A low-foam high-bacterium-inhibiting concentrated liquid for a support and a preparation method thereof

Abstract

The application provides a low-foaming high-bacterium-inhibiting concentrated liquid for hydraulic support and a preparation method thereof. The low-foaming high-bacterium-inhibiting concentrated liquid for hydraulic support comprises a lubricant, an emulsion stabilizer and a bacteriostatic agent. The lubricant comprises at least one of isooctyl octanoate, isomeric tridecyl alcohol ether and ethoxylated fatty alcohol modified vegetable oil. The emulsion stabilizer comprises at least one of isomeric decanol ether, acetylenic diol modified polyether, diethylene glycol tert-butyl ether and glycerol. The bacteriostatic agent comprises at least one of isothiazolinone and tetramethylthiuram monosulfate. The low-foaming high-bacterium-inhibiting concentrated liquid for hydraulic support provided by the application uses low-foaming lubricants and emulsion stabilizers to replace conventional easy-foaming additives, and simultaneously uses low-foaming bacteriostatic agents. The defoaming time of the transmission medium is within 60 seconds, the bacteriostatic capacity is above 99.9%, air cavity corrosion and blockage caused by the growth of bacterial colonies can be reduced, the replacement frequency of hydraulic support accessories can be reduced, the stability of the supply hydraulic pressure can be ensured, and the intelligent working face construction is favorable.

Description

Technical Field

[0001] This application relates to the field of hydraulic transmission medium technology, and in particular to a concentrated solution for a low-foaming, high-antibacterial-pressure stent and its preparation method. Background Technology

[0002] As a key piece of equipment in fully mechanized mining faces, coal mine hydraulic supports rely on high-water-content hydraulic fluid (an emulsified oil or concentrate mixed with mine water in a certain proportion) as the power transmission medium for their hydraulic transmission system. Currently, mainstream emulsified fluid products on the market have two major problems: first, foaming issues, especially under the high pressure and high flow conditions of intelligent hydraulic supports, traditional emulsified fluids easily generate a large amount of foam, leading to system pressure fluctuations, poor lubrication, and accelerated component wear; second, insufficient antibacterial properties. Traditional emulsified fluids often rely on formaldehyde-releasing bactericides or boron-containing bactericides and other preservatives, but these are prone to bacterial / fungal growth, causing emulsion stratification, precipitates clogging filters, and hydraulic support failures. While the current coal industry standard MT / T 76-2011, "Emulsified Oil, Concentrated Oil and High-Water-Content Hydraulic Fluids for Hydraulic Supports," specifies indicators such as defoaming properties (foam volume ≤ 2 mL / 10 min) for high-water-content hydraulic fluids, it does not clearly define specific requirements for microbial inhibition, relying solely on traditional preservatives for antibacterial purposes.

[0003] Intelligent hydraulic supports have higher requirements for the stability of emulsions, and their precision sensors and automated control systems are extremely sensitive to foam and microbial exudates in the emulsion. Foam can interfere with pressure sensing and flow control, leading to delays or false triggers; microbial growth can clog precision filters, affecting system stability. These problems are particularly prominent under high-pressure, high-flow conditions and have become a major bottleneck restricting the intelligent construction of coal mines.

[0004] Traditional emulsions mainly consist of lubricants, emulsion stabilizers, and rust inhibitors, with emulsion stabilizers often being ionic surfactants (such as sodium dodecyl sulfate). These surfactants have an amphiphilic molecular structure, with a hydrophilic polar group (-OH, -NH2, etc.) at one end and a lipophilic nonpolar group at the other. In hydraulic systems, they adsorb at the gas-liquid interface, forming an elastic film that stabilizes the foam and prevents it from breaking. Studies have shown that when the return flow rate is high, especially when the return pipe inlet is above the liquid surface, a large amount of foam is generated. This foam is atomized by the pump's agitation and, after being ejected at high speed through the valve port, forms emulsion-like bubbles that are difficult to float to the oil surface and eliminate on their own. The foam problem in traditional emulsions not only affects the performance of hydraulic systems but also causes energy loss, increases system pressure, generates vibration and noise, and even affects the appearance of the emulsion tank and the replenishment of water and fluid.

[0005] Existing antibacterial technologies have limitations. Currently, most antibacterial emulsions use formaldehyde-releasing or boron-containing bactericides. The former relies primarily on the release of formaldehyde for indiscriminate chemical attack, while the latter interferes with specific metabolic processes of microorganisms through boric acid molecules. However, formaldehyde and its release agents are toxic to aquatic organisms, and boron is difficult to degrade in the environment and is persistent, posing a risk to aquatic life and failing to meet increasingly stringent environmental protection requirements.

[0006] Therefore, developing a low-foaming, high-antibacterial transmission medium for hydraulic supports in coal mines not only meets the requirements of national environmental protection policies but also contributes to the construction of green and intelligent mines, and has significant practical significance and application prospects. Summary of the Invention

[0007] The inventors discovered that the relevant emulsions have the following problems: the defoaming time is relatively long and the antibacterial ability is relatively low. When encountering high flow and high pressure conditions, the foam is prone to aggregate, which affects the anti-corrosion effect and the stability of the hydraulic pressure supply, and cannot meet the stability requirements of the emulsion for intelligent hydraulic supports.

[0008] To address the aforementioned issues, one objective of this application is to provide a low-foaming, high-antibacterial-pressure hydraulic support concentrate. This concentrate uses low-foaming lubricants and emulsifying stabilizers to replace traditional easily foaming additives, while also incorporating low-foaming antibacterial agents. The defoaming time of the transmission medium is within 60 seconds, and the antibacterial capacity reaches over 99.9%. It can inhibit the corrosion of various metals, reduce cavitation corrosion, and prevent blockages caused by bacterial growth. This reduces the replacement frequency of hydraulic support components, ensures stable hydraulic pressure, and is beneficial for the construction of intelligent working surfaces.

[0009] Another objective of this application is to provide a method for preparing a concentrated solution for a low-foaming, high-antibacterial-pressure stent.

[0010] To achieve the above objectives, the first aspect of this application provides a low-foaming, high-antibacterial-pressure stent concentrate, comprising a lubricant, an emulsion stabilizer, and an antibacterial agent. The lubricant comprises at least one of isooctyl octanoate, isotactic tridecyl alcohol ether, and ethoxylated fatty alcohol modified vegetable oil. The emulsion stabilizer comprises at least one of isotactic decadecyl alcohol ether, acetylacetonate-modified polyether, diethylene glycol tert-butyl ether, and glycerol. The antibacterial agent comprises at least one of isothiazolinone and tetramethylphosphoric acid sulfate.

[0011] The low-foaming, high-antibacterial-pressure stent concentrate described in this application can bring at least the following beneficial effects: By using low-foaming lubricants and emulsifying stabilizers to replace traditional foaming additives, and compounding low-foaming antibacterial agents, the defoaming time of the transmission medium is within 60 seconds, and the antibacterial ability reaches more than 99.9%. It can inhibit the corrosion of various metals, reduce cavitation corrosion and avoid blockage caused by bacterial growth, reduce the replacement frequency of hydraulic support parts, ensure the stability of hydraulic power supply, and facilitate the construction of intelligent working faces.

[0012] In some embodiments, the lubricant content in the low-foaming, high-antibacterial-pressure stent concentrate is 6-13% by weight.

[0013] In some embodiments, the emulsifying stabilizer is present in the concentrate for the low-foaming, high-antibacterial-pressure stent at a mass percentage of 3-9%.

[0014] In some embodiments, the antibacterial agent is present in the concentrate for the low-foaming, high-antibacterial-pressure stent at a mass percentage of 0.05-0.1%.

[0015] In some embodiments, the lubricant is composed of isooctyl octanoate, isotretinoin ether, and ethoxylated fatty alcohol modified vegetable oil, and the mass ratio of isooctyl octanoate, isotretinoin ether, and ethoxylated fatty alcohol modified vegetable oil is (1-2):(1-2):(1-2), optionally 1:1:1.

[0016] In some embodiments, the emulsifying stabilizer is composed of isomeric decacarbonyl ether, acetylation diol modified polyether, diethylene glycol tert-butyl ether and glycerol, and the mass ratio of isomeric decacarbonyl ether, acetylation diol modified polyether, diethylene glycol tert-butyl ether and glycerol is (1-3):(1-2):(0.5-1):(1-3), optionally 1:1:0.5:3.

[0017] In some embodiments, the hydrophilic-lipophilic balance value of the emulsifying stabilizer is 14-18.

[0018] In some embodiments, the antibacterial agent is composed of isothiazolinone and tetrahydroxymethylphosphonic acid, and the mass ratio of isothiazolinone to tetrahydroxymethylphosphonic acid is 1:(1.6-2.4), optionally 1:2.

[0019] In some embodiments, the ethoxylated fatty alcohol modified vegetable oil includes at least one of YS-FAE and castor oil polyoxyethylene ether.

[0020] In some embodiments, the acetylenic diol modified polyether includes at least one of FS-620 and butynediol diethoxy ether.

[0021] In some embodiments, the concentrate for low-foaming, high-antibacterial-pressure stents further includes other additives and solvents, said other additives including at least one of a buffer, a first corrosion inhibitor, a second corrosion inhibitor, a fluoroalkyl polyether-modified polysiloxane, and an antifreeze, said solvent including water.

[0022] In some embodiments, the corrosion inhibitor includes at least one of citrate and triethanolamine.

[0023] In some embodiments, the first corrosion inhibitor includes at least one of sebacic acid, dodecanoic acid, and polyalkylepoxycarboxylate.

[0024] In some embodiments, the fluoroalkyl polyether modified polysiloxane includes at least one of fluoroalkyl polyether modified polysiloxane and alkyl polyether modified fluorosilicone oil.

[0025] In some embodiments, the antifreeze includes at least one of propylene glycol and ethylene glycol, with propylene glycol being the preferred choice.

[0026] In some embodiments, the second corrosion inhibitor includes at least one of benzotriazole and methylbenzotriazole, with benzotriazole being the preferred choice.

[0027] In some embodiments, the corrosion inhibitor is composed of citrate and triethanolamine, and the mass ratio of citrate to triethanolamine is (1-2):(1-2), optionally 1:2.

[0028] In some embodiments, the first corrosion inhibitor is composed of sebacic acid, dodecanoic acid and polyalkylepoxycarboxylate, and the mass ratio of sebacic acid, dodecanoic acid and polyalkylepoxycarboxylate is 1:(0.8-1.2):(2.4-3.6), optionally 1:1:3.

[0029] In some embodiments, the corrosion inhibitor is present in 4-10% by mass percentage in the concentrate for the low-foaming, high-antibacterial-pressure stent.

[0030] In some embodiments, the first corrosion inhibitor is present in 8-15% by mass percentage in the concentrate for the low-foaming, high-antibacterial-pressure stent.

[0031] In some embodiments, the second corrosion inhibitor is present in the concentrate for the low-foaming, high-antibacterial-pressure stent at a mass percentage of 0.05-0.1%.

[0032] In some embodiments, the fluoroalkyl polyether modified polysiloxane is present in the concentrate for the low-foaming, high-antibacterial-pressure stent at a mass percentage of 0.05-0.1%.

[0033] In some embodiments, the antifreeze content in the concentrate for the low-foaming, high-antibacterial-pressure stent is 10-15% by mass percentage.

[0034] In some embodiments, the pH of the concentrate for the low-foaming, high-antibacterial-pressure stent is 7.5-10.0.

[0035] The second aspect of this application discloses a method for preparing a concentrated solution for a low-foaming, high-antibacterial-pressure stent, comprising: The solvent, the lubricant, and the emulsion stabilizer are mixed in a first step to obtain a first mixture. The first mixture, the corrosion inhibitor, the first corrosion inhibitor, the second corrosion inhibitor, and a portion of the fluoroalkyl polyether modified polysiloxane are mixed a second time to obtain a second mixture. The second mixture is then mixed with the antifreeze to obtain a third mixture; The third mixture, the antibacterial agent, and the remaining fluoroalkyl polyether modified polysiloxane are mixed in a fourth mixture to obtain a fourth mixture; The fourth mixture is cooled and filtered to obtain the concentrate for the low-foaming, high-antibacterial-pressure stent.

[0036] The method for preparing the low-foaming, high-antibacterial-pressure stent concentrate described in this application has at least the beneficial effects of the low-foaming, high-antibacterial-pressure stent concentrate described in this application.

[0037] In some embodiments, the temperature of the first mixture and the temperature of the second mixture are each independently 60-70°C.

[0038] In some embodiments, the temperature of the fourth mixing is below 50°C, and can be selected as 25-50°C.

[0039] In some embodiments, the filtration includes filtering the cooled product sequentially through a 300-mesh filter, a 500-mesh filter, and an 800-mesh filter.

[0040] In some embodiments, the first mixing, the second mixing, the third mixing, and the fourth mixing are all carried out under stirring conditions.

[0041] In some embodiments, the stirring speed of the first mixture is 80-120 rpm.

[0042] In some embodiments, the stirring speed of the second mixture is 100-200 rpm.

[0043] In some embodiments, the stirring speed of the fourth mixture is 60-120 rpm, and the stirring time of the fourth mixture is 20-30 min.

[0044] Additional aspects and advantages of this application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of this application. Attached Figure Description

[0045] The above and / or additional aspects and advantages of this application will become apparent and readily understood from the following description of the embodiments taken in conjunction with the accompanying drawings. in: Figure 1 This is a flowchart illustrating a method for preparing a concentrated solution for a low-foaming, high-antibacterial-pressure stent, as shown in an exemplary embodiment of this application.

[0046] Figure 2 The graph shows a comparison of the antibacterial performance of the test samples from the blank control group, Examples 1-3, and Comparative Examples 1-6. K represents the antibacterial performance test graph of the test samples in the blank control group; a is a test diagram of the antibacterial performance of the test sample corresponding to the hydraulic support concentrate of Example 1; b is a test diagram of the antibacterial performance of the test sample corresponding to the hydraulic support concentrate of Example 2; c is a test diagram of the antibacterial performance of the test sample corresponding to the hydraulic support concentrate of Example 3; d is the antibacterial performance test diagram of the test sample corresponding to the hydraulic support concentrate of Comparative Example 1. e is a graph showing the antibacterial performance of the test sample corresponding to the hydraulic support concentrate in Comparative Example 2. f is a graph showing the antibacterial performance of the test sample corresponding to the hydraulic support concentrate of Comparative Example 3. g is a graph showing the antibacterial performance of the test sample corresponding to the hydraulic support concentrate of Comparative Example 4. h is a graph showing the antibacterial performance of the test sample corresponding to the hydraulic support concentrate of Comparative Example 5. i represents the antibacterial performance test diagram of the test sample corresponding to the hydraulic support concentrate of Comparative Example 6. Detailed Implementation

[0047] The embodiments of this application are described in detail below. These embodiments are exemplary and intended to explain this application, and should not be construed as limiting this application.

[0048] In this application, the disclosure of numerical ranges includes all values ​​throughout the range and the disclosure of further subdivisions of the range, including the endpoints and subranges given for these ranges.

[0049] Unless otherwise specified, all raw materials and equipment involved in this application are self-made through commercial means or known methods; and all methods involved are conventional methods unless otherwise specified.

[0050] In this application, room temperature refers to 20-30℃.

[0051] In this application, high pressure refers to 32 MPa or higher, and can be selected as 32 MPa-40 MPa.

[0052] The inventors discovered that mainstream emulsion products in related technologies suffer from problems such as excessive foaming and insufficient antibacterial properties, failing to meet the stability requirements of emulsions for intelligent hydraulic supports. Therefore, this application, while ensuring the overall product system meets the MT / T 76 standard, develops a low-foaming or high-antibacterial compound system. By replacing traditional easily foaming or low-antibacterial components with low-foaming or high-antibacterial additives, the defoaming time of the transmission medium is controlled within 1 minute, and no bacterial colony growth is observed at a concentration of 1%. This significantly reduces the impact of foam on hydraulic system pressure instability and the frequency of filtration system clogging, lowering maintenance costs while meeting environmental standards.

[0053] <Concentrated solution for low-foaming, high-antibacterial-pressure stents> The low-foaming, high-antibacterial-pressure stent concentrate of this application includes a lubricant, an emulsion stabilizer, and an antibacterial agent. The lubricant includes at least one of isooctyl octanoate, isotretinoin ether, and ethoxylated fatty alcohol modified vegetable oil. The emulsion stabilizer includes at least one of isotretinoin ether, acetylacetonate modified polyether, diethylene glycol tert-butyl ether, and glycerol. The antibacterial agent includes at least one of isothiazolinone and tetramethylphosphoric acid sulfate.

[0054] This low-foaming, high-antibacterial hydraulic support concentrate uses low-foaming lubricants and emulsifying stabilizers instead of traditional foaming additives. It also incorporates low-foaming antibacterial agents. The defoaming time of the transmission medium is within 60 seconds, and the antibacterial capacity reaches over 99.9%. It can inhibit corrosion of various metals, reduce cavitation corrosion, and prevent blockages caused by bacterial growth. This reduces the replacement frequency of hydraulic support components, ensures stable hydraulic pressure, and is beneficial for the construction of intelligent working faces. Specifically: The lubricant provides lubrication performance and is made from deeply refined isooctyl ester, isotridecyl alcohol ether, and ethoxylated fatty alcohol modified vegetable oil with moderate viscosity to ensure good lubrication performance.

[0055] Emulsion stabilizers promote dispersibility in water. A composite emulsion stabilizer consisting of isomeric decacarbonyl ether, acetylacetonate-modified polyether, diethylene glycol tert-butyl ether, and glycerol is used. By adjusting the ratio, the HLB value of the emulsion stabilizer is controlled between 14 and 18 to form a stable emulsion.

[0056] The antibacterial agent provides antibacterial and bactericidal properties. It uses isothiazolinone and tetramethyl phosphate to replace traditional formaldehyde-releasing or boron-containing bactericides, which can provide rapid, efficient and broad-spectrum antibacterial and bactericidal properties for hydraulic support concentrate, while being environmentally friendly and boron-free.

[0057] In some embodiments, the lubricant content in the low-foaming, high-antibacterial-pressure stent concentrate is 6-13% by mass, including but not limited to 8%, 10%, or 12%. Controlling the lubricant content within this range ensures the product meets the lubricity requirements of industry standard MT / T 76 while maintaining relatively low foaming capacity. Below 6%, the product's effectiveness in meeting the lubricity requirements of MT / T 76 is slightly reduced; above 13%, the product meets the lubricity requirements of MT / T 76, but its foaming capacity increases.

[0058] In the embodiments of this application, when the lubricant is selected from two or three of isooctyl octanoate, isotridecyl alcohol ether, and ethoxylated fatty alcohol modified vegetable oil, the lubricant can be understood as a composite lubricant.

[0059] As an alternative example, the lubricant consists of isooctyl octanoate, isotridecyl alcohol ether, and ethoxylated fatty alcohol modified vegetable oil.

[0060] In the embodiments of this application, isooctyl octanoate, isotridecyl alcohol ether, and ethoxylated fatty alcohol modified vegetable oil are used as lubricants, resulting in better lubrication performance.

[0061] Furthermore, the mass ratio of isooctyl octanoate, isotridecyl alcohol ether, and ethoxylated fatty alcohol modified vegetable oil is 1: (1-2): (1-2): (1-2), including but not limited to 1.5:1:2, 2:1.5:1.5, or 1:1.5:2, and optionally 1:1:1. This setting is more conducive to improving lubrication performance and controlling the low foaming properties of the product.

[0062] In some embodiments, the ethoxylated fatty alcohol modified vegetable oil includes, but is not limited to, at least one of YS-FAE, castor oil polyoxyethylene ether, etc.

[0063] For example, YS-FAE includes, but is not limited to, products with the model number YS-FAE produced by Guangzhou Junxin Chemical Technology Co., Ltd. (hereinafter referred to as Junxin Chemical).

[0064] For example, castor oil polyoxyethylene ether includes, but is not limited to, the EL-20 product manufactured by Liaoyang Aoke Polyether Co., Ltd.

[0065] In some embodiments, the emulsifying stabilizer is present in the concentrate for the low-foaming, high-antibacterial-pressure stent at a mass percentage of 3-9%, including but not limited to 5% or 7%.

[0066] In some embodiments, the hydrophilic-lipophilic balance value of the emulsifying stabilizer is 14-18, including but not limited to 15 or 16.

[0067] As an alternative example, the emulsifying stabilizer is composed of isomeric decacarbonyl ether, acetylsyl glycol modified polyether, diethylene glycol tert-butyl ether, and glycerol.

[0068] In the embodiments of this application, isomeric decacarbonyl ether, acetylacetonate-modified polyether, diethylene glycol tert-butyl ether and glycerol are used together as emulsion stabilizers, which is more conducive to controlling the HLB value of the emulsion stabilizer between 14 and 18 by adjusting the ratio, thus forming a stable emulsion.

[0069] Furthermore, the mass ratio of isomeric decacarbonyl ether, acetylsyl glycol modified polyether, diethylene glycol tert-butyl ether, and glycerol is (1-3):(1-2):(0.5-1):(1-3), including but not limited to 1:1.5:0.5:3, 1.5:2:0.8:2, 3:1:0.8:2, or 2:1:0.5:2, etc., and can be selected as 1:1:0.5:3. This setting allows for better control of the HLB value of the emulsion stabilizer between 14 and 18, forming a stable emulsion.

[0070] In some embodiments, the acetylenic diol modified polyether includes, but is not limited to, at least one of FS-620, butyne diol diethoxy ether, etc.

[0071] For example, FS-620 includes, but is not limited to, products with the model number FS-620 manufactured by Tianjin Hepfele New Materials Co., Ltd.

[0072] For example, butynediol diethoxy ether includes, but is not limited to, butynediol diethoxy ether produced by Wuhan Jihechang New Materials Co., Ltd.

[0073] In some embodiments, the antibacterial agent is present in the concentrate for the low-foaming, high-antibacterial-pressure stent at a mass percentage of 0.05-0.1%, including but not limited to 0.07% or 0.09%.

[0074] As an alternative example, the antibacterial agent consists of isothiazolinone and tetrahydroxymethylphosphonic acid.

[0075] In the embodiments of this application, isothiazolinone and tetrahydroxymethylsulfate are used together as antibacterial agents, which can better provide rapid, efficient, and broad-spectrum antibacterial and bactericidal performance.

[0076] Furthermore, the mass ratio of isothiazolinone to tetrahydroxymethylphosphonic acid is 1:(1.6-2.4), including but not limited to 1:1.8, 1:2, or 1:2.2, with 1:2 being the most suitable. This setting is more conducive to providing rapid, efficient, and broad-spectrum antibacterial and bactericidal properties.

[0077] In some embodiments, the concentrate for low-foaming, high-antibacterial-pressure stents further includes other additives and solvents, said other additives including at least one of a buffer, a first corrosion inhibitor, a second corrosion inhibitor, a fluoroalkyl polyether-modified polysiloxane, and an antifreeze, said solvent including water.

[0078] Among them, the corrosion inhibitor is used to maintain the stability of the pH value of the system, the first corrosion inhibitor provides basic rust prevention performance, the second corrosion inhibitor works with the first corrosion inhibitor to prevent rust and protect the metal surface, the role of fluoroalkyl polyether modified polysiloxane is to solve the foaming, wear and stability problems of the working fluid (diluted concentrate) on the high pressure, high flow intelligent working surface, and the antifreeze is used to maintain the stability of the product's freeze-thaw performance.

[0079] In some embodiments, the corrosion inhibitor includes at least one of citrate and triethanolamine. Choosing such a buffer system (citrate / triethanolamine) can maintain the pH of the hydraulic support concentrate within the range of 7.5-10.0, avoiding corrosion of metal components by an acidic environment, while also being less prone to foaming or having low antibacterial properties, thus exhibiting good environmental performance.

[0080] As an alternative example, the corrosion inhibitor consists of citrate and triethanolamine.

[0081] Furthermore, the mass ratio of citrate to triethanolamine is (1-2):(1-2), including but not limited to 1:1.8, 1.5:1, or 2:1.5, with 1:2 being a possible choice. This setting helps maintain the stability of the system's pH value.

[0082] In some embodiments, citrates include, but are not limited to, at least one of sodium citrate and potassium citrate.

[0083] In some embodiments, the corrosion inhibitor is present in the concentrate for the low-foaming, high-antibacterial-pressure stent at a mass percentage of 4-10%, including but not limited to 6% or 8%.

[0084] In some embodiments, the first corrosion inhibitor includes at least one of sebacic acid, dodecanoic acid, and polyalkylepoxycarboxylate. Selecting these substances as the first corrosion inhibitor is beneficial for suppressing the corrosion of various metals.

[0085] As an alternative example, the first corrosion inhibitor is composed of sebacic acid, dodecanoic acid, and polyalkylepoxycarboxylate.

[0086] Furthermore, the mass ratio of sebacic acid, dodecanoic acid and polyalkylepoxycarboxylate is 1:(0.8-1.2):(2.4-3.6), including but not limited to 1:0.9:3, 1:1.1:2.4, 1:1:3.3 or 1:1:2.7, etc., and can be selected as 1:1:3.

[0087] In some embodiments, the polyalkyl epoxy carboxylate includes, but is not limited to, at least one of sodium polyepoxysuccinate, sodium alkyl epoxy carboxylate, etc.

[0088] For example, sodium polyepoxysuccinate includes, but is not limited to, sodium polyepoxysuccinate (PESA-Na) products manufactured by Changzhou Hanshi Environmental Protection Technology Co., Ltd.

[0089] For example, sodium alkylepoxycarboxylate includes, but is not limited to, sodium alkylepoxycarboxylate (AEC-Na) products produced by Shanghai Fakai Chemical Co., Ltd.

[0090] In some embodiments, the first corrosion inhibitor is present in the concentrate for the low-foaming, high-antibacterial-pressure stent at a mass percentage of 8-15%, including but not limited to 10% or 12%.

[0091] In some embodiments, the second corrosion inhibitor includes, but is not limited to, at least one of benzotriazole and methylbenzotriazole, and may be selected as benzotriazole.

[0092] In some embodiments, the content of the second corrosion inhibitor in the concentrate for the low-foaming, high-antibacterial-pressure stent is 0.05-0.1% by mass, including but not limited to 0.07% or 0.09%.

[0093] In the embodiments of this application, the first corrosion inhibitor (sebacic acid: dodecanoic acid: polyalkyl epoxy carboxylate) is used as the main rust inhibitor and benzotriazole (BTA) is used as the auxiliary rust inhibitor. The two work synergistically to provide excellent rust prevention performance, and neither is prone to foaming or has low antibacterial properties.

[0094] In some embodiments, the fluoroalkyl polyether modified polysiloxane includes, but is not limited to, at least one of fluoroalkyl polyether modified polysiloxane and alkyl polyether modified fluorosilicone oil.

[0095] For example, fluoroalkyl polyether modified polysiloxanes include, but are not limited to, antifoaming agents such as IOTA 23350 produced by Anhui Aiyota Silicon Oil Co., Ltd.

[0096] For example, alkyl polyether modified fluorosilicone oils include, but are not limited to, antifoaming agents such as TPD-FS8015 produced by Taipuda New Materials Co., Ltd.

[0097] In some embodiments, the fluoroalkyl polyether modified polysiloxane is present in the concentrate for the low-foaming, high-antibacterial-pressure stent at a mass percentage of 0.05-0.1%, including but not limited to 0.07% or 0.09%.

[0098] In some embodiments, the antifreeze agent includes, but is not limited to, at least one of propylene glycol and ethylene glycol, with propylene glycol being a possible alternative.

[0099] In some embodiments, the antifreeze content in the concentrate for the low-foaming, high-antibacterial-pressure stent is 10-15% by mass, including but not limited to 12% or 14%.

[0100] In some embodiments, the pH of the concentrate for the low-foaming, high-antibacterial-pressure stent is 7.5-10.0, including but not limited to 8 or 9.

[0101] In the embodiments of this application, the pH of the concentrated solution for the low-foaming, high-antibacterial-pressure stent is controlled to be 7.5-10.0. The purpose is to ensure the anti-rust and anti-corrosion capabilities and antibacterial properties of the working fluid, while also meeting the technical requirements of the MT / T 76 standard.

[0102] As an optional example, the low-foaming, high-antibacterial-pressure stent concentrate of this embodiment comprises the following components by mass percentage: 6-13% lubricant, 3-9% emulsifying stabilizer, 4-10% buffer, 8-15% primary corrosion inhibitor, 0.05-0.1% secondary corrosion inhibitor, 0.05-0.1% antibacterial agent, 0.05-0.1% fluoroalkyl polyether modified polysiloxane, 10-15% antifreeze, and the balance being solvent.

[0103] The lubricant consists of isooctyl octanoate, isotridecyl alcohol ether, and ethoxylated fatty alcohol modified vegetable oil; the emulsifying stabilizer consists of isodecyl alcohol ether, acetylsyl glycol modified polyether, diethylene glycol tert-butyl ether, and glycerol; the buffer consists of citrate and triethanolamine; the primary corrosion inhibitor consists of sebacic acid, dodecanoic acid, and polyalkylepoxycarboxylate; the secondary corrosion inhibitor is benzotriazole (BTA); the antibacterial agent consists of isothiazolinone and tetramethylolphosphine sulfate; the antifreeze agent is propylene glycol; and the solvent is water.

[0104] Further optionally, the lubricant contains isooctyl octanoate, isotridecyl alcohol ether, and ethoxylated fatty alcohol modified vegetable oil in a mass ratio of 1:1:1; the emulsifying stabilizer contains isodecyl alcohol ether, acetylacetonate modified polyether, diethylene glycol tert-butyl ether, and glycerol in a mass ratio of 1:1:0.5:3; the corrosion inhibitor contains citrate and triethanolamine in a mass ratio of 1:2; the primary corrosion inhibitor contains sebacic acid, dodecanoic acid, and polyalkylepoxycarboxylate in a mass ratio of 1:1:3; and the antibacterial agent contains isothiazolinone and tetramethylphosphoric acid sulfate in a mass ratio of 1:2.

[0105] <Preparation Method of Concentrated Solution for Low-Foaming, High-Antibacterial-Pressure Stents> The method for preparing the concentrate for the low-foaming, high-antibacterial-pressure stent of this application embodiment can be used to prepare the concentrate for the low-foaming, high-antibacterial-pressure stent of this application embodiment.

[0106] Figure 1 This is a flowchart illustrating a method for preparing a concentrated solution for a low-foaming, high-antibacterial-pressure stent, as shown in an exemplary embodiment of this application.

[0107] like Figure 1 As shown, the preparation method includes the following steps: S101. The solvent, the lubricant, and the emulsifying stabilizer are mixed to obtain a first mixture.

[0108] Step S101 is the oil-water balance control step. In the embodiments of this application, the purpose of mixing the solvent, lubricant and emulsion stabilizer first is to provide a hydrophilic and oleophilic carrier for the subsequent dissolution of other additives.

[0109] In some embodiments, the temperature of the first mixing is 60-70°C, for example 65°C.

[0110] In some embodiments, the first mixing is carried out under stirring conditions.

[0111] In some embodiments, the stirring speed of the first mixture is 80-120 rpm, including but not limited to 90 rpm, 100 rpm or 110 rpm.

[0112] As an optional example, in step S101, the solvent, the lubricant, and the emulsion stabilizer are first mixed, including the following steps: (1) Solvent (e.g., water) and lubricant are added sequentially to a reaction vessel to obtain solution A; (2) Add emulsifying stabilizer to solution A, turn on the stirring device, and mix evenly at a stirring speed of 80-120 rpm to obtain solution B; (3) Heat solution B to 60-70℃ to promote the full dissolution of each component and obtain the first mixture.

[0113] S102. The first mixture, the corrosion inhibitor, the first corrosion inhibitor, the second corrosion inhibitor, and a portion of the fluoroalkyl polyether modified polysiloxane are mixed a second time to obtain a second mixture.

[0114] Step S102 is the acid-base balance control step. In the embodiments of this application, the solvent, lubricant and emulsion stabilizer are mixed and then corrosion inhibitor, preservative and partially fluoroalkyl polyether modified polysiloxane are added. The purpose is to maintain the acid-base balance suitable for cast iron, steel and copper, inhibit the corrosion of the three metals, and at the same time ensure that the product meets the technical requirements of MT / T 76.

[0115] In some embodiments, the temperature of the second mixing is 60-70°C, such as 65°C.

[0116] In some embodiments, the second mixing is carried out under stirring conditions.

[0117] In some embodiments, the stirring speed of the second mixing is 100-200 rpm, including but not limited to 120 rpm, 150 rpm or 180 rpm.

[0118] In some embodiments, the mass of the fluoroalkyl polyether modified polysiloxane added in step S102 is 40-60% of the total mass of the fluoroalkyl polyether modified polysiloxane, including but not limited to 45%, 50% or 55%.

[0119] As an optional example, in step S102, the first mixture, the corrosion inhibitor, the first corrosion inhibitor, the second corrosion inhibitor, and a portion of the fluoroalkyl polyether-modified polysiloxane are mixed a second time, including the following steps: 1) Under continuous stirring (100-200 rpm), buffer, first corrosion inhibitor, second corrosion inhibitor and fluoroalkyl polyether modified polysiloxane are added slowly in sequence to obtain solution C.

[0120] 2) Keep solution C at 60-70℃ to ensure that all components are fully mixed to obtain the second mixture.

[0121] S103. The second mixture is mixed with the antifreeze to obtain a third mixture.

[0122] Step S103 is a cooling step, specifically a step of cooling the second mixture. In the embodiments of this application, the purpose of adding antifreeze to the second mixture for cooling is to: absorb some heat through the dissolution of the antifreeze, save energy used in production, and at the same time provide a suitable temperature and solubilizing effect for the subsequent addition of heat-sensitive additives.

[0123] In some embodiments, the third mixing is carried out under stirring conditions.

[0124] In the embodiments of this application, the stirring speed of the third mixture is not limited; it can be the same as the stirring speed of the second mixture, or other stirring speeds can be selected.

[0125] S104. The third mixture, the antibacterial agent, and the remaining fluoroalkyl polyether modified polysiloxane are mixed in a fourth mixture to obtain a fourth mixture.

[0126] Step S104 is the preparation step. After cooling, the antibacterial agent and the remaining fluoroalkyl polyether modified polysiloxane are added. The purpose is to ensure the effectiveness of the antibacterial agent and the low foaming and rapid defoaming ability of the entire product system.

[0127] In some embodiments, the fourth mixing is carried out under stirring conditions.

[0128] In some embodiments, the stirring speed of the fourth mixture is 60-120 rpm, and the stirring time of the fourth mixture is 20-30 min.

[0129] For example, the stirring speed of the fourth mixing includes, but is not limited to, 80 rpm or 100 rpm.

[0130] For example, the stirring time for the fourth mixing includes, but is not limited to, 23 min or 27 min.

[0131] In some embodiments, the temperature of the fourth mixture is below 50°C, including but not limited to below 40°C or below 30°C, and may be 25-50°C.

[0132] As an optional example, in step 104, the third mixture, the antibacterial agent, and the remaining fluoroalkyl polyether-modified polysiloxane are mixed in a fourth mixture, comprising: Add the antibacterial agent and the remaining fluoroalkyl polyether modified polysiloxane to the third mixture at a temperature below 50°C, stir until completely transparent, set the stirring speed to 60-120 rpm, and stir for 20-30 minutes.

[0133] S105. Cool and filter the fourth mixture to obtain the concentrated solution for the low-foaming, high-antibacterial-pressure stent.

[0134] Step S105 is a cooling and filtering step. In the embodiments of this application, the purpose of filtering the fourth mixed solution is to remove impurities.

[0135] In some embodiments, the fourth mixture is cooled to room temperature.

[0136] In some embodiments, the filtration includes filtering the cooled product sequentially through a 300-mesh (50 μm) filter, a 500-mesh (30 μm) filter, and an 800-mesh (15 μm) filter.

[0137] In some embodiments, when the lubricant, emulsifying stabilizer, buffer, first corrosion inhibitor, and bactericide each comprise multiple substances, the preparation method of the concentrate for the low-foaming, high-antibacterial-pressure stent further includes a step of mixing the multiple substances of each substance before step S101, which can also be understood as a raw material pretreatment step.

[0138] For example, the raw material pretreatment steps include: (a) Isooctyl octanoate, isotridecyl alcohol ether, and ethoxylated fatty alcohol modified vegetable oil are mixed in a mass ratio to form a composite lubricant; (b) Mix isomeric decacarbon alcohol ether, acetylacetonate-modified polyether, diethylene glycol tert-butyl ether and glycerol in a mass ratio to form an emulsion stabilizer; (c) Prepare a citrate / triethanolamine buffer by mixing citrate and triethanolamine in a mass ratio; (d) Sebacic acid: dodecanoic acid: polyalkyl epoxy carboxylate are mixed in a mass ratio to form the first corrosion inhibitor; (e) Mix isothiazolinone and tetrahydroxymethylphosphonic acid in a mass ratio to prepare an antibacterial agent.

[0139] In some embodiments, the preparation method of the low-foaming high antibacterial pressure stent concentrate further includes a step of testing the performance of the obtained low-foaming high antibacterial pressure stent concentrate after step S105 to ensure that the low-foaming high antibacterial pressure stent concentrate meets the requirements of the standard "MT / T 76-2011 Emulsified oil, concentrate and high water content hydraulic fluid for hydraulic stents"; at the same time, bubbling test and antibacterial test are performed.

[0140] The following non-limiting embodiments further illustrate certain features of the present technology.

[0141] I. Examples and Comparative Examples Example 1 (Concentrated solution for low-foaming, high-antibacterial-pressure stents) The low-foaming, high-antibacterial-pressure stent concentrate of this embodiment comprises the following components by mass percentage: 8% lubricant, 6% emulsifying stabilizer, 10% corrosion inhibitor, 8% primary corrosion inhibitor, 0.05% secondary corrosion inhibitor, 0.05% antibacterial agent, 0.05% fluoroalkyl polyether modified polysiloxane, 12% antifreeze, and the balance being water.

[0142] in: The lubricant is composed of isooctyl octanoate, isotriadecyl alcohol ether, and ethoxylated fatty alcohol modified vegetable oil, with a mass ratio of isooctyl octanoate, isotriadecyl alcohol ether, and ethoxylated fatty alcohol modified vegetable oil of 2:1:1; the ethoxylated fatty alcohol modified vegetable oil is YS-FAE produced by Junxin Chemical; and the isotriadecyl alcohol ether is lubricant model E-1309 produced by Jiangsu Haian Petrochemical Plant.

[0143] The emulsifying stabilizer is composed of isomeric decacarbon alcohol ether, acetylation diol modified polyether, diethylene glycol tert-butyl ether, and glycerol, with a mass ratio of 1:1:0.5:3. The acetylation diol modified polyether is FS-620 produced by Tianjin Hepufele New Materials Co., Ltd., and the isomeric decacarbon alcohol ether is emulsifier model E1005 produced by Jiangsu Haian Petrochemical Plant. The corrosion inhibitor is composed of citrate and triethanolamine, with a mass ratio of citrate to triethanolamine of 2:1; the citrate is sodium citrate.

[0144] The first corrosion inhibitor is composed of sebacic acid, dodecanoic acid, and polyalkyl epoxy carboxylate, with a mass ratio of sebacic acid, dodecanoic acid, and polyalkyl epoxy carboxylate of 1:1:3; the polyalkyl epoxy carboxylate is PESA-Na produced by Changzhou Hanshi Environmental Protection Technology Co., Ltd.

[0145] The second corrosion inhibitor is benzotriazole (BTA).

[0146] The antibacterial agent is composed of isothiazolinone and tetrahydroxymethylphosphonic acid, and the mass ratio of isothiazolinone to tetrahydroxymethylphosphonic acid is 1:2.

[0147] Fluoroalkyl polyether modified polysiloxane is a foam suppressant, model IOTA23350, produced by Anhui Aiyota Silicon Oil Co., Ltd.

[0148] The antifreeze is propylene glycol.

[0149] The water is deionized.

[0150] (Preparation method of concentrated solution for low-foaming, high-antibacterial-pressure stents) The preparation method of the concentrate for the low-foaming, high-antibacterial-pressure stent in this embodiment includes the following steps: 1. Raw material pretreatment: (1) Mix isooctyl octanoate, isotridecyl alcohol ether and ethoxylated fatty alcohol modified vegetable oil in a mass ratio of 2:1:1 to form a lubricant.

[0151] (2) Mix isomeric decacarbon alcohol ether, alkynyl diol modified polyether, diethylene glycol tert-butyl ether and glycerol in a mass ratio of 1:1:0.5:3 to form an emulsion stabilizer.

[0152] (3) Mix citrate and triethanolamine at a mass ratio of 2:1 to form a corrosion inhibitor.

[0153] (4) Sebacic acid, dodecanoic acid and polyalkyl epoxy carboxylate are mixed evenly in a mass ratio of 1:1:3 to form the first corrosion inhibitor.

[0154] (5) Mix isothiazolinone and tetrahydroxymethylphosphoric acid at a mass ratio of 1:2 to form an antibacterial agent.

[0155] 2. Oil-water balance control: (1) Water and lubricant are added to the reaction vessel in sequence to obtain solution A.

[0156] (2) Add emulsifying stabilizer to solution A and mix evenly with stirring at 50 rpm to obtain solution B.

[0157] (3) Heat solution B to 65°C to obtain the first mixture.

[0158] 3. Acid-base balance control: (1) Under continuous stirring (200 rpm), the corrosion inhibitor, the first corrosion inhibitor, the second corrosion inhibitor and 40% of the total mass of the fluoroalkyl polyether modified polysiloxane were added in sequence to obtain solution C. (2) Keep the temperature of solution C at 65℃ and stir for 30 minutes to obtain the second mixture.

[0159] 4. Cooling and Adjustment: (1) Add antifreeze to the second mixture to promote the temperature reduction of the second mixture and obtain the third mixture; (2) Add the antibacterial agent and the remaining fluoroalkyl polyether modified polysiloxane to the third mixture at 40°C, stir until completely transparent, set the stirring speed to 60 rpm, and stir for 30 minutes to obtain the fourth mixture.

[0160] 5. Cooling and Filtration: The fourth mixture was cooled to room temperature (25°C) and then filtered sequentially through a 300-mesh (50μm) filter, a 500-mesh (30μm) filter, and an 800-mesh (15μm) filter to remove impurities, thus obtaining the concentrated solution for the low-foaming, high-antibacterial-pressure stent of this embodiment.

[0161] Example 2 (Concentrated solution for low-foaming, high-antibacterial-pressure stents) The low-foaming, high-antibacterial-pressure stent concentrate of this embodiment comprises the following components by mass percentage: 13% lubricant, 6% emulsifying stabilizer, 8% corrosion inhibitor, 10% first corrosion inhibitor, 0.08% second corrosion inhibitor, 0.08% antibacterial agent, 0.08% fluoroalkyl polyether modified polysiloxane, 10% antifreeze, and the balance being water.

[0162] in: The lubricant is composed of isooctyl octanoate, isotriadecyl alcohol ether, and ethoxylated fatty alcohol modified vegetable oil, with a mass ratio of isooctyl octanoate, isotriadecyl alcohol ether, and ethoxylated fatty alcohol modified vegetable oil of 1:2:1. The ethoxylated fatty alcohol modified vegetable oil is lubricant model EL-20 produced by Liaoyang Aoke Polyether Co., Ltd., and the isotriadecyl alcohol ether is lubricant model E-1309 produced by Jiangsu Haian Petrochemical Plant.

[0163] The emulsifying stabilizer is composed of isomeric decacarbon alcohol ether, acetylenic diol modified polyether, diethylene glycol tert-butyl ether, and glycerol, with a mass ratio of 2:2:1:1; the acetylenic diol modified polyether is butyrylenic diol diethoxy ether produced by Wuhan Jihechang New Material Co., Ltd.; and the isomeric decacarbon alcohol ether is emulsifier model E1005 produced by Jiangsu Haian Petrochemical Plant. The corrosion inhibitor is composed of citrate and triethanolamine, with a mass ratio of citrate to triethanolamine of 2:1; the citrate is sodium citrate.

[0164] The first corrosion inhibitor is composed of sebacic acid, dodecanoic acid, and polyalkyl epoxy carboxylate, with a mass ratio of sebacic acid, dodecanoic acid, and polyalkyl epoxy carboxylate of 1:1:3; the polyalkyl epoxy carboxylate is sodium polyepoxysuccinate (PESA-Na) produced by Changzhou Hanshi Environmental Protection Technology Co., Ltd.

[0165] The second corrosion inhibitor is benzotriazole (BTA).

[0166] The antibacterial agent is composed of isothiazolinone and tetrahydroxymethylphosphonic acid, and the mass ratio of isothiazolinone to tetrahydroxymethylphosphonic acid is 1:2.

[0167] Fluoroalkyl polyether modified polysiloxane is a foam suppressant produced by Taipuda New Materials Co., Ltd., with the model number TPD-FS8015.

[0168] The antifreeze is propylene glycol.

[0169] The water is deionized.

[0170] (Preparation method of concentrated solution for low-foaming, high-antibacterial-pressure stents) The preparation method of the concentrate for the low-foaming, high-antibacterial-pressure stent in this embodiment includes the following steps: 1. Raw material pretreatment: (1) Mix isooctyl octanoate, isotridecyl alcohol ether and ethoxylated fatty alcohol modified vegetable oil in a mass ratio of 1:2:1 to form a lubricant.

[0171] (2) Mix isomeric decacarbon alcohol ether, alkynyl diol modified polyether, diethylene glycol tert-butyl ether and glycerol in a mass ratio of 2:2:1:1 to form an emulsion stabilizer.

[0172] (3) Mix citrate and triethanolamine at a mass ratio of 2:1 to form a corrosion inhibitor.

[0173] (4) Sebacic acid, dodecanoic acid and polyalkyl epoxy carboxylate are mixed evenly in a mass ratio of 1:1:3 to form the first corrosion inhibitor.

[0174] (5) Mix isothiazolinone and tetrahydroxymethylphosphoric acid at a mass ratio of 1:2 to form an antibacterial agent.

[0175] 2. Oil-water balance control: (1) Water and lubricant are added to the reaction vessel in sequence to obtain solution A.

[0176] (2) Add emulsifying stabilizer to solution A and mix evenly with stirring at 80 rpm to obtain solution B.

[0177] (3) Heat solution B to 65°C to obtain the first mixture.

[0178] 3. Acid-base balance control: (1) Under continuous stirring (150 rpm), the corrosion inhibitor, the first corrosion inhibitor, the second corrosion inhibitor and 50% of the total mass of the fluoroalkyl polyether modified polysiloxane were added in sequence to obtain solution C. (2) Keep the temperature of solution C at 65℃ and stir for 30 minutes to obtain the second mixture.

[0179] 4. Cooling and Adjustment: (1) Add antifreeze to the second mixture to promote the temperature reduction of the second mixture and obtain the third mixture; (2) Add the antibacterial agent and the remaining fluoroalkyl polyether modified polysiloxane to the third mixture at 30°C, stir until completely transparent, set the stirring speed to 80 rpm, and stir for 30 minutes to obtain the fourth mixture.

[0180] 5. Cooling and Filtration: The fourth mixture was cooled to room temperature (25°C) and then filtered sequentially through a 300-mesh (50μm) filter, a 500-mesh (30μm) filter, and an 800-mesh (15μm) filter to remove impurities, thus obtaining the concentrated solution for the low-foaming, high-antibacterial-pressure stent of this embodiment.

[0181] Example 3 (Concentrated solution for low-foaming, high-antibacterial-pressure stents) The low-foaming, high-antibacterial-pressure stent concentrate of this embodiment comprises the following components by mass percentage: 6% lubricant, 9% emulsifying stabilizer, 10% corrosion inhibitor, 15% first corrosion inhibitor, 0.1% second corrosion inhibitor, 0.1% antibacterial agent, 0.1% fluoroalkyl polyether modified polysiloxane, 15% antifreeze, and the balance being water.

[0182] in: The lubricant is composed of isooctyl octanoate, isotriadecyl alcohol ether, and ethoxylated fatty alcohol modified vegetable oil, with a mass ratio of isooctyl octanoate, isotriadecyl alcohol ether, and ethoxylated fatty alcohol modified vegetable oil of 1:1:2. The ethoxylated fatty alcohol modified vegetable oil is a lubricant of model YS-FAE produced by Junxin Chemical. The isotriadecyl alcohol ether is a lubricant of model E-1309 produced by Haian Petrochemical Plant in Jiangsu Province.

[0183] The emulsifying stabilizer is composed of isomeric decacarbonyl ether, acetylation diol modified polyether, diethylene glycol tert-butyl ether, and glycerol, with a mass ratio of 3:2:1:2. The acetylation diol modified polyether is emulsifier FS-620 produced by Tianjin Hepufele New Materials Co., Ltd., and the isomeric decacarbonyl ether is emulsifier E1005 produced by Jiangsu Haian Petrochemical Plant. The corrosion inhibitor is composed of citrate and triethanolamine, with a mass ratio of citrate to triethanolamine of 2:1; the citrate is sodium citrate.

[0184] The first corrosion inhibitor is composed of sebacic acid, dodecanoic acid, and polyalkyl epoxy carboxylate, with a mass ratio of 1:1:3. The polyalkyl epoxy carboxylate is sodium alkyl epoxy carboxylate (AEC-Na) produced by Shanghai Fakai Chemical Co., Ltd.

[0185] The second corrosion inhibitor is benzotriazole (BTA).

[0186] The antibacterial agent is composed of isothiazolinone and tetrahydroxymethylphosphonic acid, and the mass ratio of isothiazolinone to tetrahydroxymethylphosphonic acid is 1:2.

[0187] Fluoroalkyl polyether modified polysiloxane is a foam suppressant produced by Taipuda New Materials Co., Ltd., with the model number TPD-FS8015.

[0188] The antifreeze is propylene glycol.

[0189] The water is deionized.

[0190] (Preparation method of concentrated solution for low-foaming, high-antibacterial-pressure stents) The preparation method of the concentrate for the low-foaming, high-antibacterial-pressure stent in this embodiment includes the following steps: 1. Raw material pretreatment: (1) Mix isooctyl octanoate, isotridecyl alcohol ether and ethoxylated fatty alcohol modified vegetable oil in a mass ratio of 1:1:2 to form a lubricant.

[0191] (2) Mix isomeric decacarbon alcohol ether, acetylacetonate modified polyether, diethylene glycol tert-butyl ether and glycerol in a mass ratio of 3:2:1:2 to form an emulsion stabilizer.

[0192] (3) Mix citrate and triethanolamine at a mass ratio of 2:1 to form a corrosion inhibitor.

[0193] (4) Sebacic acid, dodecanoic acid and polyalkyl epoxy carboxylate are mixed evenly in a mass ratio of 1:1:3 to form the first corrosion inhibitor.

[0194] (5) Mix isothiazolinone and tetrahydroxymethylphosphoric acid at a mass ratio of 1:2 to form an antibacterial agent.

[0195] 2. Oil-water balance control: (1) Water and lubricant are added to the reaction vessel in sequence to obtain solution A.

[0196] (2) Add emulsifying stabilizer to solution A and mix evenly with stirring at 100 rpm to obtain solution B.

[0197] (3) Heat solution B to 70°C to obtain the first mixture.

[0198] 3. Acid-base balance control: (1) Under continuous stirring (100 rpm), the corrosion inhibitor, the first corrosion inhibitor, the second corrosion inhibitor and 60% of the total mass of the fluoroalkyl polyether modified polysiloxane were added slowly in sequence to obtain solution C; (2) Keep the temperature of solution C at 70℃ and stir for 30 minutes to obtain the second mixture.

[0199] 4. Cooling and Adjustment: (1) Add antifreeze to the second mixture to promote the temperature reduction of the second mixture and obtain the third mixture; (2) Add the antibacterial agent and the remaining fluoroalkyl polyether modified polysiloxane to the third mixture at 20°C, stir until completely transparent, set the stirring speed to 120 rpm, and stir for 30 minutes to obtain the fourth mixture.

[0200] 5. Cooling and Filtration: The fourth mixture was cooled to room temperature (25°C) and then filtered sequentially through a 300-mesh (50μm) filter, a 500-mesh (30μm) filter, and an 800-mesh (15μm) filter to remove impurities, thus obtaining the concentrated solution for the low-foaming, high-antibacterial-pressure stent of this embodiment.

[0201] Comparative Example 1 This embodiment is basically the same as Embodiment 1, except that: In the preparation method of the concentrated solution for low-foaming, high-antibacterial-pressure stents: Replace "ethoxylated fatty alcohol modified vegetable oil" in the lubricant with "triethanolamine oleic acid soap produced by Jiangsu Haian Petrochemical Plant"; The corrosion inhibitor is citrate (specifically sodium citrate).

[0202] Comparative Example 2 This embodiment is basically the same as embodiment 2, except that: In the preparation method of the concentrated solution for low-foaming, high-antibacterial-pressure stents: Replace “isomeric tridecyl alcohol ether” in the lubricant with “fatty alcohol polyoxyethylene ether, model AEO-9, produced by Jiangsu Haian Petrochemical Plant”; Replace “isomeric decacarbonyl ether” in the emulsion stabilizer with “decacarbonyl”.

[0203] Comparative Example 3 This comparative example is basically the same as Example 3, except that: In the preparation method of the concentrated solution for low-foaming, high-antibacterial-pressure stents: Replace “acetylenic diol modified polyether” with “coconut oil fatty acid diacetamide produced by Jiangsu Haian Petrochemical Plant”.

[0204] Comparative Example 4 This comparative example is basically the same as Example 1, except that: In the preparation method of the concentrated solution for low-foaming, high-antibacterial-pressure stents: It contains no or no antibacterial agents.

[0205] Comparative Example 5 This comparative example is basically the same as Example 1, except that: In the preparation method of the concentrated solution for low-foaming, high-antibacterial-pressure stents: The antibacterial agent is a mixture of dodecyl dimethyl benzyl ammonium chloride and tetrahydroxymethyl phosphoric acid in a 1:1 mass ratio.

[0206] Comparative Example 6 This comparative example is basically the same as Example 1, except that: In the preparation method of the concentrated solution for low-foaming, high-antibacterial-pressure stents: The first corrosion inhibitor is a homogeneous mixture of dodecanoic acid and polyalkylepoxycarboxylate in a mass ratio of 2:3.

[0207] The content (i.e., amount) of emulsifying stabilizer was increased to 9 wt%.

[0208] II. Performance Testing 1. Sample selection / preparation Blank control group test sample: water sample taken from the coal mine site.

[0209] Example or comparative test sample: The concentrated solution of the hydraulic support of the example or comparative example was added to the coal mine field water sample of the blank control group and mixed to obtain the test sample corresponding to the concentrated solution of the hydraulic support of the example or comparative example; in the test sample corresponding to the concentrated solution of the hydraulic support of the example or comparative example, the mass content of the concentrated solution of the hydraulic support of the example or comparative example was 1%.

[0210] 2. Testing Methods (1) The test samples corresponding to the hydraulic support concentrates prepared in Examples 1-3 and Comparative Examples 1-6 were tested according to the MT / T76-2011 standard. The test results are shown in Tables 1-1 and 1-2.

[0211] (2) Bubbling tests and antibacterial tests were performed on the test samples corresponding to the concentrated solutions for hydraulic supports prepared in Examples 1-3 and Comparative Examples 1-6, wherein: The test method for the bubbling test is as follows: GB / T12579-2002 "Determination of Foaming Characteristics of Lubricating Oils" (this standard is equivalent to the international standard ISO 6247) in steps 8.2, 8.3 and 8.4, with the test temperature changed to 25℃, 50℃ and 25℃ (the test temperature is derived from ISO 12922:2020(E), which tests foam performance according to ISO 6247), to examine the foam tendency and foam stability.

[0212] The test method for antibacterial activity detection is SN / T 4544.2-2022 "Commercial Reagent Kit Test Method for Total Colony Count - Method II". Specifically, the samples from the blank control group, the hydraulic stents prepared in each example and comparative example, and the corresponding test samples with concentrated solution are respectively dropped onto the colony test strips. After incubation for 24 hours, the colony count on the colony test strips is checked.

[0213] The bubbling test is shown in Table 2, the bacteriostatic performance test is shown in Table 2 and Figure 2 .

[0214] Table 1-1

[0215] Note: "——" in Table 1-1 indicates that no requirement is specified in the current MT / T76 standard.

[0216] Table 1-2

[0217] It can be seen from Table 1-1 that in terms of the six indicators of kinematic viscosity, solidification point, pH value, defoaming property, sealing material compatibility and lubricity, the test results of Examples 1-3 and Comparative Examples 1-6 all meet the requirements of the MT / T 76-2011 standard. Specifically, for kinematic viscosity, the standard requires ≤100 mm² / s, and the measured values of each sample are between 1.903 and 2.347 mm² / s, all far outperforming the standard limit. For solidification point, the standard requires ≤-5°C, and the measured solidification points of each sample are between -28°C and -33°C, showing excellent low-temperature fluidity that far meets the standard requirement, and can satisfy the application requirements under working conditions in cold mining areas. For pH value, all samples fall within the range of 7.5 to 10 required by the standard. For defoaming property, the residual foam volume of each sample after 10 minutes is all 0 mL, which meets the requirement of ≤2 mL specified in the standard. For sealing material compatibility, the volume expansion rate of each sample is between 2.35% and 3.46%, all falling within the qualified range of 0 to 6% specified in the standard. For lubricity, the standard requires the PB value to be ≥392 N, and the measured PB values of each sample are between 431 and 510 N, all of which are qualified. It is worth noting that the PB values of Examples 1-3 are 431 N, 510 N and 471 N respectively. While Comparative Examples 1-6 are all qualified, the PB values of Comparative Examples 4-6 are all 431 N, which just exceed the standard limit and are significantly lower than 510 N of Example 2 and 471 N of Example 3. For lubricity, an indicator that is crucial to the service life of key friction pairs such as plunger pumps and hydraulic valves of hydraulic supports, all the examples exhibit comprehensive performance superior or equal to that of the comparative examples, among which Example 2 and Example 3 are significantly superior to Comparative Examples 4-6 in terms of lubricity indicator.

[0218] It can be seen from Table 1-2 that the test results of Examples 1-3 and Comparative Examples 1-6 all meet the requirements of the MT / T 76-2011 standard, indicating that they can inhibit the corrosion of various metals including cast iron, brass and steel.

[0219] Table 2

[0220] Note: "Foam tendency (mL) / foam stability (mL), time to surface (s)" from left to right, 25℃ means the sample is tested at 25℃, 50℃ means the sample is tested by raising the temperature from 25℃ to 50℃, and the last 25℃ means the sample is tested by cooling the temperature from 50℃ to 25℃.

[0221] As shown in Table 2, regarding foam characteristics, Examples 1-3 exhibited a foaming tendency of 20-30 mL and foam stability of 0 mL under the three programs of 25℃, 50℃, and the latter 25℃. The time to the liquid surface (i.e., the time for complete foam dissipation) was 15-35 s, and the defoaming time using the shake-flask method was 24-25 s. This indicates that the examples possess low foaming tendency, zero foam stability, and rapid defoaming capability. Rapid defoaming helps reduce cavitation corrosion, and strong antibacterial properties prevent bacterial colony growth on-site. Without bacterial colony growth, filter element clogging is avoided, reducing the frequency of replacement of support components and further ensuring stable hydraulic pressure. In contrast, Comparative Examples 1-3 generally exhibited longer exposure times during bubbling tests (e.g., Comparative Example 1 had an exposure time of 207 s at 25°C, while Comparative Example 3 had an exposure time as high as 287 s at the latter 25°C). Their defoaming times using the shake-flask method were also significantly longer (67–113 s), reflecting a slower defoaming rate in the Comparative Examples 1-3 systems. This suggests that in high-pressure, high-flow-rate hydraulic systems, foam aggregation and residue are more likely to occur, potentially leading to pressure fluctuations and cavitation corrosion. Comparative Examples 4-6 performed similarly to the examples in bubbling tests (exposure times of 14–26 s), but they showed a significant weakness in another key performance indicator—antibacterial activity: Comparative Examples 4 and 5, after a 1 wt% solution concentration and 24 hours of incubation, had colony counts of 1020 CFU / mL and 106 CFU / mL, respectively. This indicates insufficient inhibition of microorganisms in mine water, easily leading to colony growth, which in turn causes media stratification and precipitates clogging the filtration system. Examples 1-3 all exhibited 0 CFU / mL bacterial colony counts under the same conditions, demonstrating excellent antibacterial effects, significantly superior to Comparative Examples 4 and 5. While Comparative Example 6 met the antibacterial standard (0 CFU / mL), its lubricity was only barely acceptable (431 N), and its sealing material compatibility volume expansion rate reached 3.46% (as shown in Table 1), close to the upper limit of the standard. In summary, only Examples 1-3 simultaneously achieved a balance of low foaming, high antibacterial activity, excellent lubricity, low freezing point, and good sealing material compatibility, demonstrating the synergistic advantages of combining low-foaming lubricating components with a highly efficient antibacterial system.

[0222] Figure 2 This is a comparison chart showing the antibacterial performance of samples from the blank control group, Examples 1-3, and Comparative Examples 1-6. From... Figure 2 It can be seen that, except for Comparative Examples 4 and 5, which showed colony growth, the other examples and comparative examples did not show colony growth.

[0223] According to Tables 1-1, 1-2 and 2, Figure 2 It can be seen that the concentrated fluid for hydraulic supports in each embodiment is suitable for mine conditions where the water hardness is ≤750mg / L.

[0224] In this application, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of this application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0225] 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 at least one of that feature. In the description of this application, "multiple" means at least two, such as two, three, etc., unless otherwise explicitly specified.

[0226] Although embodiments of this application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting this application. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of this application.

Claims

1. A concentrated solution for a low-foaming, high-antibacterial-pressure stent, characterized in that, The product includes a lubricant, an emulsion stabilizer, and an antibacterial agent. The lubricant includes at least one of isooctyl octanoate, isotridecyl alcohol ether, and ethoxylated fatty alcohol modified vegetable oil. The emulsion stabilizer includes at least one of isodecyl alcohol ether, acetylacetonate modified polyether, diethylene glycol tert-butyl ether, and glycerol. The antibacterial agent includes at least one of isothiazolinone and tetramethylphosphoric acid sulfate.

2. The concentrated solution for low-foaming, high-antibacterial-pressure stents according to claim 1, characterized in that, The lubricant comprises 6-13% by weight in the concentrate for the low-foaming, high-antibacterial-pressure stent. And / or, by weight percentage, the emulsifying stabilizer is present in the concentrate for the low-foaming, high-antibacterial-pressure stent at a concentration of 3-9%; And / or, by mass percentage, the content of the antibacterial agent in the concentrate for the low-foaming, high-antibacterial-pressure stent is 0.05-0.1%.

3. The concentrated solution for low-foaming, high-antibacterial-pressure stents according to claim 1, characterized in that, The lubricant is composed of isooctyl octanoate, isotretinoin ether, and ethoxylated fatty alcohol modified vegetable oil, and the mass ratio of isooctyl octanoate, isotretinoin ether, and ethoxylated fatty alcohol modified vegetable oil is (1-2):(1-2):(1-2), which can be 1:1:

1. And / or, the emulsifying stabilizer is composed of isomeric decacarbonyl ether, acetylation diol modified polyether, diethylene glycol tert-butyl ether and glycerol, and the mass ratio of isomeric decacarbonyl ether, acetylation diol modified polyether, diethylene glycol tert-butyl ether and glycerol is (1-3):(1-2):(0.5-1):(1-3), optionally 1:1:0.5:3; And / or, the hydrophilic-lipophilic balance value of the emulsifying stabilizer is 14-18; And / or, the antibacterial agent is composed of isothiazolinone and tetrahydroxymethylphosphonic acid, and the mass ratio of isothiazolinone to tetrahydroxymethylphosphonic acid is 1:(1.6-2.4), optionally 1:

2.

4. The concentrated solution for low-foaming, high-antibacterial-pressure stents according to claim 1, characterized in that, The ethoxylated fatty alcohol modified vegetable oil includes at least one of YS-FAE and castor oil polyoxyethylene ether; And / or, the acetylenic diol modified polyether includes at least one of FS-620 and butynediol diethoxy ether.

5. The concentrated solution for low-foaming, high-antibacterial-pressure stents according to any one of claims 1 to 4, characterized in that, The concentrate for the low-foaming, high-antibacterial-pressure stent also includes other additives and solvents, wherein the other additives include at least one of a buffer, a first corrosion inhibitor, a second corrosion inhibitor, a fluoroalkyl polyether-modified polysiloxane, and an antifreeze, and the solvent includes water.

6. The concentrated solution for low-foaming, high-antibacterial-pressure stents according to claim 5, characterized in that, The corrosion inhibitor includes at least one of citrate and triethanolamine; And / or, the first corrosion inhibitor includes at least one of sebacic acid, dodecanoic acid, and polyalkylepoxycarboxylate; And / or, the fluoroalkyl polyether modified polysiloxane includes at least one of fluoroalkyl polyether modified polysiloxane and alkyl polyether modified fluorosilicone oil; And / or, the antifreeze includes at least one of propylene glycol and ethylene glycol, optionally propylene glycol; And / or, the second corrosion inhibitor includes at least one of benzotriazole and methylbenzotriazole, optionally benzotriazole.

7. The concentrated solution for low-foaming, high-antibacterial-pressure stents according to claim 6, characterized in that, The corrosion inhibitor is composed of citrate and triethanolamine, and the mass ratio of citrate to triethanolamine is (1-2):(1-2), which can be 1:

2. And / or, the first corrosion inhibitor is composed of sebacic acid, dodecanoic acid and polyalkylepoxycarboxylate, and the mass ratio of sebacic acid, dodecanoic acid and polyalkylepoxycarboxylate is 1:(0.8-1.2):(2.4-3.6), optionally 1:1:

3.

8. The concentrated solution for low-foaming, high-antibacterial-pressure stents according to any one of claims 5 to 7, characterized in that, The corrosion inhibitor is present in the concentrate for the low-foaming, high-antibacterial-pressure stent at a mass percentage of 4-10%. And / or, by weight percentage, the first corrosion inhibitor is present in 8-15% of the concentrate for the low-foaming, high-antibacterial-pressure stent; And / or, by weight percentage, the content of the second corrosion inhibitor in the concentrate for the low-foaming, high-antibacterial-pressure stent is 0.05-0.1%; And / or, by mass percentage, the content of the fluoroalkyl polyether modified polysiloxane in the concentrate for the low-foaming, high-antibacterial-pressure stent is 0.05-0.1%; And / or, by weight percentage, the antifreeze content in the concentrate for the low-foaming, high-antibacterial-pressure stent is 10-15%; And / or, the pH of the concentrate for the low-foaming, high-antibacterial-pressure stent is 7.5-10.

0.

9. A method for preparing a concentrated solution for a low-foaming, high-antibacterial-pressure stent as described in any one of claims 5 to 8, characterized in that, include: The solvent, the lubricant, and the emulsion stabilizer are mixed in a first step to obtain a first mixture. The first mixture, the corrosion inhibitor, the first corrosion inhibitor, the second corrosion inhibitor, and a portion of the fluoroalkyl polyether modified polysiloxane are mixed a second time to obtain a second mixture. The second mixture is then mixed with the antifreeze to obtain a third mixture; The third mixture, the antibacterial agent, and the remaining fluoroalkyl polyether modified polysiloxane are mixed in a fourth mixture to obtain a fourth mixture; The fourth mixture is cooled and filtered to obtain the concentrate for the low-foaming, high-antibacterial-pressure stent.

10. The preparation method according to claim 9, characterized in that, The temperature of the first mixture and the temperature of the second mixture are each independently 60-70°C; And / or, the temperature of the fourth mixture is below 50°C, optionally between 25-50°C; And / or, the filtration includes: filtering the cooled product sequentially through a 300-mesh filter, a 500-mesh filter, and an 800-mesh filter; And / or, the first mixing, the second mixing, the third mixing, and the fourth mixing are all carried out under stirring conditions; Preferably, the stirring speed of the first mixture is 80-120 rpm; Preferably, the stirring speed of the second mixing is 100-200 rpm; Preferably, the stirring speed of the fourth mixture is 60-120 rpm, and the stirring time of the fourth mixture is 20-30 min.

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