymer

[0084] The dehydrated polyether polyol is heated to 40-50℃, and hydrophilic modified isocyanate and unmodified isocyanate are added in proportion. The chain extender dimethylolpropionic acid is added, and the temperature is raised to 70-90℃ for 2-4 hours. After the reaction is completed, the mixture is cooled to obtain the polyurethane prepolymer.

[0085] The diluent is propylene glycol carbonate; the additives include plasticizers, surfactants and flame retardants. Specifically, the plasticizer is a phthalate plasticizer; the surfactant can be sodium dodecylbenzene sulfonate, fatty alcohol polyoxyethylene ether, etc.; and the flame retardant is tris(2-chloroethyl) phosphate.

[0086] For information on polyurethane prepolymers and their preparation process, please refer to CN110643017B: A hydrophilic and environmentally friendly polyurethane grouting material, its preparation method, and its application.

[0087] 1) Place the polyether polyol (in this example, the tetrafunctional Puranol P8040) in a three-necked flask, heat and stir it in an oil bath at 120°C for 1 hour, and then vacuum dehydrate it at -0.1MPa using a circulating water multi-purpose vacuum pump until the water content is <0.05%. After cooling to 40°C, the dehydrated raw material is obtained.

[0088] 2) Under a high-purity N2 atmosphere, a polyisocyanate compound (isophorone diisocyanate is used in this example) is added to the dehydrated raw material obtained in step 1). The mixture is heated at 60°C for 0.5 h, then heated to 70°C for 1.5 h, and then cooled to obtain a polyurethane prepolymer. The weight ratio of tetrafunctional Puranol P8040 to isophorone diisocyanate is 58:17.

[0089] The micro-powder filler is a mixture of sodium acrylate hydrogel micro-powder and sodium alginate hydrogel micro-powder. In this embodiment, the combination of sodium acrylate hydrogel micro-powder and sodium alginate hydrogel micro-powder enables the prepared polymeric waterproofing material to have both adhesion and compressive strength in humid environments. The mass ratio of sodium acrylate hydrogel micro-powder to sodium alginate hydrogel micro-powder affects the adhesion and compressive strength of the prepared polymeric waterproofing material. Preferably, the mass ratio of sodium acrylate hydrogel micro-powder to sodium alginate hydrogel micro-powder is 10:(1.0-2.0), and more preferably, the mass ratio of sodium acrylate hydrogel micro-powder to sodium alginate hydrogel micro-powder is 10:(1.5-2.0).

[0090] Preferably, the sodium acrylate hydrogel micropowder contains montmorillonite, which is added to the sodium hydroxide aqueous solution during the crosslinking process of preparing the sodium acrylate hydrogel micropowder. Preferably, the concentration of montmorillonite in the sodium hydroxide aqueous solution is 8-15 g / L. Specifically, the preparation process of the sodium acrylate hydrogel micropowder containing montmorillonite is as follows:

[0091] A 20 wt.% sodium hydroxide aqueous solution was prepared. Montmorillonite ultrafine powder was ultrasonically dispersed in the sodium hydroxide aqueous solution at a dispersion ratio (concentration) of 10 g / L. The particle size of the montmorillonite ultrafine powder was 2-3 μm. Under ice-water bath conditions, acrylic acid and 3 wt.% N-(3,4-dihydroxyphenylethyl)methacrylamide in an amount equal to that of sodium hydroxide were slowly added to obtain solution A. Under a nitrogen atmosphere, 0.5 wt.% ammonium persulfate (APS) and 0.05 wt.% polyethylene glycol diacrylate (PEGDA) were added to solution A. After mixing thoroughly, the mixture was treated with ultraviolet light for 10 min and reacted in a water bath at 65℃ for 2 h. After cooling, a hydrogel was obtained. The hydrogel was dried in a forced-air dryer at 110℃ for 12 h, then vacuum dried at 90℃ for 48 h. It was then mechanically pulverized into micronized powder and sieved to obtain hydrogel micronized powder with a particle size of 40-70 μm, thus obtaining sodium acrylate hydrogel micronized powder. The preparation process of sodium acrylate hydrogel micropowder without montmorillonite is the same as above, except that montmorillonite is not used; the dosage and addition process of other components are the same.

[0092] Preferably, the sodium alginate hydrogel micropowder contains calcium carbonate and carbon nanotubes, which are added during the preparation of the sodium alginate hydrogel micropowder. Preferably, the total amount of calcium carbonate and carbon nanotubes is 5%-8% by weight of the sodium alginate hydrogel micropowder.

[0093] The preparation process of sodium alginate hydrogel micropowder is as follows:

[0094] 10g of sodium alginate was dissolved in 10L of deionized water to obtain a viscous sodium alginate aqueous solution. 20g of acrylic acid was added to the sodium alginate aqueous solution, and sodium hydroxide was added to adjust the pH to alkaline (specifically, the pH value was about 8.5). Under nitrogen protection, 0.025g of N,N-methylenebisacrylamide, 0.085g of potassium persulfate initiator, and 450μL of N,N,N',N'-tetramethylethylenediamine aqueous solution were added. After reacting for 2h, 1.5g of calcium chloride was added, and the reaction was continued for 30min to obtain sodium alginate hydrogel. The hydrogel was dried at 110 ℃ for 12h by forced air drying, then vacuum dried at 90 ℃ for 48h, mechanically pulverized into micronized powder, and sieved to obtain hydrogel micronized powder with a particle size of 20-30μm, thus obtaining sodium alginate hydrogel micronized powder.

[0095] When sodium alginate hydrogel micropowder contains calcium carbonate and carbon nanotubes, the pH value is adjusted to alkaline before adding calcium carbonate and carbon nanotubes.

[0096] In this embodiment, the dihydrogen phosphate diphosphate is a monovalent ionic salt; a monovalent ionic salt refers to a dihydrogen phosphate diphosphate whose cations are monovalent ions. Preferably, the dihydrogen phosphate diphosphate includes disodium hydrogen phosphate and dipotassium hydrogen phosphate. The dihydrogen phosphate diphosphate in this embodiment can provide an alkaline environment for the automatic density enhancement of carboxymethyl cellulose, and can also prevent divalent or trivalent cations from reacting with COO₂. - Complexation affects the crosslinking density of carboxymethyl cellulose auto-reinforcing waterproofing materials.

[0097] Preferably, the content of dihydrogen phosphate is 25%-30% based on the weight of carboxymethyl cellulose.

[0098] The preparation method of the polymer waterproofing material in this embodiment includes the following steps:

[0099] S1. Prepare polyurethane prepolymer, mix sodium acrylate hydrogel powder and sodium alginate hydrogel powder to obtain micro powder filler, mix carboxymethyl cellulose and dihydrogen phosphate to obtain mixture.

[0100] S2. Mix the polyurethane prepolymer with diluent and additives in the specified proportions.

[0101] S3. Add micro powder filler and mixture, mix evenly to obtain a slurry-like polymer waterproof material.

[0102] The polymeric impermeable material prepared in this embodiment has excellent impermeability (water and oil resistance) and high adhesion, making it suitable for grouting in humid environments, especially for seepage prevention in underground water-sealed rock cavern oil depots.

[0103] To better illustrate the technical effects of this embodiment, the following specific examples are used for explanation:

[0104] Example 1:

[0105] A polymeric waterproofing material that combines oil resistance and impermeability is composed of the following components in parts by weight:

[0106] The composition includes 120 parts of polyurethane prepolymer, 40 parts of propylene glycol carbonate, 6 parts of di(2-ethylhexyl) phthalate, 8 parts of sodium dodecylbenzenesulfonate, 12 parts of tri(2-chloroethyl) phosphate, 15 parts of micro powder filler, 12 parts of carboxymethyl cellulose, and 3 parts of disodium hydrogen phosphate.

[0107] The polyurethane prepolymer was prepared by reacting dehydrated tetrafunctional Puranol P8040 with isophorone diisocyanate. For the specific preparation process, please refer to the above examples.

[0108] The micro powder filler is obtained by mixing sodium acrylate hydrogel micro powder and sodium alginate hydrogel micro powder in a mass ratio of 10:1.5. The preparation process of sodium acrylate hydrogel micro powder and sodium alginate hydrogel micro powder is as described in the above example. The particle size of sodium acrylate hydrogel micro powder and sodium alginate hydrogel micro powder is similar, both being 50-60 μm.

[0109] In this embodiment, the content of disodium hydrogen phosphate is 25% based on the weight of carboxymethyl cellulose.

[0110] Example 2:

[0111] This embodiment is based on Embodiment 1, and the difference between it and Embodiment 1 is as follows:

[0112] The amount of micronized filler was increased from 15 parts to 17 parts.

[0113] Example 3:

[0114] This embodiment is based on Embodiment 1, and the difference between it and Embodiment 1 is as follows:

[0115] The amount of micronized filler was increased from 15 parts to 20 parts.

[0116] Comparative Example 1:

[0117] This comparative example is based on Example 1, and differs from Example 1 in that:

[0118] The amount of micronized filler was reduced from 15 parts to 13 parts.

[0119] Comparative Example 2:

[0120] This comparative example is based on Example 1, but differs from Example 1 in that the formulation does not contain micronized fillers.

[0121] Example 4:

[0122] This embodiment is based on Embodiment 1, but differs from Embodiment 1 in that the amounts of carboxymethyl cellulose and disodium hydrogen phosphate are different.

[0123] In this embodiment, 15 parts of carboxymethyl cellulose and 4.5 parts of disodium hydrogen phosphate were used;

[0124] In this embodiment, the content of disodium hydrogen phosphate is 30% based on the weight of carboxymethyl cellulose.

[0125] Example 5:

[0126] This embodiment is based on Embodiment 1, but differs from Embodiment 1 in that the amounts of carboxymethyl cellulose and disodium hydrogen phosphate are different.

[0127] In this embodiment, 15 parts of carboxymethyl cellulose and 6 parts of disodium hydrogen phosphate were used;

[0128] In this embodiment, the content of disodium hydrogen phosphate is 40% based on the weight of carboxymethyl cellulose.

[0129] Example 6:

[0130] This embodiment is based on Embodiment 1, but differs from Embodiment 1 in that the amounts of carboxymethyl cellulose and disodium hydrogen phosphate are different.

[0131] In this embodiment, 15 parts of carboxymethyl cellulose and 8 parts of disodium hydrogen phosphate were used;

[0132] In this embodiment, the content of disodium hydrogen phosphate is 53% based on the weight of carboxymethyl cellulose.

[0133] Comparative Example 3:

[0134] This comparative example is based on Example 1, but differs from Example 1 in that the amounts of carboxymethyl cellulose and disodium hydrogen phosphate are different. Specifically, the amount of carboxymethyl cellulose is reduced, while the mass ratio of disodium hydrogen phosphate to carboxymethyl cellulose remains unchanged at 25%.

[0135] In this embodiment, there are 8 parts of carboxymethyl cellulose and 2 parts of disodium hydrogen phosphate.

[0136] Comparative Example 4:

[0137] This comparative example is based on Example 1, but differs from Example 1 in that the amounts of carboxymethyl cellulose and disodium hydrogen phosphate are different. Specifically, the amount of carboxymethyl cellulose is reduced, while the mass ratio of disodium hydrogen phosphate to carboxymethyl cellulose remains unchanged at 25%.

[0138] In this embodiment, there are 6 parts of carboxymethyl cellulose and 1.5 parts of disodium hydrogen phosphate.

[0139] Comparative Example 5:

[0140] This comparative example is based on Example 1, but differs from Example 1 in that the amounts of carboxymethyl cellulose and disodium hydrogen phosphate are different. Specifically, the amount of carboxymethyl cellulose is increased, while the mass ratio of disodium hydrogen phosphate to carboxymethyl cellulose remains unchanged at 25%.

[0141] In this embodiment, there are 18 parts of carboxymethyl cellulose and 4.5 parts of disodium hydrogen phosphate.

[0142] Comparative Example 6:

[0143] This comparative example is based on Example 1, but differs from Example 1 in that the amounts of carboxymethyl cellulose and disodium hydrogen phosphate are different. Specifically, the amount of carboxymethyl cellulose is increased, while the mass ratio of disodium hydrogen phosphate to carboxymethyl cellulose remains unchanged at 25%.

[0144] In this embodiment, 20 parts of carboxymethyl cellulose and 5.0 parts of disodium hydrogen phosphate were used.

[0145] Comparative Example 7:

[0146] This comparative example is based on Example 1, but differs from Example 1 in that the formulation does not contain carboxymethyl cellulose and disodium hydrogen phosphate.

[0147] Comparative Example 8:

[0148] This comparative example is based on Example 1, but differs from Example 1 in that the formulation does not contain carboxymethyl cellulose, disodium hydrogen phosphate, or micronized filler.

[0149] Example 7:

[0150] This embodiment is based on Embodiment 1, but differs from Embodiment 1 in that: an equal amount of dipotassium hydrogen phosphate is used to replace disodium hydrogen phosphate, and fatty alcohol polyoxyethylene ether AEO-9 is used as the surfactant;

[0151] The scanning electron microscope image of the polymeric impermeable material prepared in this embodiment at 20 μm is shown below. Figure 15 As shown, some elemental energy spectra are as follows: Figure 16 As shown. By Figure 15-16 It can be known that:

[0152] In this embodiment, sodium element was successfully introduced, and sodium alginate hydrogel micropowder was introduced.

[0153] Example 8:

[0154] This embodiment is based on Embodiment 1, but differs from Embodiment 1 in that an equal amount of diammonium hydrogen phosphate ((NH4)2HPO4) is used to replace disodium hydrogen phosphate.

[0155] Comparative Example 9:

[0156] This comparative example is based on Example 1, but differs from Example 1 in that it does not contain disodium hydrogen phosphate.

[0157] Comparative Example 10:

[0158] This comparative example is based on Example 1, except that an equal amount of magnesium chloride is used to replace disodium hydrogen phosphate.

[0159] Comparative Example 11:

[0160] This comparative example is based on Example 1, except that an equal amount of aluminum chloride is used to replace disodium hydrogen phosphate.

[0161] Example 9:

[0162] This embodiment is based on Embodiment 1, but differs from Embodiment 1 in that the mass ratio of sodium acrylate hydrogel micropowder and sodium alginate hydrogel micropowder is 10:1.0.

[0163] Example 10:

[0164] This embodiment is based on Embodiment 1, but differs from Embodiment 1 in that the mass ratio of sodium acrylate hydrogel micropowder and sodium alginate hydrogel micropowder to the micropowder filler is 10:2.0.

[0165] Comparative Example 12:

[0166] This comparative example is based on Example 1, but differs from Example 1 in that the mass ratio of sodium acrylate hydrogel micropowder and sodium alginate hydrogel micropowder is 10:0.8.

[0167] Comparative Example 13:

[0168] This comparative example is based on Example 1, but differs from Example 1 in that the mass ratio of sodium acrylate hydrogel micropowder and sodium alginate hydrogel micropowder is 10:2.2.

[0169] Comparative Example 14:

[0170] This comparative example is based on Example 1, but differs from Example 1 in that the micro powder filler is sodium acrylate hydrogel micro powder.

[0171] Example 11:

[0172] This embodiment is based on Embodiment 1, but differs from Embodiment 1 in that the particle sizes of the sodium acrylate hydrogel micropowder and the sodium alginate hydrogel micropowder are different. Specifically:

[0173] The particle size of sodium acrylate hydrogel micropowder is 50-60 μm; the particle size of sodium alginate hydrogel micropowder is 20-30 μm.

[0174] Example 12:

[0175] This embodiment is based on Embodiment 1, but differs from Embodiment 1 in that the particle sizes of the sodium acrylate hydrogel micropowder and the sodium alginate hydrogel micropowder are different. Specifically:

[0176] The particle size of sodium acrylate hydrogel micropowder is 60-70 μm; the particle size of sodium alginate hydrogel micropowder is 15-25 μm.

[0177] Example 13:

[0178] This embodiment is based on Example 1, but differs from Example 1 in that: the sodium acrylate hydrogel micro powder contains montmorillonite, and the dispersion ratio of montmorillonite in the sodium hydroxide aqueous solution is 10 g / L; the sodium alginate hydrogel micro powder contains calcium carbonate and carbon nanotubes, and the amount of calcium carbonate and carbon nanotubes is 2% and 3% respectively, based on the sodium alginate hydrogel micro powder, that is, the total amount of calcium carbonate and carbon nanotubes is 5%.

[0179] Example 14:

[0180] This embodiment is based on Example 1, but differs from Example 1 in that: the sodium acrylate hydrogel micro powder contains montmorillonite, and the dispersion ratio of montmorillonite in the sodium hydroxide aqueous solution is 8 g / L; the sodium alginate hydrogel micro powder contains calcium carbonate and carbon nanotubes, and the amount of calcium carbonate and carbon nanotubes is 2% and 3% respectively based on the sodium alginate hydrogel micro powder, that is, the total amount of calcium carbonate and carbon nanotubes is 5%.

[0181] Example 15:

[0182] This embodiment is based on Example 1, but differs from Example 1 in that: the sodium acrylate hydrogel micro powder contains montmorillonite, and the dispersion ratio of montmorillonite in the sodium hydroxide aqueous solution is 15 g / L; the sodium alginate hydrogel micro powder contains calcium carbonate and carbon nanotubes, and the amount of calcium carbonate and carbon nanotubes is 2% and 3% respectively, based on the sodium alginate hydrogel micro powder, that is, the total amount of calcium carbonate and carbon nanotubes is 5%.

[0183] Example 16:

[0184] This embodiment is based on Example 1, but differs from Example 1 in that: the sodium acrylate hydrogel micro powder contains montmorillonite, and the dispersion ratio of montmorillonite in the sodium hydroxide aqueous solution is 10 g / L; the sodium alginate hydrogel micro powder contains calcium carbonate and carbon nanotubes, and the amounts of calcium carbonate and carbon nanotubes are 5% and 3% respectively, based on the sodium alginate hydrogel micro powder, that is, the total amount of calcium carbonate and carbon nanotubes is 8%.

[0185] Comparative Example 15:

[0186] This comparative example is based on Example 1, but differs from Example 1 in that: the sodium acrylate hydrogel micro powder contains montmorillonite, and the dispersion ratio of montmorillonite in the sodium hydroxide aqueous solution is 5 g / L; the sodium alginate hydrogel micro powder contains calcium carbonate and carbon nanotubes, and the amount of calcium carbonate and carbon nanotubes is 2% and 3% respectively based on the sodium alginate hydrogel micro powder, that is, the total amount of calcium carbonate and carbon nanotubes is 5%.

[0187] Comparative Example 16:

[0188] This comparative example is based on Example 1, but differs from Example 1 in that: the sodium acrylate hydrogel micro powder contains montmorillonite, and the dispersion ratio of montmorillonite in the sodium hydroxide aqueous solution is 20 g / L; the sodium alginate hydrogel micro powder contains calcium carbonate and carbon nanotubes, and the amounts of calcium carbonate and carbon nanotubes are 2% and 3% respectively, based on the sodium alginate hydrogel micro powder, that is, the total amount of calcium carbonate and carbon nanotubes is 5%.

[0189] Comparative Example 17:

[0190] This comparative example is based on Example 1, but differs from Example 1 in that: the sodium acrylate hydrogel micro powder contains montmorillonite, and the dispersion ratio of montmorillonite in the sodium hydroxide aqueous solution is 10 g / L; the sodium alginate hydrogel micro powder contains calcium carbonate and carbon nanotubes, and the amounts of calcium carbonate and carbon nanotubes are 1% and 2% respectively, based on the sodium alginate hydrogel micro powder, that is, the total amount of calcium carbonate and carbon nanotubes is 3%.

[0191] Comparative Example 18:

[0192] This comparative example is based on Example 1, but differs from Example 1 in that: the sodium acrylate hydrogel micro powder contains montmorillonite, and the dispersion ratio of montmorillonite in the sodium hydroxide aqueous solution is 10 g / L; the sodium alginate hydrogel micro powder contains calcium carbonate and carbon nanotubes, and the amounts of calcium carbonate and carbon nanotubes are 5% and 7% respectively, based on the sodium alginate hydrogel micro powder, that is, the total amount of calcium carbonate and carbon nanotubes is 3%.

[0193] Comparative Example 19:

[0194] This comparative example is based on Example 1, but differs from Example 1 in that: the sodium acrylate hydrogel micro powder contains montmorillonite, and the dispersion ratio of montmorillonite in the sodium hydroxide aqueous solution is 10 g / L; the sodium alginate hydrogel micro powder contains calcium carbonate, and the amount of calcium carbonate used is 5% based on the sodium alginate hydrogel micro powder.

[0195] Comparative Example 20:

[0196] This comparative example is based on Example 1, and differs from Example 1 in that: the sodium acrylate hydrogel micro powder contains montmorillonite, and the dispersion ratio of montmorillonite in the sodium hydroxide aqueous solution is 10 g / L; the sodium alginate hydrogel micro powder contains carbon nanotubes, and the amount of carbon nanotubes used is 5% based on the sodium alginate hydrogel micro powder.

[0197] The polymeric impermeable materials prepared in Examples 1-16 and Comparative Examples 1-20 were subjected to media resistance tests (water, xylene, 95# gasoline, crude oil), compressive strength, adhesion (bonding strength), and density tests. The test results are shown in Tables 1-6.

[0198] Among them, the first method of media resistance test is to conduct the test in accordance with GB / T 9274-1988 "Determination of resistance to liquid media of paints and varnishes";

[0199] One of the media resistance test methods is as follows: The polymer impermeable material is made into square sample blocks and immersed in a medium (water, crude oil, gasoline). Three sample blocks are used for each test (each sample block weighs 68-70g). The mass change of the sample blocks is measured after immersion for 72 hours and 168 hours. The calculation process for the mass change is as follows: weigh all three sample blocks together, and record the mass before immersion as M. 前 M 前 =M0 / 3, where M0 is the total weight of the 3 sample blocks after soaking, and the mass after soaking is denoted as M. 后 M 后 =M1 / 3, where M1 is the total weight of the three sample blocks after soaking, and the mass difference before and after soaking is denoted as σ (g), σ = M 后 -M 前 .

[0200] A schematic diagram of the sample block prepared in Example 1 before immersion is shown below. Figure 1 As shown; a schematic diagram of the sample block prepared in Example 1 being immersed in water is shown. Figure 2 As shown; a schematic diagram of the sample block prepared in Example 1 after being soaked in water for 72 hours is shown. Figure 3 As shown; a schematic diagram of the sample block prepared in Example 1 after being soaked in water for 168 hours is shown. Figure 4 As shown. A schematic diagram of the sample block prepared in Example 1 immersed in crude oil is shown. Figure 5 As shown; a schematic diagram of the sample block prepared in Example 1 after being immersed in crude oil for 72 hours is shown. Figure 6 As shown; a schematic diagram of the sample block prepared in Example 1 after being immersed in crude oil for 168 hours is shown. Figure 7 As shown; a schematic diagram of the sample block prepared in Example 1 immersed in gasoline is shown. Figure 8 As shown; a schematic diagram of the sample block prepared in Example 1 after being immersed in gasoline for 72 hours is shown. Figure 9As shown; a schematic diagram of the sample block prepared in Example 1 after being immersed in gasoline for 168 hours is shown. Figure 10 As shown.

[0201] Note: Since the specimen blocks prepared in the various embodiments and comparative examples are not significantly different in appearance, the specimen blocks of the various embodiments and comparative examples are not included.

[0202] Among them, the compressive strength test refers to JC / T 2041-2020 "Polyurethane Grouting Materials" 7.14 Test the compressive strength. The compression test (compressive strength) is calculated based on the load when the specimen is compressed to 50% of its original deformation.

[0203] Among them, the test of bond strength shall refer to the test 7.9 of JC / T 1041-2007 "Epoxy Resin Grouting Material for Concrete Cracks";

[0204] Density is measured as the mass-to-volume ratio.

[0205] Table 1

[0206]

[0207] The data in Table 1 shows that:

[0208] The various embodiments and comparative examples did not show significant changes in accordance with GB / T 9274-1988, which confirms that the polymeric impermeable material prepared by the present invention has certain media resistance properties. The formulations of Comparative Examples 2 and 8 do not contain micronized fillers, resulting in softening. The formulations of Comparative Examples 7-11 do not contain carboxymethyl cellulose and / or disodium hydrogen phosphate, or disodium hydrogen phosphate is replaced with other divalent or trivalent ionic salts, resulting in softening.

[0209] The scanning electron microscope image of the sample block prepared in Example 1 at 30 μm is shown below. Figure 11 As shown, the scanning electron microscope image of the sample block prepared in Example 1 at 800 nm is as follows. Figure 12 As shown; the scanning electron microscope image of the sample block prepared in Comparative Example 8 at 30 μm is shown below. Figure 13 As shown, the electron microscope scanning image of the sample block prepared in Comparative Example 8 at 800 nm is as follows. Figure 14 As shown, by Figure 11 and Figure 13 The comparison Figure 12 and Figure 14 The comparison shows that:

[0210] With the addition of micronized filler, carboxymethyl cellulose, and disodium hydrogen phosphate, a more pronounced "agglomeration effect" is observed, meaning the structure is more compact and the water and oil resistance is superior.

[0211] Therefore, it can be considered that the micro-powder filler, carboxymethyl cellulose, and disodium hydrogen phosphate have a significant impact on the prepared polymeric waterproofing material. Since the overall appearance does not change much, further testing is required. The following tests the mass difference (σ(g)) of the samples before and after immersion, as well as the compressive strength (MPa) and bonding strength (MPa), to further illustrate the differences in the effects of each embodiment and comparative example, as shown in Tables 2-6.

[0212] Table 2

[0213]

[0214] Note: The density of the unsoaked sample is calculated using the mass and volume of the unsoaked sample block.

[0215] The data in Table 2 shows that:

[0216] 1) When the other components and their contents remain unchanged in the formula, adjusting the amount of micro powder filler has little effect on the density and compressive strength of the prepared polymer waterproofing material. It mainly affects the bonding strength. That is, the micro powder filler has little effect on the waterproofing performance of the waterproofing material, but a greater effect on the bonding strength. By adding a certain amount of micro powder filler to the formula, its bonding strength can be improved, making the prepared polymer waterproofing material more adaptable to humid environments.

[0217] 2) Soaking in water and gasoline has a certain impact on the mass change of the sample block, but as the soaking time increases from 72h to 168h, the mass does not change significantly. Soaking in crude oil has almost no effect on the mass change of the sample block. The reason may be that the sample blocks prepared in Examples 1-3 and Comparative Examples 1-2 have a high density, making it difficult for the medium to enter through the pores. However, there are a small number of chain segments in the cross-linked structure of the solidified body, which can absorb a small amount of water. Water and gasoline have relatively low densities and can be absorbed in small amounts, while crude oil has a relatively high density and is not easily absorbed.

[0218] Note that the negative values ​​in Table 1 are normal measurement errors. This is mainly because the pores on the surface of the square sample block are difficult to clean, which will lead to measurement errors. Therefore, the increase or decrease of the mass difference σ before and after soaking within a certain small range can be considered as measurement errors. That is, the mass difference σ before and after soaking within a certain small range can be considered as no mass difference before and after soaking.

[0219] Table 3

[0220]

[0221] The data in Table 3 shows that:

[0222] 1) The amount of carboxymethyl cellulose added has a significant impact on the density and compressive strength of polymeric waterproofing materials. As the amount of carboxymethyl cellulose added increases, the density and compressive strength of polymeric waterproofing materials generally show an increasing trend. However, when the amount of carboxymethyl cellulose added increases to a certain extent, further increases in the amount of carboxymethyl cellulose added will no longer increase the density and compressive strength of the polymeric waterproofing materials. Therefore, it is unnecessary to add too much carboxymethyl cellulose.

[0223] 2) When the density of the sample block decreased to a certain value, the mass of the sample block increased after soaking in water, crude oil, and gasoline. Among them, the increase in mass of water and gasoline was more significant than that of crude oil, increasing to 168 after 72 hours, and the rate of increase in mass decreased thereafter.

[0224] Table 4

[0225]

[0226] The data in Table 4 shows that:

[0227] Dipotassium hydrogen phosphate and disodium hydrogen phosphate have similar effects. When diammonium hydrogen phosphate ((NH4)2HPO4) is used, the density and compressive strength of the polymeric waterproofing material decrease significantly. When magnesium chloride and aluminum chloride are used, the density and compressive strength of the polymeric waterproofing material are similar to those without disodium hydrogen phosphate. Therefore, magnesium chloride and aluminum chloride cannot play a synergistic reinforcing role for carboxymethyl cellulose.

[0228] Table 5

[0229]

[0230] As shown in Table 5:

[0231] The mass ratio of sodium acrylate hydrogel powder to sodium alginate hydrogel powder as micro-filler has little effect on the density and compressive strength of polymer waterproofing materials, but a greater effect on the bonding strength. As the amount of sodium alginate hydrogel powder increases, the bonding strength increases. However, when the amount of sodium alginate hydrogel powder increases to a certain extent, the bonding strength will not change significantly, while the compressive strength will increase. Therefore, it is necessary to control the mass ratio of sodium acrylate hydrogel powder to sodium alginate hydrogel powder to be 10:(1.0-2.0).

[0232] Table 6

[0233]

[0234] The data in Table 6 shows that:

[0235] The particle size ratio of sodium acrylate hydrogel micropowder to sodium alginate hydrogel micropowder affects the bonding strength of polymer waterproofing materials. Sodium acrylate hydrogel micropowder has a relatively larger particle size, which is more conducive to improving bonding strength. However, when the particle size difference between the two is too large, it is actually not conducive to improving bonding strength.

[0236] The dispersion ratio of montmorillonite in sodium hydroxide aqueous solution affects the bond strength. Within a certain range, the bond strength increases with the increase of the dispersion ratio. However, when the dispersion ratio reaches a certain level, its effect on improving the bond strength is not significant.

[0237] The amount of calcium carbonate and carbon nanotubes used affects the compressive strength of the impermeable material. Within a certain range, the compressive strength increases with the increase of the amount of calcium carbonate and carbon nanotubes. However, when the amount reaches a certain level, the effect on improving the compressive strength is not obvious.

[0238] The combined use of calcium carbonate and carbon nanotubes has a synergistic effect in improving compressive strength. The effect of using calcium carbonate or carbon nanotubes alone on improving the compressive strength of impermeable materials is not as good as the combined use of calcium carbonate and carbon nanotubes.

[0239] Based on the above experimental process, a better formulation combination is proposed:

[0240] Example 17:

[0241] A polymeric waterproofing material that combines oil resistance and impermeability is composed of the following components in parts by weight:

[0242] The composition includes 120 parts of polyurethane prepolymer, 40 parts of propylene glycol carbonate, 6 parts of di(2-ethylhexyl) phthalate, 8 parts of sodium dodecylbenzenesulfonate, 12 parts of tri(2-chloroethyl) phosphate, 15 parts of micro powder filler, 15 parts of carboxymethyl cellulose, and 4.5 parts of disodium hydrogen phosphate.

[0243] The filler powder consisted of sodium acrylate hydrogel micropowder and sodium alginate hydrogel micropowder in a mass ratio of 10:2.0. The sodium acrylate hydrogel micropowder contained montmorillonite, with a dispersion ratio of 15 g / L in sodium hydroxide aqueous solution. The sodium alginate hydrogel micropowder contained calcium carbonate and carbon nanotubes, with the amounts of calcium carbonate and carbon nanotubes being 5% and 3% respectively, based on the sodium alginate hydrogel micropowder, respectively, totaling 8%. The particle size of the sodium acrylate hydrogel micropowder was 50-60 μm, and the particle size of the sodium alginate hydrogel micropowder was 20-30 μm. The test data for Example 17 are shown in Table 7.

[0244] Table 7

[0245]

[0246] Example 18:

[0247] In addition, to further verify the oil and water resistance of the sample blocks prepared by the invention, a comparative analysis was conducted on natural immersion under no pressure and a 0.5 MPa pressure test. The sample blocks were weighed before and after immersion. Three samples were used in each experiment, and the mass of the three samples was weighed each time to calculate the medium absorption rate. The 0.5 MPa pressure test involved immersing the sample blocks under a pressure of 0.5 MPa. The sample blocks in this embodiment were prepared using the preparation method of Example 1. The results are shown in Tables 8 and 9.

[0248] Table 8

[0249]

[0250] Table 9

[0251]

[0252] Note that the "negative" values ​​in Tables 8 and 9 represent normal experimental errors that can lead to measurement errors. Therefore, any increase or decrease in the mass difference σ before and after soaking within a certain small range can be considered as measurement error.

[0253] As can be seen from Tables 8 and 9:

[0254] Whether immersed in gasoline, diesel, kerosene, crude oil, or water under normal pressure or 0.5MPa pressure, the difference in mass before and after immersion is not significant. This suggests that the density of the solidified body does not change much under pressure, indicating poor wetting by the medium. This, in turn, proves the good oil and water resistance.

[0255] This embodiment selects a pressure test of 0.5 MPa because the oil storage cavern has an elevation difference of 30-50 meters, meaning that when it is full, the natural pressure difference will be 0.3-0.5 MPa.

[0256] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A polymeric waterproofing material that combines oil resistance and impermeability, characterized in that, Includes the following components by weight: 120 parts of polyurethane prepolymer, 20-45 parts of diluent, 10-30 parts of additives, 15-20 parts of micro powder filler, 10-15 parts of carboxymethyl cellulose and 3-8 parts of dihydrogen phosphate. The polyurethane prepolymer is prepared by reacting a diisocyanate compound with a polyether polyol. The micro powder filler is a mixture of sodium acrylate hydrogel micro powder and sodium alginate hydrogel micro powder. Wherein, the dihydrogen phosphate is a monovalent ionic salt; The preparation process of the sodium acrylate hydrogel micropowder is as follows: Acrylic acid and N-(3,4-dihydroxyphenylethyl)methacrylamide were added to an aqueous sodium hydroxide solution under ice-water bath conditions to obtain solution A. An initiator and polyethylene glycol diacrylate were added to solution A under a nitrogen atmosphere. After ultraviolet irradiation, the solution was reacted in a water bath at 60-65°C for 1-2 hours. After cooling, a hydrogel was obtained. The hydrogel was then prepared into powder to obtain sodium acrylate hydrogel micro powder. The preparation process of the sodium alginate hydrogel micropowder is as follows: Acrylic acid was added to an aqueous solution of sodium alginate, and the pH was adjusted to be alkaline. Under nitrogen protection, N,N-methylenebisacrylamide, an initiator, and an aqueous solution of N,N,N',N'-tetramethylethylenediamine were added and reacted. Calcium chloride was added and reacted again to obtain sodium alginate hydrogel, which was then made into powder to obtain the sodium alginate hydrogel micro powder.

2. The polymeric waterproofing material with both oil resistance and impermeability according to claim 1, characterized in that, The mass ratio of the sodium acrylate hydrogel micro powder to the sodium alginate hydrogel micro powder is 10:(1.0-2.0).

3. The polymeric waterproofing material with both oil resistance and impermeability according to claim 2, characterized in that, The mass ratio of the sodium acrylate hydrogel micro powder to the sodium alginate hydrogel micro powder is 10:(1.5-2.0).

4. The polymeric waterproofing material with both oil resistance and impermeability according to claim 1, characterized in that, The sodium acrylate hydrogel micropowder contains montmorillonite, which is added during the crosslinking process of preparing the sodium acrylate hydrogel micropowder.

5. The polymeric waterproofing material with both oil resistance and impermeability according to claim 4, characterized in that, The preparation process of the sodium acrylate hydrogel micropowder is as follows: The montmorillonite was dispersed in the sodium hydroxide aqueous solution; acrylic acid and N-(3,4-dihydroxyphenylethyl)methacrylamide were added to the sodium hydroxide aqueous solution under ice-water bath conditions to obtain solution A; an initiator and polyethylene glycol diacrylate were added to solution A under a nitrogen atmosphere; after ultraviolet irradiation, the solution was reacted in a water bath at 60-65°C for 1-2 hours; after cooling, a hydrogel was obtained; the hydrogel was prepared into powder to obtain the sodium acrylate hydrogel micro powder.

6. The polymeric waterproofing material with both oil resistance and impermeability according to claim 5, characterized in that, The concentration of montmorillonite in the sodium hydroxide aqueous solution is 8-15 g / L.

7. The polymeric waterproofing material with both oil resistance and impermeability according to claim 1, characterized in that, The sodium alginate hydrogel micropowder contains calcium carbonate and carbon nanotubes, which are added during the preparation of the sodium alginate hydrogel micropowder.

8. The polymeric waterproofing material with both oil resistance and impermeability according to claim 7, characterized in that, The preparation process of the sodium alginate hydrogel micropowder is as follows: Acrylic acid was added to an aqueous solution of sodium alginate, and the pH was adjusted to be alkaline. Calcium carbonate and carbon nanotubes were then added. Under nitrogen protection, N,N-methylenebisacrylamide, an initiator, and an aqueous solution of N,N,N',N'-tetramethylethylenediamine were added, and the mixture was reacted. Calcium chloride was added, and the mixture was reacted again to obtain sodium alginate hydrogel. The hydrogel was then powdered to obtain sodium alginate hydrogel micropowder.

9. The polymeric waterproofing material with both oil resistance and impermeability according to claim 7, characterized in that, Based on the weight of the sodium alginate hydrogel micropowder, the total amount of calcium carbonate and carbon nanotubes is 5%-8%.

10. The polymeric waterproofing material with both oil resistance and impermeability according to claim 1, characterized in that, The dihydrogen phosphate is disodium hydrogen phosphate.

11. The polymeric waterproofing material with both oil resistance and impermeability according to claim 1, characterized in that, The dihydrogen phosphate is dipotassium hydrogen phosphate.

12. The polymeric waterproofing material with both oil resistance and impermeability according to claim 1, characterized in that, The content of the dihydrogen phosphate is 25%-30% based on the weight of the carboxymethyl cellulose.

13. The polymeric waterproofing material with both oil resistance and impermeability according to claim 1, characterized in that, The diisocyanate compound is an aromatic isocyanate or an aliphatic isocyanate.

14. The polymeric waterproofing material with both oil resistance and impermeability according to claim 1, characterized in that, The sodium acrylate hydrogel micropowder has a particle size of 40-70 μm; the sodium alginate hydrogel micropowder has a particle size of 20-30 μm.

15. The polymeric waterproofing material with both oil resistance and impermeability according to claim 1, characterized in that, The diluent is propylene glycol carbonate; the additives include plasticizers, surfactants, and flame retardants.

16. The method for preparing the polymeric waterproofing material according to any one of claims 1-15, characterized in that, Includes the following steps: S1. Prepare a polyurethane prepolymer, mix the sodium acrylate hydrogel micro powder and the sodium alginate hydrogel micro powder to obtain the micro powder filler, and mix the carboxymethyl cellulose and the dihydrogen phosphate to obtain a mixture; S2. Mix the polyurethane prepolymer with the diluent and the additives in a certain proportion; S3. Add the micro powder filler and the mixture, mix evenly, and obtain the polymeric waterproofing material in slurry form.

17. The application of the polymeric impermeable material as described in any one of claims 1-15 in underground water-sealed rock cavern oil depots.

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