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

Abstract

The invention relates to the technical field of anti-structuring agents, and provides a preparation method of methoxy silicone oil for a silicone rubber anti-structuring agent, and the preparation method comprises the following steps: S100, pre-mixing modified methoxy silicone oil emulsion and dimethyl silicone oil to obtain first mixed silicone oil emulsion; s200, carrying out first stirring treatment on the first mixed silicone oil emulsion, and in the first stirring treatment process, sequentially adding hydrogen-containing silicone oil, a siloxane coupling agent and an antioxidant to obtain a second mixed silicone oil emulsion; and S300, carrying out degassing treatment on the second mixed silicone oil emulsion to obtain the methoxy silicone oil for the silicone rubber anti-structuring agent. The modified methoxy silicone oil emulsion and the dimethyl silicone oil are premixed and then subjected to first stirring treatment, in the first stirring treatment process, the hydrogen-containing silicone oil, the siloxane coupling agent and the antioxidant are sequentially added, side reactions are avoided, the product performance is improved, and finally generated bubbles are removed through degassing treatment.

Description

Technical Field

[0001] The 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 silicon-oxygen bond (Si-O-Si) as the main chain. It has excellent properties such as high temperature resistance, low temperature resistance, chemical corrosion resistance and electrical insulation. It is widely used in industries such as industry, aerospace, electronics, medical treatment and daily necessities. In the preparation process of silicone rubber, fillers such as white carbon black (fumed silica) are usually added to improve the mechanical properties. However, since the surface of white carbon black contains a large number of hydroxyl groups, it is easy to form hydrogen bonds or dipole interactions with the silicone rubber molecular chain, resulting in structural problems. This structural problem usually worsens over time, seriously affecting the processability and product quality of silicone rubber.

[0003] Anti-structuring agent is an additive that can inhibit or eliminate the structuring phenomenon in the silicone rubber system. It reacts with the hydroxyl groups on the surface of white carbon black to generate hydrophobic groups, which reduce the physical or chemical adsorption of fillers on silicone rubber molecular chains, thereby reducing the tendency of fillers to agglomerate in the silicone rubber matrix and improving the dispersion of fillers, thereby avoiding the occurrence of structuring phenomena. At present, the commonly used anti-structuring agent in silicone rubber is usually methoxy silicone oil. The methoxy group in methoxy silicone oil is easily affected by moisture in the environment, and hydrolyzes to generate methanol and silanol groups, which may cause the system to crosslink prematurely or performance degradation, resulting in poor anti-structuring effect. Therefore, how to make silicone rubber have a better anti-structuring effect has always been the research direction of technicians in this field. 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, premixing 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 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;

[0008] S300, degassing the second mixed silicone oil emulsion to obtain methoxy silicone oil for silicone rubber anti-structural 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 into a first solvent, and performing a second stirring treatment to obtain a hydroxyl-modified methoxy silicone oil intermediate;

[0011] S102, adding a hydroxy-modified methoxy silicone oil intermediate, an acid anhydride compound and a second catalyst into a second solvent, and performing a third stirring treatment 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, and obtaining 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 a polyhexamethylene biguanide monomer into 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 acrylic acid ester 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 modified methoxy silicone oil emulsion to 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, 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.

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

[0025] In any of the above technical features, in S300, after the degassing treatment, it also includes: adding a dispersant for dispersion treatment; the dispersant includes: isostearate or polyether modified silicone oil; the added amount of the dispersant 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 premixes 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, a siloxane coupling agent, and an antioxidant are added in sequence to avoid side reactions and improve product performance. Finally, a degassing treatment is performed to remove bubbles generated during the first stirring treatment.

[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 the filler;

[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] In order to make the above-mentioned purposes, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention are described clearly and completely. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0031] In the related art, since fillers such as white carbon black are usually added to silicone rubber during the preparation process to improve the mechanical properties, and the surface of white carbon black contains a large number of hydroxyl groups, which are easy to hydrogen bond or dipole interaction with the silicone rubber molecular chain, resulting in structuring problems, methoxy silicone oil is usually used as an anti-structuring agent for silicone rubber; however, the methoxy group in methoxy silicone oil is easily affected by moisture in the environment, and hydrolyzes to generate methanol and silanol groups, which may cause premature cross-linking of the system 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, firstly, a modified methoxy silicone oil emulsion is mixed with dimethyl silicone oil, and then hydrogen-containing silicone oil, a siloxane coupling agent, and an antioxidant are added to make the prepared methoxy silicone oil more stable and have a better anti-structuring effect.

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

[0034] S100, premixing 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 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;

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

[0037] Preferably, the present invention performs a first stirring treatment after premixing 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. Premixing the modified methoxy silicone oil emulsion with dimethyl silicone oil can reduce viscosity and ensure more uniform dispersion when other components are added later. Then, the first mixed silicone oil emulsion is 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 crosslinking 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 first added to avoid crosslinking with the siloxane coupling agent. The hydroxy silicone oil needs to be added slowly to avoid local cross-linking reactions and prevent 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, rather than 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 being degraded 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 reduce the activity of the antioxidant. Therefore, adding an 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 the bubbles generated during the first stirring process, thereby obtaining 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] Further, the preparation method of the modified methoxy silicone oil emulsion comprises:

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

[0041] S102, adding a hydroxy-modified methoxy silicone oil intermediate, an acid anhydride compound and a second catalyst into a second solvent, and performing a third stirring treatment 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-based compound is used to react with the methoxy silicone oil, so that the methoxy group of the methoxy silicone oil and the alcohol undergo an esterification reaction 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 the compatibility with the filler is good.

[0044] Preferably, since methoxy silicone oil is hygroscopic, it is necessary to first perform vacuum drying treatment 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, initiator, emulsifier, 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 and promotes 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 the erosion of harsh environmental factors such as ultraviolet rays, high temperature, and low temperature; through this method, the prepared modified methoxy silicone oil emulsion has good emulsion stability and is suitable for preparing methoxy silicone oil for silicone rubber anti-structural agent.

[0046] Furthermore, the acrylate pre-emulsion contains polyhexamethylene biguanide monomer, which is antibacterial and anti-corrosive, thus 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 comprises:

[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 a polyhexamethylene biguanide monomer;

[0049] The dicyandiamide salt includes any one of dicyandiamide sodium, dicyandiamide calcium, and dicyandiamide zinc; 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 a polyhexamethylene biguanide monomer into 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 dropping 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 the polyhexamethylene biguanide monomer are added to deionized water, and the addition of the emulsifier can help the emulsion to be evenly mixed after the subsequent addition of the acrylate monomer, so that the prepared acrylate pre-emulsion is more stable; polyhexamethylene biguanide is antibacterial and corrosion-resistant, so the storage stability of the methoxy silicone oil emulsion can be improved, making it antibacterial and corrosion-resistant, not easy to deteriorate, and stable in performance, further improving the performance of the acrylate pre-emulsion, thereby improving the performance of the methoxy silicone oil for the silicone rubber anti-structural agent prepared subsequently.

[0054] Furthermore, the acrylate monomers include: a mixture of methyl methacrylate monomers, butyl acrylate monomers, butyl acrylate monomers, and acrylic acid, and the mass ratio of methyl methacrylate monomers, butyl acrylate monomers, butyl acrylate monomers, 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 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 ability, but also has excellent thermal stability and anti-adhesion, 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 as 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 and make the silicone rubber hard. If the amount of hydrogenated silicone oil is too little, it will lead to insufficient cross-linking and affect the wear resistance and other properties of the silicone rubber. The siloxane coupling agent is used to enhance compatibility. The siloxane coupling agent is added in an appropriate amount. 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, hydrogen-containing 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 improve 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 fail to effectively introduce hydroxyl groups; 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 introduced within an appropriate range and ensure the smooth progress of the reaction.

[0058] Furthermore, in S102, the mass ratio of the hydroxy-modified methoxy silicone oil intermediate, the anhydride compound, the second catalyst, and the second solvent is 1: (1-1.2): (0.05-0.1): (1.5-3), and an appropriate amount of the 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 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 hydroxy-modified methoxy silicone oil intermediate, the 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 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, 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), and an appropriate amount of the initiator can cause the polymerization reaction to occur; an appropriate amount of the emulsifier plays a dispersing role in the emulsion system to promote the uniform dispersion of the modified methoxy silicone oil; an appropriate amount of the 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 modified methoxy silicone oil emulsion resistant to corrosion 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 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: 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 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 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 group contained in the methoxy silicone oil easily reacts with the alcohol compound. Heating to 70°C to 120°C can effectively increase the collision frequency between molecules and improve the reaction rate. To ensure that the reaction is fully carried out 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 formation 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 to 3000rpm, which can ensure uniform distribution of all components and reduce uneven reaction areas, thereby improving reaction efficiency and product consistency. The temperature of the first stirring treatment is 20°C to 25°C, which can achieve sufficient mixing effect, improve reaction uniformity, and avoid side reactions.

[0069] Preferably, 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 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 evenly 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, which ensures the balance between the polyhexamethylene biguanide monomer and the acrylate monomer, which can not only ensure the antibacterial property 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 the degradation of product performance caused by 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. In addition, 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 -0.08MPa to -0.1MPa. 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, it also includes: adding a dispersant for dispersion treatment, the dispersion treatment can further ensure that the components in the prepared methoxy silicone oil for silicone rubber anti-structural agent are evenly dispersed, thereby improving product performance; the dispersant includes: isostearate or polyether modified silicone oil, isostearate or polyether modified silicone oil has good compatibility with silicone oil, thereby having 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] Embodiment 1

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

[0077] S100, premixing 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, subjecting the first mixed silicone oil emulsion to a first stirring treatment at 20° C. and a rotation speed of 1000 rpm, and in the process of the first stirring treatment, sequentially adding hydrogenated silicone oil, a siloxane coupling agent, and an antioxidant, 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 under a vacuum degree of -0.08 MPa to obtain methoxy silicone oil for silicone rubber anti-structuring agent;

[0080] Wherein, 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 h to obtain a hydroxyl-modified methoxy silicone oil intermediate;

[0082] S102, adding a hydroxy-modified methoxy silicone oil intermediate, carbonic anhydride and p-toluenesulfonic acid to toluene, wherein the mass ratio of the hydroxy-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 the 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] The acrylic ester pre-emulsion was purchased from outside.

[0085] Embodiment 2

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

[0087] S200, subjecting the first mixed silicone oil emulsion to a first stirring treatment at 25° C. and a rotation speed of 3000 rpm, and in the process of the first stirring treatment, sequentially adding hydrogenated silicone oil, a siloxane coupling agent, and an antioxidant, 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] Wherein, 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 the 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 acrylic ester pre-emulsion comprises:

[0094] S111, adding an emulsifier and a polyhexamethylene biguanide monomer into 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, subjecting the polyhexamethylene biguanide monomer solution to a fifth stirring treatment at 80° C. for 2 hours, and during the fifth stirring treatment, adding an acrylate monomer dropwise, wherein the mass ratio of the polyhexamethylene biguanide monomer to the acrylate monomer is 0.8:1, and among the acrylate monomers, the mass ratio of the methyl methacrylate monomer, the butyl acrylate monomer, the butyl acrylate monomer, and acrylic acid is preferably 1:0.3:0.2:0.1, to obtain an acrylate pre-emulsion;

[0096] The polyhexamethylene biguanide monomer was purchased from outside.

[0097] Embodiment 3

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

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

[0100] S200, subjecting the first mixed silicone oil emulsion to a first stirring treatment at 25° C. and a rotation speed of 2000 rpm, and in the process of the first stirring treatment, sequentially adding hydrogenated silicone oil, a siloxane coupling agent, and an antioxidant, 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] Wherein, the preparation method of modified methoxy silicone oil comprises:

[0103] S101, adding methoxy silicone oil, isopropanol and acetic acid to tetrahydrofuran, wherein the mass ratio of methoxy silicone oil, isopropanol, 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 the 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 acrylic ester pre-emulsion comprises:

[0107] S111, adding an emulsifier and a polyhexamethylene biguanide monomer into 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, subjecting the polyhexamethylene biguanide monomer solution to a fifth stirring treatment at 90° C. for 1 hour, and during the fifth stirring treatment, adding an acrylate monomer dropwise, wherein the mass ratio of the polyhexamethylene biguanide monomer to the acrylate monomer is 1.2:1, and among the acrylate monomers, the mass ratio of the methyl methacrylate monomer, the butyl acrylate monomer, the butyl acrylate monomer, and acrylic acid 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 into ethanol, and reacting at 120°C for 2h;

[0110] S122, evaporating the ethanol in S121, raising the temperature to 160°C for polymerization, and obtaining a polyhexamethylene biguanide monomer.

[0111] Embodiment 4

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

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

[0114] S200, subjecting the first mixed silicone oil emulsion to a first stirring treatment at 25° C. and a rotation speed of 2000 rpm, and in the process of the first stirring treatment, sequentially adding hydrogenated silicone oil, a siloxane coupling agent, and an antioxidant, 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 treatment on the second mixed silicone oil emulsion under the condition of a vacuum degree of -0.1 MPa, and 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-structural agent;

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

[0117] S101, adding methoxy silicone oil, isopropanol and acetic acid to tetrahydrofuran, wherein the mass ratio of methoxy silicone oil, isopropanol, 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 the 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 acrylic ester pre-emulsion comprises:

[0121] S111, adding an emulsifier and a polyhexamethylene biguanide monomer into 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 during the fifth stirring treatment, adding an acrylate monomer dropwise, wherein the mass ratio of the polyhexamethylene biguanide monomer to the acrylate monomer is 1:1, and among the acrylate monomers, the mass ratio of the methyl methacrylate monomer, the butyl acrylate monomer, the butyl acrylate monomer, and acrylic acid 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 3h;

[0124] S122, evaporating the ethanol in S121, raising the temperature to 150°C for polymerization, and obtaining a 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 the 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, and the preparation method thereof comprises the following steps:

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

[0130] S200, subjecting the first mixed silicone oil emulsion to a first stirring treatment at 20° C. and a rotation speed of 1000 rpm, and in the process of the first stirring treatment, sequentially adding hydrogenated silicone oil, a siloxane coupling agent, and an antioxidant, 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 under the condition of 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 agent in Examples 1 to 4 and Comparative Examples 1 to 2 were placed in a closed container at room temperature of 25° C., and after storage for 90 days, whether stratification or precipitation occurred was observed;

[0134] Silicone rubber was prepared, and the methoxy silicone oil for silicone rubber anti-structuring agent in Examples 1 to 4 and Comparative Examples 1 to 2 was added during the preparation process, and 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, and then the silicone rubber sample is 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: Test the tensile strength of silicone rubber by irradiating the silicone rubber with UV-A band at 60°C to simulate 365nm ultraviolet radiation for 100 hours, then test the tensile strength of the sample again and calculate the tensile strength retention rate;

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

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

[0139] Table 1

[0140]

[0141]

[0142] It can be seen from Table 1 that 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 an anti-structuring agent has better properties, especially the anti-structuring property, than the silicone rubber prepared by using the methoxy silicone oil for silicone rubber anti-structuring agent in Comparative Examples 1 to 2. This shows that the silicone rubber prepared by using the methoxy silicone oil for silicone rubber anti-structuring agent in Examples 1 to 4 as an 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 fact that the preparation method of the acrylate pre-emulsion provided by the present invention is adopted in Example 2, thereby improving the performance of the methoxy silicone oil for 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, which may be due to the fact that Examples 3 to 4 adopted the preparation method of the acrylate pre-emulsion and the preparation method of the polyhexamethylene biguanide monomer provided by the present invention, and further carried out a dispersion treatment after the degassing treatment, so that the methoxy silicone oil for the silicone rubber anti-structuring agent is more uniform, thereby making the performance of the methoxy silicone oil for the silicone rubber anti-structuring agent better; the silicone rubber prepared with methoxy silicone oil as the anti-structuring agent in Comparative Example 2 is inferior to the silicone rubber prepared with methoxy silicone oil as the anti-structuring agent in Example 1, which may be due to the fact that the modified methoxy silicone oil provided by the present invention was not used in Comparative Example 2, resulting in an 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 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, premixing 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 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 into a first solvent, and performing a second stirring treatment to obtain a hydroxyl-modified methoxy silicone oil intermediate; S102, adding the hydroxy-modified methoxy silicone oil intermediate, the acid anhydride compound and the second catalyst into the second solvent, and performing a third stirring treatment 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 acrylic ester pre-emulsion contains polyhexamethylene biguanide monomer.

2. The preparation method according to claim 1, characterized in that: The preparation method of the acrylic ester pre-emulsion comprises: S111, adding an emulsifier and a polyhexamethylene biguanide monomer into 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: a mixture of methyl methacrylate monomers, butyl acrylate monomers, butyl acrylate monomers, and acrylic acid.

3. 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).

4. 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 hydroxy-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).

5. The preparation method according to claim 1, characterized in that: 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.

6. The preparation method according to claim 1, characterized in that: In the S101, the temperature of the second stirring treatment is 70° C. to 120° C.; and / or In S101, the second stirring treatment time is 4h to 8h; and / or In S102, the temperature of the third stirring treatment is 120° C. to 160° C.; and / or In S102, the third stirring treatment lasts for 4 hours to 6 hours; and / or In S103, the temperature of the 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.

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

8. The preparation method according to claim 2, 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 the S112, the mass ratio of the polyhexamethylene biguanide monomer to the acrylate monomer is (0.8-1.2):

1.

9. The preparation method according to claim 2, characterized in that: In the 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 fifth stirring treatment lasts for 1 h to 2 h.

10. The preparation method according to any one of claims 1 to 9, characterized in that: In the S300, after the degassing treatment, the following steps are further included: Adding a dispersant to the methoxy silicone oil for silicone rubber anti-structuring agent for dispersion treatment; The dispersant includes: isostearate or polyether modified silicone oil; The added amount of the dispersant is 0.5%-1% of the mass of the modified methoxy silicone oil.

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