A polyether-modified silicone oil crosslinking agent, its preparation method and application

Abstract

This application relates to the field of organosilicon materials, specifically disclosing a polyether-modified silicone oil crosslinking agent, its preparation method, and its application. The general structural formula of the polyether-modified silicone oil crosslinking agent is: ; wherein, the structural formulas of R1 and R3 are -CH2- or -CH2-CH2-CH2-O-; and the structural formulas of R2 and R4 are -H, C1~C 10 One of the following: R5 is [formula missing]; R6 is [formula missing] or [formula missing]; the value of a is an integer between 0 and 60, the value of b is an integer between 1 and 12, and the value of c is an integer between 1 and 40. The polyether-modified silicone oil crosslinking agent of this application can significantly improve the compatibility of organosilicon monomers and hydrophilic monomers, resulting in materials with high mechanical strength. Furthermore, it can meet the needs of dry eye patients and long-term contact lens wearers in terms of comfort and safety, and has particularly promising application prospects in the preparation of silicone hydrogel lenses.

Description

Technical Field

[0001] This application relates to the field of organosilicon materials, and more specifically, to a polyether-modified silicone oil crosslinking agent, its preparation method, and its application. Background Technology

[0002] Organosilicon materials, with their unique molecular structure and chemical composition, have demonstrated immense application value in modern industry and technology. Their excellent temperature resistance allows them to operate stably in demanding environments such as aerospace and electronics, providing reliable protection for equipment operation under extreme conditions. Their outstanding weather resistance makes them widely used in outdoor fields such as construction and automotive, maintaining good performance even after long-term exposure to natural environments. Their excellent electrical insulation properties make them indispensable insulating materials in electrical equipment, effectively preventing safety hazards such as current leakage and short circuits. Their flexibility and elasticity endow them with excellent performance in sealing and shock absorption, enabling them to adapt to various complex working scenarios. Furthermore, organosilicon materials also possess good biocompatibility and high permeability, making them highly sought after in biomedicine and personal care fields, such as for the manufacture of contact lenses and medical dressings.

[0003] However, due to the helical structure of silicone molecular chains and the fact that their side groups are often hydrophobic (e.g., nonpolar methyl groups -CH3), the surface composed of methyl groups has a very low surface energy, far lower than that of water, making it a hydrophobic material. When silicone materials are used in combination with hydrophilic monomers, poor compatibility often occurs due to the significant difference in surface energy, which is very detrimental to the application of silicone materials. Take silicone hydrogel lenses as an example (but not limited to this field), which are usually copolymerized from silicone monomers and hydrophilic monomers. However, because high molecular weight silicone monomers are highly hydrophobic and have poor compatibility with hydrophilic monomers, their addition is limited, restricting the improvement of the oxygen permeability of the lens material.

[0004] To address these issues, existing technologies employ various strategies. A common approach is the addition of additives, with crosslinking agents being a frequently used additive in the preparation of silicone hydrogel lenses. Traditional crosslinking agents include ethylene glycol dimethacrylate (EDGMA) and triallyl isocyanurate (TAIC). However, in practical applications, it has been found that these traditional crosslinking agents have poor compatibility with organosilicon monomers, making it difficult to effectively promote the bonding between organosilicon monomers and hydrophilic monomers, resulting in limited improvement in material performance. Moreover, traditional crosslinking agents (such as EDGMA) are difficult to completely remove during the preparation process, and residual amounts can easily trigger ocular allergic reactions; clinical data show a sensitization rate of ≥3%. Furthermore, traditional crosslinking agents are not effective in improving the water content and mechanical properties of silicone hydrogel lenses, making it difficult for existing materials to meet the comfort and safety needs of patients with dry eye syndrome and long-term contact lens wearers. Summary of the Invention

[0005] To address the aforementioned technical problems, this application provides a polyether-modified silicone oil crosslinking agent, its preparation method, and its application.

[0006] Firstly, this application provides a polyether-modified silicone oil crosslinking agent, which adopts the following technical solution: A polyether-modified silicone oil crosslinking agent, the general structural formula of which is shown below: ; Among them, the structural formulas of R1 and R3 are -CH2- or -CH2-CH2-CH2-O-; The structural formulas for R2 and R4 are -H, C1~C 10 , , One of them; The structural formula of R5 is: ; The structural formula of R6 is: or ; The value of 'a' is an integer between 0 and 60, the value of 'b' is an integer between 1 and 12, and the value of 'c' is an integer between 1 and 40.

[0007] In the scheme of this application, the general structural formula of the polyether-modified silicone oil crosslinking agent can be: , , , , , , , , , .

[0008] In the scheme of this application, the value of 'a' can be 0, 5, 10, 15, 20, 25, 30, 35, 40, 50, or 60, but is not limited to the listed values. Other unlisted values ​​within the range of values ​​are also applicable.

[0009] In the scheme of this application, the value of b can be 1, 3, 5, 7, 9, 11, or 12, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0010] In the scheme of this application, the value of c can be 1, 5, 10, 15, 20, 25, 30, 35, or 40, but is not limited to the listed values. Other listed values ​​within the range of values ​​are also applicable.

[0011] By adopting the above technical solution, the polyether-modified silicone oil crosslinking agent of this application is composed of polysiloxane segments and polyether segments. The polysiloxane segments are compatible with organosilicon materials, and the polyether segments are compatible with hydrophilic monomers. This type of polyether-modified silicone oil not only acts as a crosslinking agent but also as a coupling agent, greatly improving the compatibility between organosilicon monomers and hydrophilic monomers. Furthermore, the double bonds in its side chains significantly increase the reaction sites and enhance the degree of crosslinking, thereby improving the mechanical properties of the material. Simultaneously, both the polysiloxane and polyether segments are biocompatible, and the resulting polyether-modified silicone oil crosslinking agent can mitigate the problem of allergic reactions easily caused by traditional crosslinking agent residues. In addition, since the polyether segments can hydrate with water, the water content of silicone hydrogel lenses can be increased.

[0012] Preferably, in the general structural formula of the polyether-modified silicone oil crosslinking agent, the structural formula of R2 or R4 is as follows: or .

[0013] Preferably, in the general structural formula of the polyether-modified silicone oil crosslinking agent, the structural formulas of R2 and R4 are both... or .

[0014] By adopting the above technical solution, this application further enables the main chain to have double bonds, which can coexist with the double bonds of the side chain to form a synergistic effect. The double bonds on the main chain provide a rigid framework, while the double bonds on the side chain increase reaction sites. The combination of the two can form a denser cross-linked network, thereby improving the mechanical strength of the material.

[0015] Secondly, this application provides a method for preparing a polyether-modified silicone oil crosslinking agent, which adopts the following technical solution: A method for preparing a polyether-modified silicone oil crosslinking agent includes the following steps: S1. Under the protection of an inert gas, organosilicon monomers and end-capping agents undergo ring-opening polymerization in the presence of catalyst A. After washing, filtration, and vacuum distillation, hydrogen-containing silicone oil is obtained. S2. Under the protection of an inert gas, hydrogen-containing silicone oil and allyl polyether undergo a hydrosilylation reaction in the presence of catalyst B. After the reaction is completed, the mixture is adsorbed by dry activated carbon and then filtered to obtain polyether-modified silicone oil. S3. Under the protection of an inert gas, polyether-modified silicone oil and isocyanate monomers undergo an addition reaction in a solvent with the aid of catalyst C. After the reaction is completed, the mixture is adsorbed by dried activated carbon, filtered, and rotary evaporated to obtain a polyether-modified silicone oil crosslinking agent.

[0016] Preferably, the organosilicon monomer includes one or more of 1,3,5,7-tetramethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecylmethylcyclohexasiloxane.

[0017] Preferably, the end-capping agent includes one or more of hexamethyldisiloxane, single-terminated hydroxypropyl silicone oil, and double-terminated hydroxypropyl silicone oil.

[0018] Preferably, the molar ratio of the organosilicon monomer to the capping agent is 1:(0.1-5.0).

[0019] In the scheme of this application, the molar ratio of the organosilicon monomer and the capping agent can be 1:0.1, 1:0.2, 1:0.5, 1:0.8, 1:0.9, 1:1.1, 1:2, 1:3, 1:4, 1:5, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0020] Preferably, the molar ratio of 1,3,5,7-tetramethylcyclotetrasiloxane to other organosilicon monomers in the organosilicon monomer is 1:(0-60).

[0021] In the scheme of this application, the molar ratio of 1,3,5,7-tetramethylcyclotetrasiloxane and other organosilicon monomers in the organosilicon monomer can be 1:0, 1:3, 1:10, 1:30, 1:40, or 1:60, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0022] Preferably, the ring-opening polymerization reaction of the organosilicon monomer and the end-capping agent is divided into two steps: first, the hydrogen-containing organosilicon monomer and the end-capping agent are reacted, and then the hydrogen-free organosilicon monomer is added to react.

[0023] By adopting the above technical solution, this application prepares hydrogen-containing silicone oil in two steps. The first step is to add a capping agent and a hydrogen-containing organosilicon monomer (1,3,5,7-tetramethylcyclotetrasiloxane D4H) and react for a period of time. Then, other non-hydrogen organosilicon monomers (hexamethylcyclotrisiloxane D3, octamethylcyclotetrasiloxane D4, decamethylcyclopentasiloxane D5, dodecylcyclohexasiloxane D6) are added and reacted for another period of time. This ensures that each molecular chain has at least a silicon-hydrogen bond, thereby increasing the degree of crosslinking and thus improving the mechanical strength of the material.

[0024] Preferably, catalyst A comprises concentrated sulfuric acid and / or trifluoromethanesulfonic acid.

[0025] Preferably, the amount of catalyst A is 0.5-5.0% of the total mass of the organosilicon monomer and the capping agent.

[0026] In the scheme of this application, the amount of catalyst A can be 0.5%, 1%, 2%, 3%, 4%, or 5% of the total mass of organosilicon monomer and capping agent, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0027] Preferably, the reaction temperature of the ring-opening polymerization reaction in S1 is 10-90℃, and the reaction time is 1-24h.

[0028] In the scheme of this application, the reaction temperature of the ring-opening polymerization reaction in S1 can be 10℃, 20℃, 30℃, 40℃, 50℃, 60℃, 70℃, 80℃, or 90℃, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0029] In the scheme of this application, the reaction time of the ring-opening polymerization reaction in S1 can be 1h, 4h, 8h, 12h, 16h, 18h, 20h, 22h, or 24h, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0030] Preferably, the washing process in S1 specifically involves: first adding an alkaline substance for a first alkaline wash, then adding deionized water for a water wash, and then adding an alkaline substance for a second alkaline wash.

[0031] Preferably, the alkaline substance includes one or more of sodium bicarbonate, sodium carbonate, potassium bicarbonate, and potassium carbonate.

[0032] Preferably, the amount of alkaline substance used in the first alkaline wash is 1-10% of the total mass of the organosilicon monomer and the capping agent.

[0033] In the scheme of this application, the amount of alkaline substance used in the first alkaline washing can be 1%, 2%, 3%, 4%, 5%, 6%, 8%, or 10% of the total mass of organosilicon monomer and capping agent, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0034] Preferably, the time for the first alkaline washing is 1-12 hours.

[0035] In the scheme of this application, the time for one alkaline washing can be 1h, 2h, 3h, 5h, 6h, 8h, 9h, 10h, or 12h, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0036] Preferably, the amount of deionized water used during the water washing is 1-10% of the total mass of the organosilicon monomer and the capping agent.

[0037] In the scheme of this application, the amount of deionized water used during water washing can be 1%, 2%, 3%, 4%, 5%, 6%, 8%, or 10% of the total mass of organosilicon monomer and capping agent, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0038] Preferably, the washing time is 1-12 hours.

[0039] In the scheme of this application, the washing time can be 1h, 2h, 3h, 5h, 6h, 8h, 9h, 10h, or 12h, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0040] Preferably, the amount of alkaline substance used in the secondary alkaline washing is 1-10% of the total mass of the organosilicon monomer and the capping agent.

[0041] In the scheme of this application, the amount of alkaline substance used in the secondary alkaline washing can be 1%, 2%, 3%, 4%, 5%, 6%, 8%, or 10% of the total mass of organosilicon monomer and capping agent, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0042] Preferably, the secondary alkaline washing time is 1-12 hours.

[0043] In the scheme of this application, the time for the secondary alkaline washing can be 1h, 2h, 3h, 5h, 6h, 8h, 9h, 10h, or 12h, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0044] Preferably, the vacuum distillation specifically involves removing low-boiling substances under vacuum at a temperature of 90-150°C for 1-24 hours.

[0045] In the scheme of this application, the temperature of vacuum distillation can be 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, or 150℃, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0046] In the scheme of this application, the time for vacuum distillation can be 1h, 4h, 8h, 10h, 15h, 20h, 25h, 30h, or 40h, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0047] Preferably, the number of repeating units -CH2-CH2-O- in the allyl polyether structure is 1-40.

[0048] In the scheme of this application, the number of repeating units -CH2-CH2-O- in the allyl polyether structure can be 1, 4, 8, 10, 15, 20, 25, 30, or 40, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0049] Preferably, the ratio of the hydrogen-containing silicone oil and allyl polyether is based on the molar ratio between the functional groups Si-H and C=C, and the molar ratio of Si-H to C=C is 1:(0.1-1.2).

[0050] In the scheme of this application, the molar ratio of Si-H and C=C can be 1:0.1, 1:0.5, 1:0.9, 1:0.95, 1:1, or 1:1.2, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0051] Preferably, catalyst B comprises one or more of chloroplatinic acid, Karstedt catalyst, and Wilkinson catalyst.

[0052] Preferably, the amount of catalyst B is 2-100 ppm of the total mass of the mixture of hydrogen-containing silicone oil and allyl polyether.

[0053] In the scheme of this application, the amount of catalyst B can be 2 ppm, 5 ppm, 8 ppm, 10 ppm, 20 ppm, 30 ppm, 40 ppm, 60 ppm, 80 ppm, or 100 ppm of the total mass of the mixture of hydrogen-containing silicone oil and allyl polyether, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0054] Preferably, the reaction temperature of the hydrosilylation reaction in S2 is 60-120℃, and the reaction time is 1-24h.

[0055] In the scheme of this application, the reaction temperature of the hydrosilylation reaction in S2 can be 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, or 120℃, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0056] In the scheme of this application, the reaction time of the hydrosilylation reaction in S2 can be 1h, 2h, 3h, 5h, 6h, 8h, 9h, 10h, or 12h, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0057] Preferably, the amount of dried activated carbon used in S2 is 0.5-10% of the total mass of the mixture of hydrogen-containing silicone oil and allyl polyether.

[0058] In the scheme of this application, the amount of dried activated carbon used in S2 can be 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 8%, or 10% of the total mass of the mixture of hydrogen-containing silicone oil and allyl polyether, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0059] Preferably, the adsorption time of the dried activated carbon in S2 is 1-12 hours.

[0060] In the scheme of this application, the adsorption time of the dried activated carbon in S2 can be 1h, 2h, 3h, 5h, 6h, 8h, 9h, 10h, or 12h, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0061] Preferably, the isocyanate monomer comprises isocyanoethyl methacrylate and / or 2-isocyanoethyl acrylate.

[0062] Preferably, the solvent includes one or more of toluene, ethyl acetate, acetone, tetrahydrofuran, dichloromethane, tetrachloromethane, diethyl ether, dimethylformamide, and dimethyl sulfoxide.

[0063] Preferably, the ratio between the polyether-modified silicone oil and the isocyanate monomer is based on the molar ratio between the functional groups -OH and -NCO, and the molar ratio of -OH to -NCO is 1:(0.1-1.2).

[0064] In the scheme of this application, the molar ratio of -OH and -NCO can be 1:0.1, 1:0.5, 1:0.9, 1:0.95, 1:1, 1:2, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0065] Preferably, the catalyst C comprises dibutyltin dilaurate and / or bismuth neodecanoate.

[0066] Preferably, the amount of catalyst C is 0.1-5.0% of the total mass of the polyether-modified silicone oil and isocyanate monomer mixture.

[0067] In the scheme of this application, the amount of catalyst C can be 0.5%, 1%, 2%, 3%, 4%, or 5% of the total mass of the polyether modified silicone oil and isocyanate monomer mixture, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0068] Preferably, the reaction temperature of the addition reaction in S3 is 10-120℃, and the reaction time is 1-24h.

[0069] In the scheme of this application, the reaction temperature of the addition reaction in S3 can be 10℃, 20℃, 30℃, 40℃, 50℃, 80℃, 90℃, 100℃, or 120℃, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0070] In the scheme of this application, the reaction time of the addition reaction in S3 can be 1h, 4h, 8h, 12h, 16h, 18h, 20h, 22h, or 24h, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0071] Preferably, the amount of dried activated carbon used in S3 is 0.5-10% of the total mass of the polyether modified silicone oil and isocyanate monomer mixture.

[0072] In the scheme of this application, the amount of dried activated carbon used in S2 can be 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 8%, or 10% of the total mass of the polyether modified silicone oil and isocyanate monomer mixture, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0073] Preferably, the adsorption time of the dried activated carbon in S3 is 1-12 hours.

[0074] In the scheme of this application, the adsorption time of the dried activated carbon in S3 can be 1h, 2h, 3h, 5h, 6h, 8h, 9h, 10h, or 12h, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0075] Thirdly, the application of the polyether-modified silicone oil crosslinking agent provided in this application adopts the following technical solution: An application of a polyether-modified silicone oil crosslinking agent, wherein the polyether-modified silicone oil crosslinking agent is used in the preparation of silicone hydrogel lenses, structural composite adhesives, optical adhesives, bonding agents, biomimetic coatings, batteries, personal care, health care, and home care.

[0076] In the scheme of this application, the polyether modified silicone oil crosslinking agent is used in the preparation of silicone hydrogel lenses, and its dosage is 0.5-1.5% of the total mass of the macromolecular silicon monomer material, silane coupling agent and hydrophilic monomer mixture.

[0077] In the scheme of this application, the amount of the polyether modified silicone oil crosslinking agent can be 0.5%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, or 1.5% of the total mass of the macromolecular silicon monomer material, silane coupling agent, and hydrophilic monomer, but is not limited to the listed values. Other listed values ​​within the range are also applicable.

[0078] It should be clarified that the polyether-modified silicone oil crosslinking agent of this application has the function of improving the compatibility between organosilicon materials and hydrophilic monomers. It can be applied to fields that require improved compatibility between organosilicon materials and hydrophilic monomers, such as the preparation of silicone hydrogel lenses, structural composite adhesives, optical adhesives, adhesives, biomimetic coatings, batteries, personal care, health care, and home care. It is not limited to the silicone hydrogel lenses exemplified in this application. This application only uses the specific field of preparing silicone hydrogel lenses to verify the effect of the polyether-modified silicone oil crosslinking agent. Other related fields should also be within the scope of protection of this application.

[0079] In summary, this application has the following beneficial technical effects: Compared with traditional crosslinking agents, the polyether-modified silicone oil crosslinking agent of this application can significantly improve the compatibility of organosilicon monomers and hydrophilic monomers, resulting in materials with high mechanical strength. Furthermore, the polyether segments in its structure can hydrate with water, resulting in a high water content. At the same time, this crosslinking agent has good biocompatibility and almost does not cause eye allergic reactions. It can meet the needs of dry eye patients and long-term contact lens wearers in terms of comfort and safety, and has good application prospects, especially in the field of preparing silicone hydrogel lenses. Detailed Implementation

[0080] The present application will be further described in detail below with reference to the embodiments. Unless otherwise specified, the raw materials used in this application are those that can be obtained conventionally through commercial channels.

[0081] <Preparation Example 1> A polyether-modified silicone oil crosslinking agent, the structural formula of which is shown below: ; The preparation method of this polyether-modified silicone oil crosslinking agent includes the following steps: S1. 1,3,5,7-Tetramethylcyclotetrasiloxane (D4H), octamethylcyclotetrasiloxane (D4), and hexamethyldisiloxane are mixed in a molar ratio of 1:1.33:1.33. Under nitrogen protection, concentrated sulfuric acid at 1% of the total mass of D4H, D4, and hexamethyldisiloxane is added. The ring-opening polymerization reaction is carried out at 25°C for 24 hours. Then, sodium bicarbonate at 2% of the total mass of D4H, D4, and hexamethyldisiloxane is added for a first alkaline wash for 2 hours. Then, deionized water at 0.5% of the total mass of D4H, D4, and hexamethyldisiloxane is added for a second alkaline wash for 2 hours. After that, the mixture is filtered and then vacuum-treated at 100°C for 4 hours to remove low-boiling substances, yielding hydrogen-containing silicone oil 1. S2. Hydrogen-containing silicone oil 1 is mixed with allyl polyether 1, which has 7 repeating units -CH2-CH2-O-, with a Si-H to C=C molar ratio of 1:1. Under nitrogen protection, 5 ppm of chloroplatinic acid (total mass of hydrogen-containing silicone oil 1 and allyl polyether 1) is added, and a hydrosilylation reaction is carried out at 90°C for 3 hours. After the reaction, 3% of dried activated carbon (total mass of hydrogen-containing silicone oil 1 and allyl polyether 1) is added for adsorption for 2 hours. After the reaction, polyether-modified silicone oil 1 is obtained by filtration. S3. Polyether-modified silicone oil 1 and isocyanate methyl methacrylate monomer are mixed in ethyl acetate with a molar ratio of -OH to -NCO of 1:1. Under nitrogen protection, dibutyltin dilaurate (1% by mass of the total mass of polyether-modified silicone oil 1 and isocyanate methyl methacrylate monomer) is added, and the addition reaction is carried out at 25°C for 8 hours. After the reaction, dried activated carbon (3% by mass of the total mass of polyether-modified silicone oil 1 and isocyanate methyl methacrylate monomer) is added for adsorption for 2 hours. After the reaction, polyether-modified silicone oil crosslinking agent 1 is obtained by vacuum filtration and rotary evaporation.

[0082] <Preparation Example 2> A polyether-modified silicone oil crosslinking agent, the structural formula of which is shown below: ; The preparation method of this polyether-modified silicone oil crosslinking agent includes the following steps: S1. 1,3,5,7-Tetramethylcyclotetrasiloxane (D4H), octamethylcyclotetrasiloxane (D4), and hexamethyldisiloxane are mixed in a molar ratio of 1:7.5:1. Under nitrogen protection, concentrated sulfuric acid of 1.5% of the total mass of D4H, D4, and hexamethyldisiloxane is added. The ring-opening polymerization reaction is carried out at 25°C for 24 hours. Then, sodium bicarbonate of 3% of the total mass of D4H, D4, and hexamethyldisiloxane is added for a first alkaline wash of 2 hours. Then, deionized water of 0.75% of the total mass of D4H, D4, and hexamethyldisiloxane is added for a second alkaline wash of 2 hours. Then, sodium bicarbonate of 1.5% of the total mass of D4H, D4, and hexamethyldisiloxane is added for a second alkaline wash of 2 hours. After that, the mixture is filtered and then vacuum-treated at 130°C for 4 hours to remove low-boiling substances, resulting in hydrogen-containing silicone oil 2. S2. Hydrogen-containing silicone oil 2 and allyl polyether 1 are mixed, with a Si-H and C=C molar ratio of 1:1. Under nitrogen protection, 8 ppm of chloroplatinic acid (total mass of hydrogen-containing silicone oil 2 and allyl polyether 1) is added, and a hydrosilylation reaction is carried out at 80°C for 3 hours. After the reaction, 3% of dried activated carbon (total mass of hydrogen-containing silicone oil 2 and allyl polyether 1) is added for adsorption for 2 hours. After the reaction, polyether-modified silicone oil 2 is obtained by filtration. S3. Polyether-modified silicone oil 2 and isocyanate methyl methacrylate monomer were mixed in ethyl acetate with a molar ratio of -OH to -NCO of 1:1. Under nitrogen protection, 1.2% of dibutyltin dilaurate (total mass of polyether-modified silicone oil 2 and isocyanate methyl methacrylate monomer) was added, and the addition reaction was carried out at 25°C for 8 hours. After the reaction was completed, 3% of dried activated carbon (total mass of polyether-modified silicone oil 2 and isocyanate methyl methacrylate monomer) was added for adsorption for 2 hours. After the reaction was completed, polyether-modified silicone oil crosslinking agent 2 was obtained by vacuum filtration and rotary evaporation.

[0083] <Preparation Example 3> A polyether-modified silicone oil crosslinking agent, the structural formula of which is shown below: ; The preparation method of this polyether-modified silicone oil crosslinking agent includes the following steps: S1. 1,3,5,7-Tetramethylcyclotetrasiloxane (D4H) and hydroxypropyl silicone oil (molecular weight approximately 1100) are mixed in a molar ratio of 1:2. Under nitrogen protection, concentrated sulfuric acid of 1.5% of the total mass of D4H and hydroxypropyl silicone oil is added, and the ring-opening polymerization reaction is carried out at 25°C for 24 hours. Then, sodium bicarbonate of 3% of the total mass of D4H and hydroxypropyl silicone oil is added for a first alkaline wash of 2 hours. Then, deionized water of 0.75% of the total mass of D4H and hydroxypropyl silicone oil is added for a water wash of 2 hours. Then, sodium bicarbonate of 1.5% of the total mass of D4H and hydroxypropyl silicone oil is added for a second alkaline wash of 2 hours. After that, the mixture is filtered, and low-boiling substances are removed under vacuum at 80°C for 4 hours to obtain hydrogen-containing silicone oil 3. S2. Mix hydrogen-containing silicone oil 3 with allyl polyether 1, with a Si-H and C=C molar ratio of 1:1. Under nitrogen protection, add 3 ppm of chloroplatinic acid (total mass of hydrogen-containing silicone oil 3 and allyl polyether 1) and carry out a hydrosilylation reaction at 90°C for 3 hours. After the reaction, add 3% of dried activated carbon (total mass of hydrogen-containing silicone oil 3 and allyl polyether 1) for adsorption for 2 hours. After the reaction, obtain polyether-modified silicone oil 3 by suction filtration. S3. Polyether-modified silicone oil 3 and isocyanate methyl methacrylate monomer were mixed in ethyl acetate with a molar ratio of -OH to -NCO of 1:1. Under nitrogen protection, 0.2% of dibutyltin dilaurate (total mass of polyether-modified silicone oil 3 and isocyanate methyl methacrylate monomer) was added, and the addition reaction was carried out at 25°C for 8 hours. After the reaction, 3% of dried activated carbon (total mass of polyether-modified silicone oil 3 and isocyanate methyl methacrylate monomer) was added for adsorption for 2 hours. After the reaction, polyether-modified silicone oil crosslinking agent 3 was obtained by vacuum filtration and rotary evaporation.

[0084] <Preparation Example 4> A polyether-modified silicone oil crosslinking agent, the structural formula of which is shown below: ; The preparation method of this polyether-modified silicone oil crosslinking agent includes the following steps: S1. 1,3,5,7-Tetramethylcyclotetrasiloxane (D4H) and hydroxypropyl silicone oil (molecular weight approximately 1000) are mixed in a molar ratio of 1:2. Under nitrogen protection, concentrated sulfuric acid of 1.5% of the total mass of D4H and hydroxypropyl silicone oil is added, and the ring-opening polymerization reaction is carried out at 25°C for 24 hours. Then, sodium bicarbonate of 3% of the total mass of D4H and hydroxypropyl silicone oil is added for a first alkaline wash of 2 hours. Then, deionized water of 0.75% of the total mass of D4H and hydroxypropyl silicone oil is added for a water wash of 2 hours. Then, sodium bicarbonate of 1.5% of the total mass of D4H and hydroxypropyl silicone oil is added for a second alkaline wash of 2 hours. After that, the mixture is filtered, and low-boiling substances are removed under vacuum at 80°C for 4 hours to obtain hydrogen-containing silicone oil 4. S2. Hydrogen-containing silicone oil 4 and allyl polyether 1 are mixed, with a Si-H and C=C molar ratio of 1:1. Under nitrogen protection, 3 ppm of chloroplatinic acid (total mass of hydrogen-containing silicone oil 4 and allyl polyether 1) is added, and a hydrosilylation reaction is carried out at 90°C for 3 hours. After the reaction, 3% of dried activated carbon (total mass of hydrogen-containing silicone oil 4 and allyl polyether 1) is added for adsorption for 2 hours. After the reaction, polyether-modified silicone oil 4 is obtained by filtration. S3. Polyether-modified silicone oil 4 and isocyanate methacrylate monomer were mixed in ethyl acetate with a molar ratio of -OH to -NCO of 1:1. Under nitrogen protection, 0.2% of dibutyltin dilaurate (total mass of polyether-modified silicone oil 4 and isocyanate methacrylate monomer) was added, and the addition reaction was carried out at 25°C for 8 hours. After the reaction was completed, 3% of dried activated carbon (total mass of polyether-modified silicone oil 4 and isocyanate methacrylate monomer) was added for adsorption for 2 hours. After the reaction was completed, polyether-modified silicone oil crosslinking agent 4 was obtained by vacuum filtration and rotary evaporation.

[0085] <Preparation Example 5> A polyether-modified silicone oil crosslinking agent, the structural formula of which is shown below: ; The preparation method of this polyether-modified silicone oil crosslinking agent includes the following steps: S1. 1,3,5,7-Tetramethylcyclotetrasiloxane (D4H), octamethylcyclotetrasiloxane (D4), and hexamethyldisiloxane are mixed in a molar ratio of 1:7.5:1. Under nitrogen protection, concentrated sulfuric acid of 1.5% of the total mass of D4H, D4, and hexamethyldisiloxane is added. The ring-opening polymerization reaction is carried out at 25°C for 24 hours. Then, sodium bicarbonate of 3% of the total mass of D4H, D4, and hexamethyldisiloxane is added for a first alkaline wash of 2 hours. Then, deionized water of 0.75% of the total mass of D4H, D4, and hexamethyldisiloxane is added for a second alkaline wash of 2 hours. Then, sodium bicarbonate of 1.5% of the total mass of D4H, D4, and hexamethyldisiloxane is added for a second alkaline wash of 2 hours. After that, the mixture is filtered and then vacuum-treated at 130°C for 4 hours to remove low-boiling substances, resulting in hydrogen-containing silicone oil 2. S2. Hydrogen-containing silicone oil 2 is mixed with allyl polyether 2, which has 10 repeating units -CH2-CH2-O-, with a Si-H to C=C molar ratio of 1:1. Under nitrogen protection, 8 ppm of chloroplatinic acid (total mass of hydrogen-containing silicone oil 2 and allyl polyether 2) is added, and a hydrosilylation reaction is carried out at 80°C for 3 hours. After the reaction, 3% of dried activated carbon (total mass of hydrogen-containing silicone oil 2 and allyl polyether 2) is added for adsorption for 2 hours. After the reaction, polyether-modified silicone oil 5 is obtained by filtration. S3. Polyether-modified silicone oil 5 and 2-isocyanate ethyl acrylate monomer were mixed in ethyl acetate with a molar ratio of -OH to -NCO of 1:1. Under nitrogen protection, 1.2% of dibutyltin dilaurate (total mass of polyether-modified silicone oil 5 and 2-isocyanate ethyl acrylate monomer) was added, and the addition reaction was carried out at 25°C for 8 hours. After the reaction, 3% of dried activated carbon (total mass of polyether-modified silicone oil 5 and 2-isocyanate ethyl acrylate monomer) was added for adsorption for 2 hours. After the reaction, polyether-modified silicone oil crosslinking agent 5 was obtained by vacuum filtration and rotary evaporation.

[0086] <Preparation Example 6> A polyether-modified silicone oil crosslinking agent, which differs from Preparation Example 2 in that its structural formula is as follows: ; The preparation method of this polyether-modified silicone oil crosslinking agent includes the following steps: S1. 1,3,5,7-Tetramethylcyclotetrasiloxane (D4H), octamethylcyclotetrasiloxane (D4), and monohydroxypropyl silicone oil (molecular weight approximately 1100) are mixed in a molar ratio of 1:4.5:1. Under nitrogen protection, 1.5% of concentrated sulfuric acid (total mass of D4H, D4, and monohydroxypropyl silicone oil) is added, and the mixture undergoes a ring-opening polymerization reaction at 25°C for 24 hours. Then, 3% of sodium bicarbonate (total mass of D4H, D4, and monohydroxypropyl silicone oil) is added for a first alkaline wash for 2 hours. Next, 0.75% of deionized water (total mass of D4H, D4, and monohydroxypropyl silicone oil) is added for a second water wash for 2 hours. Then, 1.5% of sodium bicarbonate (total mass of D4H, D4, and monohydroxypropyl silicone oil) is added for a second alkaline wash for 2 hours. After filtration, low-boiling substances are removed under vacuum at 130°C for 4 hours to obtain hydrogen-containing silicone oil 5. S2. Mix hydrogen-containing silicone oil 5 with allyl polyether 1, with a Si-H and C=C molar ratio of 1:1. Under nitrogen protection, add 8 ppm of chloroplatinic acid (total mass of hydrogen-containing silicone oil 5 and allyl polyether 1) and carry out a hydrosilylation reaction at 80°C for 3 hours. After the reaction, add 3% of dried activated carbon (total mass of hydrogen-containing silicone oil 5 and allyl polyether 1) for adsorption for 2 hours. After the reaction, obtain polyether-modified silicone oil 6 by filtration. S3. Polyether-modified silicone oil 6 and isocyanate methacrylate monomer were mixed in ethyl acetate with a molar ratio of -OH to -NCO of 1:1. Under nitrogen protection, 1.2% of dibutyltin dilaurate (total mass of polyether-modified silicone oil 6 and isocyanate methacrylate monomer) was added, and the addition reaction was carried out at 25°C for 8 hours. After the reaction was completed, 3% of dried activated carbon (total mass of polyether-modified silicone oil 6 and isocyanate methacrylate monomer) was added for adsorption for 2 hours. After the reaction was completed, polyether-modified silicone oil crosslinking agent 6 was obtained by vacuum filtration and rotary evaporation.

[0087] <Preparation Example 7> A polyether-modified silicone oil crosslinking agent, which differs from Preparation Example 2 in that its structural formula is as follows: ; The preparation method of this polyether-modified silicone oil crosslinking agent includes the following steps: S1. 1,3,5,7-Tetramethylcyclotetrasiloxane (D4H), octamethylcyclotetrasiloxane (D4), and dihydroxypropyl silicone oil (molecular weight approximately 1000) are mixed in a molar ratio of 1:5:1. Under nitrogen protection, 1.5% of concentrated sulfuric acid (total mass of D4H, D4, and dihydroxypropyl silicone oil) is added, and the mixture undergoes a ring-opening polymerization reaction at 25°C for 24 hours. Then, 3% of sodium bicarbonate (total mass of D4H, D4, and dihydroxypropyl silicone oil) is added for a first alkaline wash for 2 hours. Next, 0.75% of deionized water (total mass of D4H, D4, and monohydroxypropyl silicone oil) is added for a second alkaline wash for 2 hours. After that, the mixture is filtered, and low-boiling substances are removed under vacuum at 130°C for 4 hours to obtain hydrogen-containing silicone oil 6. S2. Hydrogen-containing silicone oil 6 and allyl polyether 1 are mixed, with a Si-H and C=C molar ratio of 1:1. Under nitrogen protection, 8 ppm of chloroplatinic acid (total mass of hydrogen-containing silicone oil 6 and allyl polyether 1) is added, and a hydrosilylation reaction is carried out at 80°C for 3 hours. After the reaction, 3% of dried activated carbon (total mass of hydrogen-containing silicone oil 6 and allyl polyether 1) is added for adsorption for 2 hours. After the reaction, polyether-modified silicone oil 7 is obtained by filtration. S3. Polyether-modified silicone oil 7 and isocyanate methyl methacrylate monomer were mixed in ethyl acetate with a molar ratio of -OH to -NCO of 1:1. Under nitrogen protection, 1.2% of dibutyltin dilaurate (total mass of polyether-modified silicone oil 7 and isocyanate methyl methacrylate monomer) was added, and the addition reaction was carried out at 25°C for 8 hours. After the reaction was completed, 3% of dried activated carbon (total mass of polyether-modified silicone oil 7 and isocyanate methyl methacrylate monomer) was added for adsorption for 2 hours. After the reaction was completed, polyether-modified silicone oil crosslinking agent 7 was obtained by vacuum filtration and rotary evaporation.

[0088] <Preparation Example 8> A polyether-modified silicone oil crosslinking agent, differing from Preparation Example 2 in that, in step S1, the ring-opening polymerization reaction of the organosilicon monomer and the capping agent is divided into two steps, specifically: S1. 1,3,5,7-Tetramethylcyclotetrasiloxane (D4H) and hexamethyldisiloxane are mixed at a molar ratio of 1:1. Under nitrogen protection, concentrated sulfuric acid at 1.5% of the total mass of D4H and hexamethyldisiloxane is added, and the ring-opening polymerization reaction is carried out at 25°C for 12 hours. Then, octamethylcyclotetrasiloxane (D4) is added, with a molar ratio of D4H to D4 of 1:7.5, and concentrated sulfuric acid at 1.5% of the mass of D4 is added. The reaction is then carried out at 25°C. The ring-opening polymerization reaction was carried out for 12 hours. Then, sodium bicarbonate with a total mass of 3% of D4H, D4 and hexamethyldisiloxane was added for a first alkaline wash for 2 hours. Then, deionized water with a total mass of 0.75% of D4H, D4 and hexamethyldisiloxane was added for a water wash for 2 hours. Then, sodium bicarbonate with a total mass of 1.5% of D4H, D4 and hexamethyldisiloxane was added for a second alkaline wash for 2 hours. After that, the mixture was filtered and then vacuum-treated at 130°C for 4 hours to remove low-boiling substances, resulting in hydrogen-containing silicone oil 7. S2. Hydrogen-containing silicone oil 7 and allyl polyether 1 are mixed, with a Si-H and C=C molar ratio of 1:1. Under nitrogen protection, 8 ppm of chloroplatinic acid (total mass of hydrogen-containing silicone oil 7 and allyl polyether 1) is added, and a hydrosilylation reaction is carried out at 80°C for 3 hours. After the reaction, 3% of dried activated carbon (total mass of hydrogen-containing silicone oil 7 and allyl polyether 1) is added for adsorption for 2 hours. After the reaction, polyether-modified silicone oil 8 is obtained by filtration. S3. Polyether-modified silicone oil 8 and isocyanate methyl methacrylate monomer were mixed in ethyl acetate with a molar ratio of -OH to -NCO of 1:1. Under nitrogen protection, 1.2% of dibutyltin dilaurate (total mass of polyether-modified silicone oil 8 and isocyanate methyl methacrylate monomer) was added, and the addition reaction was carried out at 25°C for 8 hours. After the reaction was completed, 3% of dried activated carbon (total mass of polyether-modified silicone oil 8 and isocyanate methyl methacrylate monomer) was added for adsorption for 2 hours. After the reaction was completed, polyether-modified silicone oil crosslinking agent 8 was obtained by vacuum filtration and rotary evaporation. The structural formula of the polyether-modified silicone oil crosslinking agent is shown below: .

[0089] <Examples 1-8> A silicone hydrogel material comprising the following components: 1 kg of polyether-modified silicone oil crosslinking agent, 15 kg of self-made macromolecular silicone monomer material DS-1000 (prepared by reacting single-terminated hydroxypropyl silicone oil and isocyanate methacrylate monomer in a molar ratio of 1:1 at 70°C for 5 h under the action of dibutyltin dilaurate catalyst), 35 kg of methacryloyloxypropyltris(trimethylsiloxane)silane (TRIS), 50 kg of hydrophilic monomer N,N-dimethylacrylamide (DMA), and 0.5 kg of initiator 2-hydroxy-2-methylphenylacetone (D-1173); The above components are mixed evenly, injected into a mold, and polymerized by photoinitiation. After demolding and hydration, a silicone hydrogel material is obtained. The difference between Examples 1-8 is that the polyether-modified silicone oil crosslinking agent used is the same as that prepared in Examples 1-8.

[0090] <Comparative Example 1> The difference from Example 2 is that commercially available ethylene glycol dimethacrylate (EGDMA) is used instead of the polyether-modified silicone oil crosslinking agent; otherwise, they are the same as in Example 2.

[0091] <Comparative Example 2> The difference from Example 2 is that the polyether-modified silicone oil crosslinking agent prepared in Example 2 was replaced with a polyether-modified silicone oil crosslinking agent with only double bonds in the main chain (prepared by reacting double-ended polyether-modified silicone oil and isocyanate isocyanate monomer in a molar ratio of 1:2 at 70°C for 5 hours under the action of dibutyltin dilaurate catalyst), and the rest is the same as in Example 2.

[0092] <Performance Testing> 1. The moisture content of the silicone hydrogel materials prepared in the above examples and comparative examples was measured by weighing. The moisture content was calculated as (Q2-G3) / (Q2-Q1)×100%, where Q1 is the weight of the glass slide (dry weight), Q2 is the total weight of the glass slide plus the moistened silicone hydrogel lens, and G3 is the total weight of the glass slide and the dried lens after drying the lens in an oven at 50°C to constant weight. The results are shown in Table 1.

[0093] 2. The elongation at break of the silicone hydrogel materials prepared in the above examples and comparative examples was determined by the tensile test method in GB / T 1040. The test speed was 20 mm / min. The results are shown in Table 1.

[0094] Table 1 Performance Test Results

[0095] As shown in Table 1, the water content of Examples 1-8 of this application was 48.06-50.11%, and the elongation at break was 72.85-161.22%. The experimental results indicate that the polyether-modified silicone oil crosslinking agent of this application, composed of polysiloxane segments and polyether segments, not only acts as a crosslinking agent but also as a coupling agent in the material, significantly improving the compatibility between the organosilicon monomer and the hydrophilic monomer. Simultaneously, the polyether segments can hydrate with water, thus increasing the water content. Furthermore, both the polysiloxane and polyether segments are biocompatible, and the resulting polyether-modified silicone oil crosslinking agent can mitigate the problem of allergic reactions easily caused by traditional crosslinking agent residues. Among these, Examples 5-6 showed an increase in both water content and elongation at break compared to Example 2, indicating that further introduction of double bonds into the main chain can coordinate with the double bonds in the side chains, further improving the mechanical strength and water content of the material.

[0096] Compared to Example 2, Comparative Example 1 showed a significant decrease in both water content and elongation at break. Experimental data indicates that, compared to traditional crosslinking agents, the crosslinking agent of this application can significantly improve the mechanical strength and water content of the silicone hydrogel material. Compared to Example 2, Comparative Example 2 also showed a significant decrease in both water content and elongation at break. Experimental data indicates that, compared to crosslinking agents with double bonds in the main chain, the crosslinking agent of this application can give the material higher mechanical strength and water content.

[0097] The embodiments described in this specific implementation are preferred embodiments of this application and are not intended to limit the scope of protection of this application. Therefore, all equivalent changes made in accordance with the structure, shape and principle of this application should be covered within the scope of protection of this application.

Claims

1. A method for preparing a polyether-modified silicone oil crosslinking agent, characterized in that, Includes the following steps: S1. Under the protection of an inert gas, organosilicon monomers and end-capping agents undergo ring-opening polymerization in the presence of catalyst A. After washing, filtration, and vacuum distillation, hydrogen-containing silicone oil is obtained. S2. Under the protection of an inert gas, hydrogen-containing silicone oil and allyl polyether undergo a hydrosilylation reaction in the presence of catalyst B. After the reaction is completed, the mixture is adsorbed by dry activated carbon and then filtered to obtain polyether-modified silicone oil. S3. Under the protection of an inert gas, polyether-modified silicone oil and isocyanate monomers are subjected to an addition reaction in a solvent under the action of catalyst C. After the reaction is completed, the active adsorption is dried, filtered and evaporated to obtain polyether-modified silicone oil crosslinking agent. The ring-opening polymerization reaction of the organosilicon monomer and the end-capping agent is divided into two steps. Specifically, the hydrogen-containing organosilicon monomer and the end-capping agent are reacted first, and then the hydrogen-free organosilicon monomer is added to react. The general structural formula of the polyether-modified silicone oil crosslinking agent is shown below: ； Among them, the structural formulas of R1 and R3 are -CH2- or -CH2-CH2-CH2-O-; The structural formulas for R2 and R4 are both... or ; The structural formula of R5 is: ; The structural formula of R6 is: or ; The value of 'a' is an integer between 0 and 60, the value of 'b' is an integer between 1 and 12, and the value of 'c' is an integer between 1 and 40.

2. The method for preparing a polyether-modified silicone oil crosslinking agent according to claim 1, characterized in that, The organosilicon monomers include one or more of 1,3,5,7-tetramethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecylmethylcyclohexasiloxane.

3. The method for preparing a polyether-modified silicone oil crosslinking agent according to claim 1, characterized in that, The end-capping agent includes one or more of hexamethyldisiloxane, single-terminated hydroxypropyl silicone oil, and double-terminated hydroxypropyl silicone oil.

4. The method for preparing a polyether-modified silicone oil crosslinking agent according to claim 1, characterized in that, The repeating unit -CH2-CH2-O- in the allyl polyether structure has 1-40 chain segments.

5. The method for preparing a polyether-modified silicone oil crosslinking agent according to claim 1, characterized in that, The isocyanate monomers include isocyanoethyl methacrylate and / or 2-isocyanoethyl acrylate.

6. A polyether-modified silicone oil crosslinking agent prepared by the method of any one of claims 1-5.

7. The application of the polyether-modified silicone oil crosslinking agent according to claim 6, characterized in that, The polyether-modified silicone oil crosslinking agent is used in the preparation of silicone hydrogel lenses, structural composite adhesives, optical adhesives, bonding agents, biomimetic coatings, batteries, personal care, health care, and home care products.

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