Preparation method of methoxy silicone oil for silicone rubber anti-structuring agent

Abstract

The present invention relates to the technical field of anti-structuring agents, and provides a method for preparing methoxy silicone oil for silicone rubber anti-structuring agents, comprising: S100, pre-mixing a modified methoxy silicone oil emulsion with dimethyl silicone oil to obtain a first mixed silicone oil emulsion; S200, performing a first stirring treatment on the first mixed silicone oil emulsion, and sequentially adding hydrogenated silicone oil, a siloxane coupling agent, and an antioxidant during the first stirring treatment to obtain a second mixed silicone oil emulsion; S300, degassing the second mixed silicone oil emulsion to obtain methoxy silicone oil for silicone rubber anti-structuring agents. The present invention performs a first stirring treatment on the modified methoxy silicone oil emulsion with dimethyl silicone oil, and then performs a first stirring treatment, and sequentially adds hydrogenated silicone oil, a siloxane coupling agent, and an antioxidant during the first stirring treatment to avoid side reactions and improve product performance, and finally removes bubbles generated by degassing.

Description

Technical Field

[0001] The present invention relates to the technical field of anti-structuring agents, and in particular to a method for preparing methoxy silicone oil for a silicone rubber anti-structuring agent. Background Art

[0002] Silicone rubber is a polymer elastomer with a silicon-oxygen bond (Si-O-Si) as its backbone. It exhibits excellent properties such as high-temperature resistance, low-temperature resistance, chemical corrosion resistance, and electrical insulation, making it widely used in industries such as industry, aerospace, electronics, medical care, and daily necessities. During the preparation of silicone rubber, fillers such as silica (fumed silica) are often added to improve its mechanical properties. However, because silica contains a large number of hydroxyl groups on its surface, it easily forms hydrogen bonds or dipole interactions with the silicone rubber molecular chains, leading to structural problems. These structural problems often worsen over time, seriously affecting the processability and product quality of silicone rubber.

[0003] Antistructurants are additives that inhibit or eliminate the structuring phenomenon in silicone rubber systems. They react with hydroxyl groups on the surface of silica to form hydrophobic groups, reducing the physical or chemical adsorption of fillers onto silicone rubber molecular chains. This reduces the tendency of fillers to aggregate within the silicone rubber matrix, improves filler dispersion, and thus prevents the occurrence of structuring. Currently, the most commonly used antistructurants in silicone rubber are methoxy silicone oils. The methoxy groups in methoxy silicone oils are susceptible to moisture in the environment, hydrolyzing to form methanol and silanol groups. This can cause premature crosslinking or performance degradation, resulting in poor antistructuring effectiveness. Therefore, how to improve the antistructuring effect of silicone rubber has long been a research topic for those skilled in the art. Summary of the Invention

[0004] The present invention aims to solve at least one of the above technical problems.

[0005] The present invention provides a method for preparing methoxy silicone oil for silicone rubber anti-structuring agent, comprising:

[0006] S100, pre-mixing the modified methoxy silicone oil emulsion and dimethyl silicone oil to obtain a first mixed silicone oil emulsion;

[0007] S200, performing a first stirring treatment on the first mixed silicone oil emulsion, and sequentially adding hydrogenated silicone oil, a siloxane coupling agent, and an antioxidant during the first stirring treatment to obtain a second mixed silicone oil emulsion;

[0008] S300, degassing the second mixed silicone oil emulsion to obtain methoxy silicone oil for silicone rubber anti-structuring agent;

[0009] Wherein, the preparation method of modified methoxy silicone oil emulsion comprises:

[0010] S101, adding methoxy silicone oil, an alcohol compound, and a first catalyst to a first solvent, and performing a second stirring process to obtain a hydroxyl-modified methoxy silicone oil intermediate;

[0011] S102, adding a hydroxyl-modified methoxy silicone oil intermediate, an acid anhydride compound, and a second catalyst to a second solvent, and performing a third stirring process to obtain a modified methoxy silicone oil;

[0012] S103, adding modified methoxy silicone oil, initiator, emulsifier, stabilizer and deionized water to the acrylate pre-emulsion, performing a fourth stirring treatment to obtain a modified methoxy silicone oil emulsion;

[0013] The acrylate pre-emulsion contains polyhexamethylene biguanide monomer.

[0014] In any of the above technical features, the preparation method of the acrylate pre-emulsion comprises:

[0015] S111, adding an emulsifier and polyhexamethylene biguanide monomer to deionized water and stirring evenly to obtain a polyhexamethylene biguanide monomer solution;

[0016] S112, performing a fifth stirring treatment on the polyhexamethylene biguanide monomer solution, and dropwise adding an acrylate monomer during the fifth stirring treatment to obtain an acrylate pre-emulsion;

[0017] The acrylate monomers include: methyl methacrylate monomers, butyl acrylate monomers, butyl acrylate monomers, and a mixture of acrylic acid.

[0018] In any of the above technical features, in S100, the mass ratio of the modified methoxy silicone oil emulsion to the dimethyl silicone oil is (1-3):1; and / or in S200, the mass ratio of the first mixed silicone oil emulsion, hydrogenated silicone oil, siloxane coupling agent, and antioxidant is (6-9):(0.5-1):(0.1-0.3):(0.01-0.05).

[0019] In any of the above technical features, in S101, the mass ratio of methoxy silicone oil, alcohol compound, first catalyst, and first solvent is 1: (0.5-0.8): (0.05-0.1): (1-2); and / or in S102, the mass ratio of hydroxyl-modified methoxy silicone oil intermediate, acid anhydride compound, second catalyst, and second solvent is 1: (1-1.2): (0.05-0.1): (1.5-3); and / or in S103, the mass ratio of modified methoxy silicone oil, initiator, emulsifier, stabilizer, deionized water, and acrylate pre-emulsion is 1: (0.2-0.5): (0.2-0.5): (0.01-0.1): (1-6): (1-8).

[0020] In any of the above technical features, in S101, the first catalyst includes: any one of p-toluenesulfonic acid, hydrogen chloride, and acetic acid; and / or in S101, the first solvent includes: any one of toluene, xylene, and tetrahydrofuran; and / or in S102, the second catalyst includes: any one of p-toluenesulfonic acid, triethylamine, and sodium hydroxide; and / or in S102, the second solvent includes: any one of toluene, xylene, and tetrahydrofuran.

[0021] In any of the above technical features, in S101, the temperature of the second stirring treatment is 70℃~120℃; and / or in S101, the time of the second stirring treatment is 4h~8h; and / or in S102, the temperature of the third stirring treatment is 120℃~160℃; and / or in S102, the time of the third stirring treatment is 4h~6h; and / or in S103, the temperature of the fourth stirring treatment is 80℃~100℃; and / or in S103, the time of the fourth stirring treatment is 2h~5h.

[0022] In any of the above technical features, in S200, the rotation speed of the first stirring treatment is 1000rpm~3000rpm; and / or in S200, the temperature of the first stirring treatment is 20℃~25℃; and / or in S300, the degassing treatment is a vacuum degassing treatment.

[0023] In any of the above technical features, in S111, the mass ratio of the emulsifier, polyhexamethylene biguanide monomer, and deionized water is 1:(0.01~0.3):(1~10); and / or in S112, the mass ratio of the polyhexamethylene biguanide monomer to the acrylate monomer is (0.8~1.2):1.

[0024] In any of the above technical features, in S112, the rotation speed of the fifth stirring treatment is 450 rpm to 650 rpm; and / or the temperature of the fifth stirring treatment is 80° C. to 90° C.; and / or the time of the fifth stirring treatment is 1 hour to 2 hours.

[0025] In any of the above technical features, in S300, after the degassing treatment, the method further includes: adding a dispersant for dispersion treatment; the dispersant includes: isostearate or polyether modified silicone oil; the amount of the dispersant added is 0.5%-1% of the mass of the modified methoxy silicone oil.

[0026] After adopting the technical solution of the present invention, the following technical effects can be achieved:

[0027] 1. The present invention pre-mixes a modified methoxy silicone oil emulsion with dimethyl silicone oil, and then performs a first stirring process. During the first stirring process, hydrogenated silicone oil, a siloxane coupling agent, and an antioxidant are added in sequence to avoid side reactions and improve product performance. Finally, a degassing process is performed to remove bubbles generated during the first stirring process.

[0028] 2. The methoxy silicone oil is modified by introducing carboxyl groups into the methoxy silicone oil. Due to the presence of carboxyl groups, the methoxy silicone oil is more likely to react with the hydroxyl groups on the surface of silica to generate hydrophobic groups, and has good compatibility with fillers;

[0029] 3. The acrylate pre-emulsion contains polyhexamethylene biguanide monomer. Acrylate has high weather resistance and can resist the erosion of harsh environmental factors such as ultraviolet rays, high temperature and low temperature. Polyhexamethylene biguanide is antibacterial and corrosion-resistant, so it can improve the storage stability of methoxy silicone oil emulsion, making it antibacterial and corrosion-resistant, not easy to deteriorate, and with stable performance. DETAILED DESCRIPTION

[0030] To make the above-mentioned objectives, features, and advantages of the present invention more clearly understood, the technical solutions in the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. All other embodiments obtained by persons of ordinary skill in the art based on the embodiments of the present invention without creative effort shall fall within the scope of protection of the present invention.

[0031] In the related art, since fillers such as silica are usually added to silicone rubber during the preparation process to improve the mechanical properties, and silica surface contains a large number of hydroxyl groups, which are easy to form hydrogen bonds or dipole interactions with the silicone rubber molecular chains, leading to structuring problems, methoxy silicone oil is usually used as an anti-structuring agent for silicone rubber; however, the methoxy groups in methoxy silicone oil are easily affected by moisture in the environment, and hydrolyze to form methanol and silanol groups, which may cause the system to crosslink prematurely or performance degradation, resulting in poor anti-structuring effect.

[0032] In view of this, the present invention provides a method for preparing methoxy silicone oil for silicone rubber anti-structuring agent. First, a modified methoxy silicone oil emulsion is mixed with dimethyl silicone oil, and then hydrogenated silicone oil, a siloxane coupling agent, and an antioxidant are added to make the prepared methoxy silicone oil more stable and have better anti-structuring effect.

[0033] Specifically, an embodiment of the present invention provides a method for preparing methoxy silicone oil for a silicone rubber anti-structuring agent, comprising:

[0034] S100, pre-mixing the modified methoxy silicone oil emulsion and dimethyl silicone oil to obtain a first mixed silicone oil emulsion;

[0035] S200, performing a first stirring treatment on the first mixed silicone oil emulsion, and sequentially adding hydrogenated silicone oil, a siloxane coupling agent, and an antioxidant during the first stirring treatment to obtain a second mixed silicone oil emulsion;

[0036] S300, degassing the second mixed silicone oil emulsion to obtain methoxy silicone oil for silicone rubber anti-structuring agent.

[0037] Preferably, the present invention performs a first stirring treatment after pre-mixing the modified methoxy silicone oil emulsion with dimethyl silicone oil, and then performs a first stirring treatment. During the first stirring treatment, hydrogenated silicone oil, siloxane coupling agent, and antioxidant are added in sequence to avoid side reactions and improve product performance. Finally, bubbles generated during the first stirring treatment are removed by degassing. Pre-mixing the modified methoxy silicone oil emulsion with dimethyl silicone oil can reduce viscosity and ensure more uniform dispersion when other components are added later. The first mixed silicone oil emulsion is then subjected to a first stirring treatment to ensure uniformity and low viscosity. During the first stirring treatment, hydrogenated silicone oil, siloxane coupling agent, and antioxidant need to be added in sequence until the components are evenly dispersed to obtain a second mixed silicone oil emulsion. Hydroxyl silicone oil is first added. Hydroxyl silicone oil can adjust the molecular cross-linking activity of the anti-structural agent. When the first mixed silicone oil emulsion is stirred to a relatively uniform state after the first stirring treatment, hydroxyl silicone oil is added first to avoid cross-linking with the siloxane coupling agent. and other components to produce side reactions, thereby affecting their cross-linking effect. In addition, hydroxy silicone oil needs to be added slowly to avoid local cross-linking reactions and prevent it from having side reactions with moisture. Then, a siloxane coupling agent is added. The siloxane coupling agent is used to enhance compatibility and interfacial properties. The siloxane coupling agent is added after the hydrogen-containing silicone oil has been evenly dispersed to ensure that the coupling agent can fully act on the interface of the silicone oil system instead of having unnecessary side reactions with the hydrogen-containing silicone oil, thereby reducing the effect of the coupling agent on interfacial modification. Finally, an antioxidant is added. The main function of the antioxidant is to prevent the system from degrading due to oxidation during processing or use. Since there may be certain interactions between the antioxidant and the hydrogen-containing silicone oil or siloxane coupling, adding it in advance may lead to a decrease in the activity of the antioxidant. Therefore, adding the antioxidant after all chemical reactions are basically completed can effectively protect the material from oxidation or aging. Finally, the second mixed silicone oil emulsion is degassed to remove bubbles generated during the first stirring process to obtain methoxy silicone oil for silicone rubber anti-structural agent.

[0038] Preferably, in order to further reduce the adverse effects of moisture, the dimethyl silicone oil, hydrogenated silicone oil, siloxane coupling agent, and antioxidant may be dried to remove any moisture that may be present therein and minimize the interference of moisture.

[0039] Furthermore, the preparation method of the modified methoxy silicone oil emulsion comprises:

[0040] S101, adding methoxy silicone oil, an alcohol compound, and a first catalyst to a first solvent, and performing a second stirring process to obtain a hydroxyl-modified methoxy silicone oil intermediate;

[0041] S102, adding a hydroxyl-modified methoxy silicone oil intermediate, an acid anhydride compound, and a second catalyst to a second solvent, and performing a third stirring process to obtain a modified methoxy silicone oil;

[0042] S103, adding modified methoxy silicone oil, initiator, emulsifier, stabilizer and deionized water to the acrylate pre-emulsion, performing a fourth stirring treatment, and obtaining a modified methoxy silicone oil emulsion.

[0043] Preferably, when preparing the modified methoxy silicone oil emulsion, the methoxy silicone oil needs to be modified first. First, an alcohol compound is reacted with the methoxy silicone oil to cause an esterification reaction between the methoxy group of the methoxy silicone oil and the alcohol to generate a hydroxyl-grafted silicone oil, thereby introducing a hydroxyl group on the methoxy silicone oil; then, an acid anhydride compound is reacted with the hydroxyl group on the methoxy silicone oil to introduce a carboxyl group on the methoxy silicone oil; the presence of the carboxyl group makes it easier for the methoxy silicone oil to react with the hydroxyl group on the surface of silica to generate a hydrophobic group, and has good compatibility with the filler.

[0044] Preferably, since methoxy silicone oil is hygroscopic, it is necessary to first perform vacuum drying on the methoxy silicone oil at 60°C to 80°C for 2h to 4h before reacting with the alcohol compound to avoid moisture interference, thereby affecting the modification process; the methoxy silicone oil can be selected from single-end methoxy silicone oil or double-end methoxy silicone oil; the carboxyl content in the modified methoxy silicone oil is preferably 5% to 10% of the total mass of the modified methoxy silicone oil, the molecular weight of the modified methoxy silicone oil is preferably 300g / mol to 1000g / mol, and the viscosity is preferably less than 10mm 2 / s.

[0045] Preferably, after the modified methoxy silicone oil is prepared, the modified methoxy silicone oil, an initiator, an emulsifier, a stabilizer, and deionized water are added to the acrylate pre-emulsion. The addition of the initiator can cause a polymerization reaction to occur; the emulsifier plays a dispersing role in the emulsion system, promoting the uniform dispersion of the modified methoxy silicone oil; the stabilizer can further stabilize the system and further ensure the stability of the modified methoxy silicone oil emulsion; the acrylate has high weather resistance and can resist erosion by harsh environmental factors such as ultraviolet rays, high temperature, and low temperature; through this method, the modified methoxy silicone oil emulsion prepared has good emulsion stability and is suitable for use in preparing methoxy silicone oil for silicone rubber anti-structuring agent.

[0046] Furthermore, the acrylate pre-emulsion contains polyhexamethylene biguanide monomer, which is antibacterial and corrosion-resistant, thereby improving the storage stability of the modified methoxy silicone oil emulsion, making it antibacterial and corrosion-resistant, not easy to deteriorate, and having stable performance; the preparation method of the polyhexamethylene biguanide monomer includes:

[0047] S121, adding dicyandiamide salt and hexamethylenediamine in a mass ratio of 1: (1-1.2) to an organic solvent, and reacting at 80° C. to 120° C. for 2 h to 4 h;

[0048] S122, evaporating the organic solvent in S121, raising the temperature to 140° C. to 160° C. for polymerization to obtain polyhexamethylene biguanide monomer;

[0049] The dicyandiamide salt includes any one of dicyandiamide sodium, dicyandiamide calcium, and dicyandiamide zinc; and the organic solvent includes any one of ethanol, propanol, and ether.

[0050] Preferably, the preparation method of the acrylate pre-emulsion comprises:

[0051] S111, adding an emulsifier and polyhexamethylene biguanide monomer to deionized water and stirring evenly to obtain a polyhexamethylene biguanide monomer solution;

[0052] S112, performing a fifth stirring treatment on the polyhexamethylene biguanide monomer solution, and dropwise adding an acrylate monomer during the fifth stirring treatment to obtain an acrylate pre-emulsion.

[0053] Preferably, the acrylate has high weather resistance and can resist erosion by harsh environmental factors such as ultraviolet rays, high temperature, and low temperature. The emulsifier and polyhexamethylene biguanide monomer are added to deionized water. The addition of the emulsifier can help the emulsion to be evenly mixed after the subsequent addition of the acrylate monomer, making the prepared acrylate pre-emulsion more stable. Polyhexamethylene biguanide is antibacterial and corrosion-resistant, and thus can improve the storage stability of the methoxy silicone oil emulsion, making it antibacterial and corrosion-resistant, not easy to deteriorate, and having stable performance, further improving the performance of the acrylate pre-emulsion, thereby improving the performance of the methoxy silicone oil used as the silicone rubber anti-structural agent prepared subsequently.

[0054] Furthermore, the acrylate monomers include: a mixture of methyl methacrylate monomer, butyl acrylate monomer, butyl acrylate monomer, and acrylic acid, and the mass ratio of methyl methacrylate monomer, butyl acrylate monomer, butyl acrylate monomer, and acrylic acid is preferably 1: (0.3-0.5): (0.2-0.6): (0.1-0.2); methyl methacrylate has strong polymerization ability, butyl acrylate is an acrylate monomer with a low polymerization temperature and good flexibility, butyl acrylate is a monomer with good chemical resistance and high adhesion performance, acrylic acid is an unreacted basic acid monomer, and copolymerization with other acrylate monomers can obtain better performance; by mixing different acrylate monomers, the weather resistance of the acrylate can be further optimized, and the prepared acrylate pre-emulsion can be made more stable.

[0055] Preferably, in S100, the mass ratio of modified methoxy silicone oil to dimethyl silicone oil is (1-3):1. Methoxy silicone oil, as the main anti-structuring agent for silicone rubber, can not only improve fluidity and dispersibility, enhance anti-sedimentation and anti-rheological capabilities, but also has excellent thermal stability and anti-adhesion properties, and can significantly improve the processability and stability of silicone rubber. The appropriate addition of dimethyl silicone oil can improve dispersibility and matrix compatibility. Therefore, the mass ratio of methoxy silicone oil to dimethyl silicone oil is (1-3):1, so that the methoxy silicone oil used in the anti-structuring agent for silicone rubber not only has good fluidity, stability and other properties, but also gives it good collective compatibility.

[0056] Furthermore, in S200, the mass ratio of the first mixed silicone oil emulsion, hydrogenated silicone oil, siloxane coupling agent, and antioxidant is (6-9): (0.5-1): (0.1-0.3): (0.01-0.05). The hydrogenated silicone oil can adjust the molecular cross-linking activity of the anti-structural agent. If the amount of hydrogenated silicone oil is too much, it will lead to excessive cross-linking, making the silicone rubber hard. If the amount of hydrogenated silicone oil is too little, it will lead to insufficient cross-linking, affecting the wear resistance and other properties of the silicone rubber. The siloxane coupling agent is used to enhance compatibility, and an appropriate amount of siloxane coupling agent is added. It can ensure sufficient surface reactivity; antioxidants can effectively protect materials from oxidation or aging. If the amount of antioxidant is too little, the antioxidant effect is not ideal. If the amount of antioxidant is too much, it will affect the compatibility with other ingredients. Therefore, the mass ratio of the first mixed silicone oil emulsion, hydrogenated silicone oil, siloxane coupling agent, and antioxidant is (6-9): (0.5-1): (0.1-0.3): (0.01-0.05). At this time, the ratio between the components is appropriate, and the performance of the prepared methoxy silicone oil for silicone rubber anti-structural agent is better.

[0057] Preferably, in S101, the mass ratio of methoxy silicone oil, alcohol compound, first catalyst, and first solvent is 1: (0.5-0.8): (0.05-0.1): (1-2), and an appropriate amount of alcohol compound can affect the degree of hydroxyl modification, prevent overreaction, and avoid excessive introduction of hydroxyl groups, thereby affecting the smooth progress of subsequent reactions; an appropriate amount of first solvent helps to increase the solubility of the reactants, reduce viscosity, and ensure the smooth progress of the reaction; an appropriate amount of catalyst helps to accelerate the introduction reaction of hydroxyl groups and increase the reaction rate; too little catalyst may cause the reaction speed to be too slow and the hydroxyl groups cannot be effectively introduced; too much catalyst may cause side reactions and affect the stability of the final product; therefore, the mass ratio of methoxy silicone oil, alcohol compound, first catalyst, and first solvent is 1: (0.5-0.8): (0.05-0.1): (1-2), which can make the amount of hydroxyl groups introduced within an appropriate range and ensure the smooth progress of the reaction.

[0058] Furthermore, in S102, the mass ratio of the hydroxyl-modified methoxy silicone oil intermediate, the acid anhydride compound, the second catalyst, and the second solvent is 1: (1-1.2): (0.05-0.1): (1.5-3). An appropriate amount of the acid anhydride compound can ensure the formation of a stable carboxyl group, thereby making it easier for the methoxy silicone oil to react with the hydroxyl group on the surface of silica; an appropriate amount of the catalyst can promote the rate of carboxyl group formation; an appropriate amount of the second solvent helps to adjust the solvent environment of the reaction, control the solubility and reaction temperature, and avoid the adverse effects of excessive viscosity on the reaction; therefore, the mass ratio of the hydroxyl-modified methoxy silicone oil intermediate, the acid anhydride compound, the second catalyst, and the second solvent is 1: (1-1.2): (0.05-0.1): (1.5-3), which can make the amount of carboxyl group introduced within an appropriate range and ensure the smooth progress of the reaction.

[0059] Furthermore, in S103, the mass ratio of the modified methoxy silicone oil, initiator, emulsifier, stabilizer, deionized water, and acrylate pre-emulsion is 1: (0.2-0.5): (0.2-0.5): (0.01-0.1): (1-6): (1-8), and an appropriate amount of initiator can cause the polymerization reaction to occur; an appropriate amount of emulsifier plays a dispersing role in the emulsion system, promoting the uniform dispersion of the modified methoxy silicone oil; an appropriate amount of stabilizer can further stabilize the system and further ensure the modified Stability of methoxy silicone oil emulsion; an appropriate amount of acrylate monomer can make the prepared modified methoxy silicone oil emulsion resistant to erosion by harsh environmental factors such as ultraviolet rays, high temperature and low temperature; therefore, controlling the mass ratio of modified methoxy silicone oil, initiator, emulsifier, stabilizer, deionized water, and acrylate pre-emulsion to 1: (0.2~0.5): (0.2~0.5): (0.01~0.1): (1~6): (1~8) can ensure that the prepared modified methoxy silicone oil emulsion has better performance.

[0060] Preferably, in S101, the first catalyst includes: any one of p-toluenesulfonic acid, hydrogen chloride, and acetic acid. P-toluenesulfonic acid can better promote the introduction of hydroxyl groups into methoxy silicone oil; hydrogen chloride can promote the reaction under relatively mild conditions; acetic acid can improve the selectivity of the reaction and effectively prevent the formation of by-products.

[0061] Preferably, in S101, the first solvent includes: any one of toluene, xylene, and tetrahydrofuran. Toluene and xylene have good solubility for silicone oil substances; tetrahydrofuran can effectively dissolve polar compounds; using any one of toluene, xylene, and tetrahydrofuran as the first solvent can promote the dissolution of methoxy silicone oil and alcohol compounds, which is beneficial to the reaction.

[0062] Preferably, in S102, the second catalyst includes: any one of p-toluenesulfonic acid, triethylamine, and sodium hydroxide. P-toluenesulfonic acid can effectively increase the reaction rate and promote the formation of carboxyl groups; triethylamine can adjust the reaction environment and promote the formation of carboxyl groups; sodium hydroxide can reduce the formation of acidic by-products and promote the reaction of acid anhydride compounds with hydroxyl groups to form carboxyl groups.

[0063] Preferably, in S102, the second solvent includes: toluene, xylene, and any one of tetrahydrofuran. Toluene and xylene have good solubility for silicone oil substances; tetrahydrofuran can effectively dissolve polar compounds; using any one of toluene, xylene, and tetrahydrofuran as the second solvent can promote the dissolution of the hydroxyl-modified methoxy silicone oil intermediate and the acid anhydride compound, which is beneficial to the reaction.

[0064] Furthermore, the alcohol compound includes any one of methanol, ethanol, isopropanol, n-butanol, and glycerol; the acid anhydride compound includes any one of carbonic anhydride, acetic anhydride, benzoic anhydride, and phthalic anhydride.

[0065] Preferably, in S101, the temperature of the second stirring treatment is 70°C to 120°C, and the time of the second stirring treatment is 4h to 8h. The methoxy groups contained in the methoxy silicone oil easily react with alcohol compounds. Heating to 70°C to 120°C can effectively increase the frequency of collisions between molecules and improve the reaction rate. To ensure that the reaction proceeds fully and a sufficient amount of hydroxyl groups can be introduced into the methoxy silicone oil, the reaction time should be controlled within 4h to 8h, which can avoid the generation of side reactions and ensure that the reaction is complete.

[0066] Furthermore, in S102, the temperature of the third stirring treatment is 120°C to 160°C, at which time the acid anhydride compound reacts with the hydroxyl group and the reaction can proceed smoothly; since by-products will be generated if the reaction time is too long, in order to avoid the generation of by-products, the time of the third stirring treatment is controlled to 4h to 6h.

[0067] Preferably, the temperature of the fourth stirring treatment is 80°C to 100°C. Stirring at this temperature can allow the initiator to promote the generation of the polymerization reaction, thereby causing the acrylate monomer to undergo free radical polymerization and gradually form an emulsion. If the reaction time is controlled within 2h to 5h, better results can be obtained.

[0068] Preferably, in S200, the rotation speed of the first stirring treatment is 1000rpm~3000rpm, which can ensure that all components are evenly distributed, reduce uneven reaction areas, thereby improving the efficiency of the reaction and the consistency of the product. The temperature of the first stirring treatment is 20℃~25℃, which can achieve sufficient mixing effect, improve the uniformity of the reaction, and avoid side reactions.

[0069] Preferably, in S111, the mass ratio of the emulsifier, the polyhexamethylene biguanide monomer, and deionized water is 1:(0.01-0.3):(1-10), and the amount of the emulsifier and the polyhexamethylene biguanide monomer added is appropriate to ensure the balance between the emulsifier and the polyhexamethylene biguanide monomer, thereby ensuring the stability and dispersibility of the emulsion, and enabling it to be uniformly dispersed after the subsequent addition of the acrylate monomer to form an acrylate pre-emulsion.

[0070] Preferably, the mass ratio of the polyhexamethylene biguanide monomer to the acrylate monomer is (0.8-1.2):1, ensuring a balance between the polyhexamethylene biguanide monomer and the acrylate monomer, which can not only ensure the antibacterial properties of the emulsion but also provide good physical properties; and, at this ratio, the ratio helps to control the degree of polymerization and cross-linking, avoiding degradation of product performance due to excessive polymerization or cross-linking.

[0071] Furthermore, in S112, the rotation speed of the fifth stirring treatment is 450rpm~650rpm, which can effectively promote the full mixing of the polyhexamethylene biguanide monomer and the acrylate monomer, avoid particles or uneven dispersion caused by insufficient stirring, and help maintain the stability of the emulsion and prevent the emulsion from phase separation or precipitation; the temperature of the fifth stirring treatment is 80℃~90℃, and the time is 1h~2h. The reaction between the polyhexamethylene biguanide monomer and the acrylate monomer can maintain a high activity and ensure the stability of the emulsion formation, and the time of the fifth stirring treatment is short, which can make the emulsion more uniform without causing adverse effects.

[0072] Preferably, in S300, the degassing treatment is a vacuum degassing treatment, and the vacuum degree of the degassing treatment is -0.08 MPa to -0.1 MPa. The vacuum degassing treatment can remove bubbles, volatile substances and possible moisture in the reaction mixture, thereby improving the purity and stability of the product.

[0073] Furthermore, in S300, after the degassing treatment, the following steps are further included: adding a dispersant for dispersion treatment, which can further ensure that the components in the methoxy silicone oil for the silicone rubber anti-structural agent are evenly dispersed, thereby improving product performance; the dispersant includes: isostearate or polyether modified silicone oil, which has good compatibility with silicone oil and thus has a better dispersion effect; the amount of dispersant added is 0.5%-1% of the mass of the modified methoxy silicone oil to avoid excessive dispersion caused by excessive dispersant, thereby reducing product performance.

[0074] Preferably, the dispersion treatment is carried out under ultrasonic conditions, the ultrasonic power is preferably 50W-100W, and the time is preferably 2min-5min. Ultrasonic dispersion can further improve the effect of the dispersion treatment, making the prepared methoxy silicone oil for silicone rubber anti-structural agent more uniform. The time of ultrasonic dispersion treatment should not be too long to avoid affecting the product performance.

[0075] Example 1

[0076] This embodiment provides a methoxy silicone oil for a silicone rubber anti-structuring agent, the preparation method of which comprises the following steps:

[0077] S100, pre-mixing the methoxy silicone oil emulsion and the dimethyl silicone oil in a mass ratio of 1:1 to obtain a first mixed silicone oil emulsion;

[0078] S200, performing a first stirring treatment on the first mixed silicone oil emulsion at 20° C. and a rotation speed of 1000 rpm. During the first stirring treatment, hydrogenated silicone oil, a siloxane coupling agent, and an antioxidant are sequentially added, wherein the mass ratio of the first mixed silicone oil emulsion, the hydrogenated silicone oil, the siloxane coupling agent, and the antioxidant is 6:0.5:0.1:0.01, to obtain a second mixed silicone oil emulsion;

[0079] S300, performing vacuum degassing treatment on the second mixed silicone oil emulsion at a vacuum degree of -0.08 MPa to obtain methoxy silicone oil for silicone rubber anti-structuring agent;

[0080] The preparation method of modified methoxy silicone oil comprises:

[0081] S101, adding methoxy silicone oil, methanol and p-toluenesulfonic acid to toluene, wherein the mass ratio of methoxy silicone oil, methanol, p-toluenesulfonic acid and toluene is 1:0.5:0.05:1, and performing a second stirring treatment at 70° C. for 8 hours to obtain a hydroxyl-modified methoxy silicone oil intermediate;

[0082] S102, adding a hydroxyl-modified methoxy silicone oil intermediate, carbonic anhydride, and p-toluenesulfonic acid to toluene, wherein the mass ratio of the hydroxyl-modified methoxy silicone oil intermediate, carbonic anhydride, p-toluenesulfonic acid, and toluene is 1:1:0.05:1.5, and performing a third stirring treatment at 120° C. for 6 hours to obtain modified methoxy silicone oil;

[0083] S103, adding modified methoxy silicone oil, initiator, emulsifier, stabilizer and deionized water to the acrylate pre-emulsion, wherein the mass ratio of modified methoxy silicone oil, initiator, emulsifier, stabilizer, deionized water and acrylate pre-emulsion is 1:0.2:0.2:0.01:1:1, and performing a fourth stirring treatment at 80° C. for 5 hours to obtain a modified methoxy silicone oil emulsion;

[0084] Acrylate pre-emulsion was purchased from outside.

[0085] Example 2

[0086] S100, pre-mixing methoxy silicone oil emulsion and dimethyl silicone oil in a mass ratio of 3:1 to obtain a first mixed silicone oil emulsion;

[0087] S200, performing a first stirring treatment on the first mixed silicone oil emulsion at 25° C. and a rotation speed of 3000 rpm. During the first stirring treatment, hydrogenated silicone oil, a siloxane coupling agent, and an antioxidant are sequentially added, wherein the mass ratio of the first mixed silicone oil emulsion, the hydrogenated silicone oil, the siloxane coupling agent, and the antioxidant is 9:1:0.3:0.05, to obtain a second mixed silicone oil emulsion;

[0088] S300, performing vacuum degassing treatment on the second mixed silicone oil emulsion under a vacuum degree of -0.1 MPa to obtain methoxy silicone oil for silicone rubber anti-structuring agent;

[0089] The preparation method of modified methoxy silicone oil comprises:

[0090] S101, adding methoxy silicone oil, ethanol and hydrogen chloride to xylene, wherein the mass ratio of methoxy silicone oil, ethanol, hydrogen chloride and xylene is 1:0.8:0.1:2, and performing a second stirring treatment at 120° C. for 4 hours to obtain a hydroxyl-modified methoxy silicone oil intermediate;

[0091] S102, adding a hydroxy-modified methoxy silicone oil intermediate, acetic anhydride, and triethylamine to xylene, wherein the mass ratio of the hydroxy-modified methoxy silicone oil intermediate, acetic anhydride, triethylamine, and xylene is 1:1.2:0.1:3, and performing a third stirring treatment at 160° C. for 4 hours to obtain modified methoxy silicone oil;

[0092] S103, adding modified methoxy silicone oil, initiator, emulsifier, stabilizer and deionized water to the acrylate pre-emulsion, wherein the mass ratio of modified methoxy silicone oil, initiator, emulsifier, stabilizer, deionized water and acrylate pre-emulsion is 1:0.5:0.5:0.1:6:8, and performing a fourth stirring treatment at 100° C. for 2 hours to obtain a modified methoxy silicone oil emulsion;

[0093] The preparation method of the acrylate pre-emulsion comprises:

[0094] S111, adding an emulsifier and a polyhexamethylene biguanide monomer to deionized water and stirring evenly, wherein the mass ratio of the emulsifier, the polyhexamethylene biguanide monomer, and the deionized water is 1:0.01:1, to obtain a polyhexamethylene biguanide monomer solution;

[0095] S112, performing a fifth stirring treatment on the polyhexamethylene biguanide monomer solution at 80° C. for 2 hours, and adding an acrylate monomer dropwise during the fifth stirring treatment, wherein the mass ratio of the polyhexamethylene biguanide monomer to the acrylate monomer is 0.8:1, and the mass ratio of the methyl methacrylate monomer, the butyl acrylate monomer, the butylene acrylate monomer, and the acrylic acid in the acrylate monomer is preferably 1:0.3:0.2:0.1, to obtain an acrylate pre-emulsion;

[0096] Polyhexamethylene biguanide monomer was purchased from outside.

[0097] Example 3

[0098] This embodiment provides a methoxy silicone oil for a silicone rubber anti-structuring agent, the preparation method of which comprises the following steps:

[0099] S100, pre-mixing methoxy silicone oil emulsion and dimethyl silicone oil in a mass ratio of 2:1 to obtain a first mixed silicone oil emulsion;

[0100] S200, performing a first stirring treatment on the first mixed silicone oil emulsion at 25° C. and a rotation speed of 2000 rpm. During the first stirring treatment, hydrogenated silicone oil, a siloxane coupling agent, and an antioxidant are sequentially added, wherein the mass ratio of the first mixed silicone oil emulsion, the hydrogenated silicone oil, the siloxane coupling agent, and the antioxidant is 7:0.8:0.2:0.03, to obtain a second mixed silicone oil emulsion;

[0101] S300, vacuum degassing the second mixed silicone oil emulsion at a vacuum degree of -0.09 MPa, adding isostearate and performing ultrasonic dispersion treatment at an ultrasonic frequency of 50 W for 5 minutes to obtain methoxy silicone oil for silicone rubber anti-structuring agent;

[0102] The preparation method of modified methoxy silicone oil comprises:

[0103] S101, adding methoxy silicone oil, isopropyl alcohol and acetic acid to tetrahydrofuran, wherein the mass ratio of methoxy silicone oil, isopropyl alcohol, acetic acid and tetrahydrofuran is 1:0.6:0.08:1.5, and performing a second stirring treatment at 100° C. for 6 hours to obtain a hydroxyl-modified methoxy silicone oil intermediate;

[0104] S102, adding a hydroxy-modified methoxy silicone oil intermediate, benzoic anhydride, and sodium hydroxide to tetrahydrofuran, wherein the mass ratio of the hydroxy-modified methoxy silicone oil intermediate, benzoic anhydride, sodium hydroxide, and tetrahydrofuran is 1:1.1:0.08:2.5, and performing a third stirring treatment at 140° C. for 5 hours to obtain modified methoxy silicone oil;

[0105] S103, adding modified methoxy silicone oil, initiator, emulsifier, stabilizer and deionized water to the acrylate pre-emulsion, wherein the mass ratio of modified methoxy silicone oil, initiator, emulsifier, stabilizer, deionized water and acrylate pre-emulsion is 1:0.3:0.3:0.08:5:6, and performing a fourth stirring treatment at 90° C. for 4 hours to obtain a modified methoxy silicone oil emulsion;

[0106] The preparation method of the acrylate pre-emulsion comprises:

[0107] S111, adding an emulsifier and a polyhexamethylene biguanide monomer to deionized water and stirring evenly, wherein the mass ratio of the emulsifier, the polyhexamethylene biguanide monomer, and the deionized water is 1:0.3:10, to obtain a polyhexamethylene biguanide monomer solution;

[0108] S112, performing a fifth stirring treatment on the polyhexamethylene biguanide monomer solution at 90° C. for 1 hour, and adding an acrylate monomer dropwise during the fifth stirring treatment, wherein the mass ratio of the polyhexamethylene biguanide monomer to the acrylate monomer is 1.2:1, and the mass ratio of the methyl methacrylate monomer, the butyl acrylate monomer, the butylene acrylate monomer, and the acrylic acid in the acrylate monomer is preferably 1:0.5:0.6:0.2, to obtain an acrylate pre-emulsion;

[0109] S121, adding sodium dicyandiamide and hexamethylenediamine in a mass ratio of 1:1.2 to ethanol, and reacting at 120°C for 2 hours;

[0110] S122. Evaporate the ethanol in S121, raise the temperature to 160°C for polymerization, and obtain polyhexamethylene biguanide monomer.

[0111] Example 4

[0112] This embodiment provides a methoxy silicone oil for a silicone rubber anti-structuring agent, the preparation method of which comprises the following steps:

[0113] S100, pre-mixing methoxy silicone oil emulsion and dimethyl silicone oil in a mass ratio of 2:1 to obtain a first mixed silicone oil emulsion;

[0114] S200, performing a first stirring treatment on the first mixed silicone oil emulsion at 25° C. and a rotation speed of 2000 rpm. During the first stirring treatment, hydrogenated silicone oil, a siloxane coupling agent, and an antioxidant are sequentially added, wherein the mass ratio of the first mixed silicone oil emulsion, the hydrogenated silicone oil, the siloxane coupling agent, and the antioxidant is 8:0.8:0.2:0.03, to obtain a second mixed silicone oil emulsion;

[0115] S300, performing vacuum degassing on the second mixed silicone oil emulsion at a vacuum degree of -0.1 MPa, then adding polyether modified silicone oil and performing ultrasonic dispersion treatment at an ultrasonic frequency of 100 W for 2 minutes to obtain methoxy silicone oil for silicone rubber anti-structuring agent;

[0116] The preparation method of the modified methoxy silicone oil comprises:

[0117] S101, adding methoxy silicone oil, isopropyl alcohol and acetic acid to tetrahydrofuran, wherein the mass ratio of methoxy silicone oil, isopropyl alcohol, acetic acid and tetrahydrofuran is 1:0.6:0.08:1.5, and performing a second stirring treatment at 100° C. for 6 hours to obtain a hydroxyl-modified methoxy silicone oil intermediate;

[0118] S102, adding a hydroxy-modified methoxy silicone oil intermediate, benzoic anhydride, and sodium hydroxide to tetrahydrofuran, wherein the mass ratio of the hydroxy-modified methoxy silicone oil intermediate, benzoic anhydride, sodium hydroxide, and tetrahydrofuran is 1:1.1:0.08:2.5, and performing a third stirring treatment at 140° C. for 5 hours to obtain modified methoxy silicone oil;

[0119] S103, adding modified methoxy silicone oil, initiator, emulsifier, stabilizer and deionized water to the acrylate pre-emulsion, wherein the mass ratio of modified methoxy silicone oil, initiator, emulsifier, stabilizer, deionized water and acrylate pre-emulsion is 1:0.3:0.3:0.08:5:6, and performing a fourth stirring treatment at 90° C. for 4 hours to obtain a modified methoxy silicone oil emulsion;

[0120] The preparation method of the acrylate pre-emulsion comprises:

[0121] S111, adding an emulsifier and a polyhexamethylene biguanide monomer to deionized water and stirring evenly, wherein the mass ratio of the emulsifier, the polyhexamethylene biguanide monomer, and the deionized water is 1:0.3:10, to obtain a polyhexamethylene biguanide monomer solution;

[0122] S112, performing a fifth stirring treatment on the polyhexamethylene biguanide monomer solution at 90° C. for 1 hour, and adding an acrylate monomer dropwise during the fifth stirring treatment, wherein the mass ratio of the polyhexamethylene biguanide monomer to the acrylate monomer is 1:1, and the mass ratio of the methyl methacrylate monomer, the butyl acrylate monomer, the butylene acrylate monomer, and acrylic acid in the acrylate monomer is preferably 1:0.3:0.3:0.2, to obtain an acrylate pre-emulsion;

[0123] S121, adding dicyandiamide calcium and hexamethylenediamine in a mass ratio of 1:1.1 to ethanol, and reacting at 100°C for 3 hours;

[0124] S122. Evaporate the ethanol in S121, raise the temperature to 150°C, and polymerize to obtain polyhexamethylene biguanide monomer.

[0125] Comparative Example 1

[0126] This comparative example provides a methoxy silicone oil for a silicone rubber anti-structuring agent. The methoxy silicone oil for a silicone rubber anti-structuring agent is purchased from outside, and its main component is methoxy silicone oil.

[0127] Comparative Example 2

[0128] This comparative example provides a methoxy silicone oil for a silicone rubber anti-structuring agent, the preparation method of which comprises the following steps:

[0129] S100, after vacuum drying the methoxy silicone oil at 60° C. for 6 h, pre-mixing the modified methoxy silicone oil and dimethyl silicone oil in a mass ratio of 1:1 to obtain a first mixed silicone oil emulsion;

[0130] S200, performing a first stirring treatment on the first mixed silicone oil emulsion at 20° C. and a rotation speed of 1000 rpm. During the first stirring treatment, hydrogenated silicone oil, a siloxane coupling agent, and an antioxidant are sequentially added, wherein the mass ratio of the first mixed silicone oil emulsion, the hydrogenated silicone oil, the siloxane coupling agent, and the antioxidant is 6:0.5:0.1:0.01, to obtain a second mixed silicone oil emulsion;

[0131] S300, performing vacuum degassing treatment on the second mixed silicone oil emulsion at a vacuum degree of -0.08 MPa to obtain methoxy silicone oil for silicone rubber anti-structuring agent.

[0132] Performance Testing

[0133] Stability Test: The methoxy silicone oil samples for silicone rubber anti-structuring agents in Examples 1 to 4 and Comparative Examples 1 to 2 were placed in a sealed container at room temperature of 25° C. and stored for 90 days to observe whether stratification or precipitation occurred.

[0134] Silicone rubber was prepared, and the methoxy silicone oils for silicone rubber anti-structuring agents in Examples 1 to 4 and Comparative Examples 1 to 2 were added during the preparation process. The following tests were performed on the silicone rubber samples:

[0135] Anti-structural test: The initial hardness of the silicone rubber is measured using a Shore hardness tester. The silicone rubber sample is then placed in an oven and aged at 70°C to 100°C for 100 hours. The hardness of the silicone rubber is measured again using a Shore hardness tester, and the hardness change is recorded.

[0136] UV aging test: To test the tensile strength of silicone rubber, a UV aging chamber was used to irradiate the silicone rubber with UV-A band at 60°C to simulate 365nm ultraviolet radiation for 100 hours. The tensile strength of the sample was then tested again, and the tensile strength retention rate was calculated.

[0137] Thermal stability test: The thermal decomposition temperature of silicone rubber was measured in the range of 0℃~800℃ using a thermogravimetric analyzer;

[0138] The test results are shown in Table 1:

[0139] Table 1

[0140]

[0141]

[0142] As can be seen from Table 1, the methoxy silicone oil for silicone rubber anti-structuring agent in Examples 1 to 4 still has good stability even after being placed for a long time; the silicone rubber prepared by using the methoxy silicone oil for silicone rubber anti-structuring agent in Examples 1 to 4 as the anti-structuring agent is better than the silicone rubber prepared by using the methoxy silicone oil for silicone rubber anti-structuring agent in Comparative Examples 1 to 2. The various properties are better, especially the anti-structuring property, indicating that the silicone rubber prepared by using the methoxy silicone oil for silicone rubber anti-structuring agent in Examples 1 to 4 as the anti-structuring agent has a longer service life; the methoxy silicone oil for silicone rubber anti-structuring agent in Example 2 has better performance than that in Example 1, which may be due to the use of the preparation method of the acrylate pre-emulsion provided by the present invention in Example 2, thereby improving the performance of the silicone rubber anti-structuring agent. The performance of methoxy silicone oil; especially the silicone rubber prepared with methoxy silicone oil as the anti-structuring agent in Examples 3 to 4, this may be because Examples 3 to 4 adopt the preparation method of the acrylate pre-emulsion and the preparation method of the polyhexamethylene biguanide monomer provided by the present invention, and further perform a dispersion treatment after degassing treatment, so that the methoxy silicone oil for the anti-structuring agent of silicone rubber is more uniform, thereby making the performance of the methoxy silicone oil for the anti-structuring agent of silicone rubber better; the silicone rubber prepared with methoxy silicone oil as the anti-structuring agent in Comparative Example 2 has poorer performance than the silicone rubber prepared with methoxy silicone oil as the anti-structuring agent in Example 1, which may be because the modified methoxy silicone oil provided by the present invention is not used in Comparative Example 2, resulting in unsatisfactory anti-structuring effect.

[0143] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A method for preparing methoxy silicone oil for silicone rubber anti-structuring agent, characterized in that: include: S100, pre-mixing the modified methoxy silicone oil emulsion and dimethyl silicone oil to obtain a first mixed silicone oil emulsion; S200, performing a first stirring treatment on the first mixed silicone oil emulsion, and during the first stirring treatment, sequentially adding hydrogenated silicone oil, a siloxane coupling agent, and an antioxidant to obtain a second mixed silicone oil emulsion; S300, degassing the second mixed silicone oil emulsion to obtain the methoxy silicone oil for the silicone rubber anti-structuring agent; Wherein, the preparation method of the modified methoxy silicone oil emulsion comprises: S101, adding methoxy silicone oil, an alcohol compound, and a first catalyst to a first solvent, and performing a second stirring process to obtain a hydroxyl-modified methoxy silicone oil intermediate; S102, adding the hydroxyl-modified methoxy silicone oil intermediate, the acid anhydride compound, and the second catalyst to the second solvent, and performing a third stirring process to obtain modified methoxy silicone oil; S103, adding the modified methoxy silicone oil, initiator, emulsifier, stabilizer and deionized water to the acrylate pre-emulsion, performing a fourth stirring treatment to obtain the modified methoxy silicone oil emulsion; The acrylate pre-emulsion contains polyhexamethylene biguanide monomer, and the preparation method of the acrylate pre-emulsion comprises: S111, adding an emulsifier and polyhexamethylene biguanide monomer to deionized water and stirring evenly to obtain a polyhexamethylene biguanide monomer solution; S112, performing a fifth stirring treatment on the polyhexamethylene biguanide monomer solution, and dropwise adding an acrylate monomer during the fifth stirring treatment to obtain the acrylate pre-emulsion; The acrylic acid ester monomers include: methyl methacrylate monomers, butyl acrylate monomers, butyl acrylate monomers, and a mixture of acrylic acid; The preparation method of polyhexamethylene biguanide monomer comprises: S121, adding dicyandiamide salt and hexamethylenediamine in a mass ratio of 1:(1-1.2) to an organic solvent, and reacting at 80°C-120°C for 2h-4h; S122, evaporating the organic solvent in S121, raising the temperature to 140°C to 160°C for polymerization to obtain polyhexamethylene biguanide monomer; The dicyandiamide salt includes any one of dicyandiamide sodium, dicyandiamide calcium, and dicyandiamide zinc; and the organic solvent includes any one of ethanol, propanol, and ether.

2. The preparation method according to claim 1, characterized in that In the S100, the mass ratio of the modified methoxy silicone oil emulsion to the dimethyl silicone oil is (1-3):1; and / or In S200, the mass ratio of the first mixed silicone oil emulsion, the hydrogenated silicone oil, the siloxane coupling agent, and the antioxidant is (6-9): (0.5-1): (0.1-0.3): (0.01-0.05).

3. The preparation method according to claim 1, characterized in that In S101, the mass ratio of the methoxy silicone oil, the alcohol compound, the first catalyst, and the first solvent is 1: (0.5-0.8): (0.05-0.1): (1-2); and / or In S102, the mass ratio of the hydroxyl-modified methoxy silicone oil intermediate, the acid anhydride compound, the second catalyst, and the second solvent is 1: (1-1.2): (0.05-0.1): (1.5-3); and / or In S103, the mass ratio of the modified methoxy silicone oil, the initiator, the emulsifier, the stabilizer, the deionized water, and the acrylate pre-emulsion is 1: (0.2~0.5): (0.2~0.5): (0.01~0.1): (1~6): (1~8).

4. The preparation method according to claim 1, characterized in that In said S101, said first catalyst comprises: any one of p-toluenesulfonic acid, hydrogen chloride, and acetic acid; and / or In said S101, the first solvent comprises: any one of toluene, xylene, and tetrahydrofuran; and / or In S102, the second catalyst includes: any one of p-toluenesulfonic acid, triethylamine, and sodium hydroxide; and / or In S102, the second solvent includes any one of toluene, xylene, and tetrahydrofuran.

5. The preparation method according to claim 1, characterized in that In said S101, the temperature of said second stirring treatment is 70°C to 120°C; and / or In said S101, the time of the second stirring treatment is 4h~8h; and / or In said S102, the temperature of said third stirring treatment is 120°C to 160°C; and / or In said S102, the time of said third stirring treatment is 4h~6h; and / or In said S103, the temperature of said fourth stirring treatment is 80°C to 100°C; and / or In S103, the fourth stirring process is performed for 2 hours to 5 hours.

6. The preparation method according to claim 1, characterized in that In said S200, the rotation speed of said first stirring process is 1000 rpm to 3000 rpm; and / or In said S200, the temperature of said first stirring treatment is 20°C to 25°C; and / or In the S300 , the degassing process is a vacuum degassing process.

7. The preparation method according to claim 1, characterized in that In S111, the mass ratio of the emulsifier, the polyhexamethylene biguanide monomer, and the deionized water is 1: (0.01-0.3): (1-10); and / or In S112, the mass ratio of the polyhexamethylene biguanide monomer to the acrylate monomer is (0.8-1.2):

1.

8. The preparation method according to claim 1, characterized in that In the above S112, The rotation speed of the fifth stirring process is 450 rpm to 650 rpm; and / or The temperature of the fifth stirring treatment is 80° C. to 90° C.; and / or the time of the fifth stirring treatment is 1 hour to 2 hours.

Images