Synthesis method and application of high-performance moisture-curing organic silicon resin

Abstract

The invention relates to the technical field of organic silicon resin preparation, in particular to a synthesis method and application of high-performance moisture-curing organic silicon resin. The preparation method of the organic silicon resin comprises the following steps: step 1, adding an epoxy monomer and 2-vinylpyridine into a solvent, and then adding an initiator to obtain a mixed solution; step 2, adding an organic silicon monomer into a solvent, adding a composite catalyst, and stirring for reaction to obtain an organic silicon prepolymer; and step 3, adding the modified filler into the mixed solution at room temperature, carrying out stirring reaction under the protection of inert gas, then adding the organic silicon prepolymer, carrying out copolymerization reaction, and carrying out reduced pressure distillation to obtain the organic silicon resin. The prepared organic silicon resin has the advantages of excellent mechanical property, high tensile strength, large elongation at break, excellent tear strength, waterproofness, good bonding strength, high curing efficiency, short surface drying and hard drying time, mechanical strength and flexibility, and reliable waterproofness and cohesive force.

Description

Technical Field

[0001] The present invention relates to the technical field of preparation of organic silicon resins, and more particularly to a synthesis method of a high-performance moisture-curing organic silicon resin and its application. Background Art

[0002] Moisture-curing silicone resins are a type of functional material that crosslinks when exposed to ambient moisture and are widely used in building sealing, electronic packaging, industrial protection, and other fields. However, conventional moisture-curing silicone resins still face the following core issues in practical applications: (1) Conventional alkoxysilane systems rely on moisture in the air to complete the hydrolysis-condensation reaction, but the curing speed is significantly affected by humidity and temperature. In low-humidity environments (such as dry areas or winter), the curing time is prolonged or even incomplete crosslinking occurs, resulting in low construction efficiency. (2) Conventional moisture-curing resins have a low crosslinking density, resulting in the hardness, tensile strength, and tear resistance of the cured material being difficult to meet the requirements of high-end applications. At the same time, long-term exposure to ultraviolet light, salt spray, or chemical media can easily lead to yellowing, embrittlement, or surface powdering, which affects the service life. (3) Moisture-curing silicone resins generally have weak adhesion to non-silicon substrates and require primers or complex surface treatments (such as sandblasting and plasma activation) to achieve reliable bonding, which increases process complexity and cost. In addition, uneven filler dispersion or insufficient interfacial bonding can easily lead to coating delamination or cracking. Summary of the Invention

[0003] In order to solve the technical problems mentioned in the background technology, the present invention provides a synthesis method and application of high-performance moisture-curing silicone resin, optimizes the comprehensive performance of traditional moisture-curing silicone resin, and provides a new path for the green and high-performance development of silicone functional materials.

[0004] The present invention provides a method for synthesizing a high-performance moisture-curing silicone resin, which adopts the following technical solution: A method for synthesizing a high-performance moisture-curing silicone resin comprises the following preparation steps: Step 1: adding epoxy monomer and 2-vinyl pyridine to a solvent, then adding an initiator, and stirring evenly to obtain a mixed solution; Step 2: Add the organosilicon monomer to the solvent, stir evenly, heat to 30-40°C, add the composite catalyst, stir and react for 2-4 hours to obtain the organosilicon prepolymer; Step 3: Add the modified filler to the mixed liquid at room temperature, raise the temperature to 40-50°C under the protection of inert gas, stir and react for 1-2 hours, then add it to the silicone prepolymer, stir evenly, raise the temperature to 60-80°C, copolymerize for 3-4 hours, and distill under reduced pressure to obtain a high-performance moisture-curing silicone resin.

[0005] Preferably, the epoxy monomer is one or more of 3,4-epoxycyclohexyl methacrylate, allyl glycidyl ether, and glycidyl methacrylate.

[0006] Preferably, the mass ratio of the epoxy monomer, 2-vinylpyridine, solvent and azobisisobutyronitrile is 18-25:10-12:60-80:0.2-0.5.

[0007] Preferably, the solvent is prepared by compounding dimethyl carbonate and propylene glycol methyl ether acetate in a volume ratio of 7-9:1-3.

[0008] Preferably, the organosilicon monomer is composed of methyltrimethoxysilane, perfluorooctyltriethoxysilane and an organosilicon monomer containing an oxime group in a mass ratio of 10-15:5-8:2-5.

[0009] Preferably, the oxime-containing organosilicon monomer is composed of tetrakis(4-methyl-2-pentanoneoxime)silane and vinyltributylanoneoximesilane in a mass ratio of 8-10:1-3.

[0010] Preferably, the mass ratio of the organosilicon monomer, the solvent and the composite catalyst is 20-30:60-80:0.1-0.2.

[0011] Preferably, the composite catalyst is composed of dibutyltin dilaurate and triethylamine in a mass ratio of 3-8:1-2.

[0012] Preferably, the mass ratio of the mixed liquid, the modified filler and the silicone prepolymer is 30-40:10-20:50-60.

[0013] Preferably, the preparation method of the modified filler is as follows: dispersing the nanofiller in a polyvinyl alcohol aqueous solution, ultrasonically treating for 10-30 minutes, magnetically stirring at 60-80°C for 1-2 hours, and drying to obtain a hydroxylated filler; adding the hydroxylated filler to an ethanol solution of a mercaptosilane coupling agent, adding acetic acid to adjust the pH to 4-6, heating to 50-80°C, stirring under nitrogen protection for 2-4 hours, filtering, washing, and drying at 60-80°C for 4-6 hours to obtain a modified filler.

[0014] Preferably, the mercaptosilane coupling agent is one or more of γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane and γ-mercaptopropylmethyldimethoxysilane.

[0015] Preferably, the nanofiller is one or more of nano-silicon dioxide, nano-silicon carbide, and nano-boron nitride.

[0016] The present invention also provides a high-performance moisture-curable organic silicon resin prepared by the above method for use in the field of coatings.

[0017] In summary, the present invention has the following beneficial effects: The present invention selects a combination of epoxy monomer and 2-vinylpyridine as polymerization monomers. The epoxy groups in the epoxy monomer can serve as active crosslinking points in the subsequent copolymerization and curing processes, thereby increasing the rigidity of the copolymer chain segments. The synergistic crosslinking of the epoxy groups and the silicone prepolymer can form a denser network structure, reducing the penetration path of solvent molecules or water molecules. The pyridine ring and vinyl chain segments of 2-vinylpyridine can provide a certain degree of flexibility. The combination of the two can balance the rigidity and flexibility of the resin. The polar groups of the pyridine ring and the polar structure of the epoxy group can improve the adhesion of the resin to polar substrates (such as metal and glass). During the wet curing process, the weakly basic groups of the pyridine ring in 2-vinylpyridine can catalyze the hydrolysis of alkoxy groups in the silicone prepolymer to generate silanol groups, thereby accelerating the condensation crosslinking reaction.

[0018] The present invention selects methyltrimethoxysilane, perfluorooctyltriethoxysilane and an organic silicon monomer containing an oxime group to be compounded as the organic silicon resin synthesis monomer. Among them, methyltrimethoxysilane has a fast hydrolysis rate and provides initial strength for the resin, while the oxime group has a delayed crosslinking effect. The oxime group slowly hydrolyzes in moisture to release ketoxime and generate silanol groups. Its reaction rate is lower than that of methoxy, tetra(4-methyl-2-pentanone oxime) Silane provides four oxime groups, with high crosslinking density but slow reaction. The vinyl group of vinyl trisbutyl ketoxime silane can participate in free radical copolymerization, and the three oxime groups provide a moderate crosslinking rate, avoiding the uneven curing caused by a single oxime silane and resulting in cracks. In this silicone resin, methyltrimethoxysilane provides rapid initial crosslinking, and the silicone monomer containing oxime groups fills the network defects by delayed crosslinking. Perfluorooctyl triethoxysilane is selected, and the low surface energy and chemical stability of the fluorocarbon segment and the crosslinking ability of the silane group give the resin excellent waterproof and anti-fouling properties. Its compound system with methyltrimethoxysilane and oxime silane breaks through the performance limitations of a single silane monomer through functional complementarity.

[0019] In the present invention, a silane coupling agent containing a mercapto group is used to treat the nanofiller. The mercapto group can undergo a thiol-ene click reaction with the double bonds in 2-vinylpyridine and 3,4-epoxycyclohexyl methacrylate in the mixed solution to form a stable CS bond. At the same time, the silane alkoxy group is hydrolyzed and condensed with the hydroxyl groups on the surface of the nanosilica to form a Si-O-Si covalent bond. Through the bridging structure, the interfacial bonding strength between the filler and the resin matrix is significantly improved, reducing stress concentration. In addition, the mixed solution and the modified nanosilica first undergo a partial click reaction between the mercapto group and the double bond, so that the filler is evenly dispersed in the polymer matrix. When the organosilicon prepolymer is added, its silanol group can further react with the epoxy group or residual double bond in the mixed solution, further polymerizing the organosilicon network and the pre-dispersed filler, thereby improving the overall strength and toughness. DETAILED DESCRIPTION

[0020] The present invention is further described in detail below with reference to the examples.

[0021] 3,4-Epoxycyclohexyl methacrylate used in the examples and comparative examples of the present invention was purchased from Wuhan Smack Biotechnology Co., Ltd.; methyltrimethoxysilane (Article No.: YJ-68) was purchased from Shandong Yuanjin New Materials Co., Ltd.; perfluorooctyltriethoxysilane was purchased from Wuhan Smack Biotechnology Co., Ltd.; tetrakis(4-methyl-2-pentanoneoxime)silane (industrial grade) was purchased from Jingzhou Yinjie Chemical Co., Ltd.; vinyltributylanoneoximesilane was purchased from Yunsheng Chemical (Shandong) Co., Ltd.; nanosilica was purchased from Shijiazhuang Huihe Yongsheng Nanotechnology Co., Ltd.; polyvinyl alcohol was purchased from Jinan Xinling Chemical Technology Co., Ltd.; and γ-mercaptopropyltrimethoxysilane was purchased from Wuhan Smack Biotechnology Co., Ltd.

[0022] Examples 1-3 provide a method for synthesizing a high-performance moisture-curable silicone resin and its application.

[0023] Example 1 A method for synthesizing a high-performance moisture-curing silicone resin comprises the following preparation steps: Step 1, adding an epoxy monomer and 2-vinylpyridine to a solvent, then adding azobisisobutyronitrile, and stirring evenly to obtain a mixed solution, wherein the mass ratio of the epoxy monomer, 2-vinylpyridine, solvent and azobisisobutyronitrile is 18:10:60:0.2, and the epoxy monomer is 3,4-epoxycyclohexyl methacrylate; Step 2: Add the organosilicon monomer to the solvent, stir evenly, heat to 30° C., add the composite catalyst, and stir the mixture for 2 hours to obtain an organosilicon prepolymer, wherein the organosilicon monomer is composed of methyltrimethoxysilane, perfluorooctyltriethoxysilane, and an oxime-containing organosilicon monomer in a mass ratio of 10:5:2, the oxime-containing organosilicon monomer is composed of tetrakis(4-methyl-2-pentanoneoxime)silane and vinyltributylanoneoximesilane in a mass ratio of 8:1, the mass ratio of the organosilicon monomer, the solvent, and the composite catalyst is 20:60:0.1, the solvent is compounded of dimethyl carbonate and propylene glycol methyl ether acetate in a volume ratio of 7:3, and the composite catalyst is composed of dibutyltin dilaurate and triethylamine in a mass ratio of 3:1; Step 3: Add modified nano-silica to the mixed solution at room temperature, raise the temperature to 40° C. under inert gas protection, stir and react for 1 hour, then add the organosilicon prepolymer, stir evenly, control the stirring speed to 100 rpm, raise the temperature to 60° C., copolymerize for 3 hours, and distill under reduced pressure to obtain a high-performance moisture-curing organosilicon resin, wherein the mass ratio of the mixed solution, modified nano-silica and organosilicon prepolymer is 30:10:50; The preparation method of modified nano-silica is as follows: dispersing nano-silica in a polyvinyl alcohol aqueous solution with a concentration of 5wt%, controlling the solid-liquid ratio to be 1:5, ultrasonically treating for 10 minutes, with an ultrasonic power of 100W and an ultrasonic frequency of 40KHz, at 60°C, magnetically stirring for 1 hour, and drying to obtain a hydroxylated filler; adding the hydroxylated filler to a γ-mercaptopropyltrimethoxysilane ethanol solution with a concentration of 2wt%, controlling the solid-liquid ratio to be 3:10, adding acetic acid to adjust the pH to 4, heating to 50°C, stirring under nitrogen protection for 2 hours, stirring at a speed of 200rpm, filtering, washing, and drying at 60°C for 4 hours to obtain modified nano-silica.

[0024] Example 2 A method for synthesizing a high-performance moisture-curing silicone resin comprises the following preparation steps: Step 1, adding an epoxy monomer and 2-vinylpyridine to a solvent, then adding azobisisobutyronitrile, and stirring evenly to obtain a mixed solution, wherein the mass ratio of the epoxy monomer, 2-vinylpyridine, solvent and azobisisobutyronitrile is 22:11:70:0.4, and the epoxy monomer is 3,4-epoxycyclohexyl methacrylate; Step 2: Add the organosilicon monomer to the solvent, stir evenly, heat to 35° C., add the composite catalyst, and stir the mixture for 3 hours to obtain an organosilicon prepolymer, wherein the organosilicon monomer is composed of methyltrimethoxysilane, perfluorooctyltriethoxysilane, and an oxime-containing organosilicon monomer in a mass ratio of 12:7:4, the oxime-containing organosilicon monomer is composed of tetrakis(4-methyl-2-pentanoneoxime)silane and vinyltributylanoneoximesilane in a mass ratio of 9:2, the mass ratio of the organosilicon monomer, the solvent, and the composite catalyst is 25:70:0.15, the solvent is compounded of dimethyl carbonate and propylene glycol methyl ether acetate in a volume ratio of 8:2, and the composite catalyst is composed of dibutyltin dilaurate and triethylamine in a mass ratio of 5:1.5; Step 3: Add modified nano-silica to the mixed solution at room temperature, raise the temperature to 45° C. under inert gas protection, stir and react for 1.5 hours, then add the organosilicon prepolymer, stir evenly, control the stirring speed to 150 rpm, raise the temperature to 70° C., copolymerize for 3.5 hours, and distill under reduced pressure to obtain a high-performance moisture-curing organosilicon resin, wherein the mass ratio of the mixed solution, modified nano-silica and organosilicon prepolymer is 35:15:55; The preparation method of modified nano-silica is as follows: dispersing nano-silica in a polyvinyl alcohol aqueous solution with a concentration of 8wt%, controlling the solid-liquid ratio to 2:7, ultrasonically treating for 20 minutes, with an ultrasonic power of 110W and an ultrasonic frequency of 50KHz, at 70°C, magnetically stirring for 1.5 hours, and drying to obtain a hydroxylated filler; adding the hydroxylated filler to a γ-mercaptopropyltrimethoxysilane ethanol solution with a concentration of 4wt%, controlling the solid-liquid ratio to 4:11, adding acetic acid to adjust the pH to 5, heating to 65°C, stirring under nitrogen protection for 3 hours, and stirring at a speed of 300rpm, filtering, washing, and drying at 70°C for 5 hours to obtain modified nano-silica.

[0025] Example 3 A method for synthesizing a high-performance moisture-curing silicone resin comprises the following preparation steps: Step 1, adding an epoxy monomer and 2-vinylpyridine to a solvent, then adding azobisisobutyronitrile, and stirring evenly to obtain a mixed solution, wherein the mass ratio of the epoxy monomer, 2-vinylpyridine, solvent and azobisisobutyronitrile is 25:12:80:0.5, and the epoxy monomer is 3,4-epoxycyclohexyl methacrylate; Step 2: Add the organosilicon monomer to the solvent, stir evenly, heat to 40° C., add the composite catalyst, and stir the mixture for 4 hours to obtain an organosilicon prepolymer, wherein the organosilicon monomer is composed of methyltrimethoxysilane, perfluorooctyltriethoxysilane, and an oxime-containing organosilicon monomer in a mass ratio of 15:8:5, the oxime-containing organosilicon monomer is composed of tetrakis(4-methyl-2-pentanoneoxime)silane and vinyltributylanoneoximesilane in a mass ratio of 10:3, the mass ratio of the organosilicon monomer, the solvent, and the composite catalyst is 30:80:0.2, the solvent is compounded of dimethyl carbonate and propylene glycol methyl ether acetate in a volume ratio of 9:1, and the composite catalyst is composed of dibutyltin dilaurate and triethylamine in a mass ratio of 8:2; Step 3: Add modified nano-silica to the mixed solution at room temperature, raise the temperature to 50° C. under inert gas protection, stir and react for 2 hours, then add the organosilicon prepolymer, stir evenly, control the stirring speed to 200 rpm, raise the temperature to 80° C., copolymerize and react for 4 hours, and distill under reduced pressure to obtain a high-performance moisture-curing organosilicon resin, wherein the mass ratio of the mixed solution, modified nano-silica and organosilicon prepolymer is 40:20:60; The preparation method of modified nano-silica is as follows: dispersing nano-silica in a polyvinyl alcohol aqueous solution with a concentration of 10wt%, controlling the solid-liquid ratio to 3:10, ultrasonically treating for 30 minutes, with an ultrasonic power of 120W and an ultrasonic frequency of 60KHz, at 80°C, magnetically stirring for 2 hours, and drying to obtain a hydroxylated filler; adding the hydroxylated filler to a γ-mercaptopropyltrimethoxysilane ethanol solution with a concentration of 5wt%, controlling the solid-liquid ratio to 5:12, adding acetic acid to adjust the pH to 6, heating to 80°C, stirring under nitrogen protection for 4 hours, and stirring at a speed of 400rpm, filtering, washing, and drying at 80°C for 6 hours to obtain modified nano-silica.

[0026] Comparative Example 1 A method for synthesizing a high-performance moisture-curing silicone resin comprises the following preparation steps: Step 1, adding 2-vinylpyridine to a solvent, then adding azobisisobutyronitrile, and stirring evenly to obtain a mixed solution, wherein the mass ratio of 2-vinylpyridine, solvent and azobisisobutyronitrile is 28:60:0.2; Step 2: Add the organosilicon monomer to the solvent, stir evenly, heat to 30° C., add the composite catalyst, and stir the mixture for 2 hours to obtain an organosilicon prepolymer, wherein the organosilicon monomer is composed of methyltrimethoxysilane, perfluorooctyltriethoxysilane, and an oxime-containing organosilicon monomer in a mass ratio of 10:5:2, the oxime-containing organosilicon monomer is composed of tetrakis(4-methyl-2-pentanoneoxime)silane and vinyltributylanoneoximesilane in a mass ratio of 8:1, the mass ratio of the organosilicon monomer, the solvent, and the composite catalyst is 20:60:0.1, the solvent is compounded of dimethyl carbonate and propylene glycol methyl ether acetate in a volume ratio of 7:3, and the composite catalyst is composed of dibutyltin dilaurate and triethylamine in a mass ratio of 3:1; Step 3: Add modified nano-silica to the mixed solution at room temperature, raise the temperature to 40° C. under inert gas protection, stir and react for 1 hour, then add the organosilicon prepolymer, stir evenly, control the stirring speed to 100 rpm, raise the temperature to 60° C., copolymerize for 3 hours, and distill under reduced pressure to obtain a high-performance moisture-curing organosilicon resin, wherein the mass ratio of the mixed solution, modified nano-silica and organosilicon prepolymer is 30:10:50; The preparation method of modified nano-silica is as follows: dispersing nano-silica in a polyvinyl alcohol aqueous solution with a concentration of 5wt%, controlling the solid-liquid ratio to be 1:5, ultrasonically treating for 10 minutes, with an ultrasonic power of 100W and an ultrasonic frequency of 40KHz, at 60°C, magnetically stirring for 1 hour, and drying to obtain a hydroxylated filler; adding the hydroxylated filler to a γ-mercaptopropyltrimethoxysilane ethanol solution with a concentration of 2wt%, controlling the solid-liquid ratio to be 3:10, adding acetic acid to adjust the pH to 4, heating to 50°C, stirring under nitrogen protection for 2 hours, stirring at a speed of 200rpm, filtering, washing, and drying at 60°C for 4 hours to obtain modified nano-silica.

[0027] Comparative Example 2 A method for synthesizing a high-performance moisture-curing silicone resin comprises the following preparation steps: Step 1, adding an epoxy monomer and 2-vinylpyridine to a solvent, then adding azobisisobutyronitrile, and stirring evenly to obtain a mixed solution, wherein the mass ratio of the epoxy monomer, 2-vinylpyridine, solvent and azobisisobutyronitrile is 18:10:60:0.2, and the epoxy monomer is 3,4-epoxycyclohexyl methacrylate; Step 2: Add the organosilicon monomer to the solvent, stir evenly, heat to 30° C., add the composite catalyst, and stir to react for 2 hours to obtain an organosilicon prepolymer, wherein the organosilicon monomer is composed of methyltrimethoxysilane and an organosilicon monomer containing an oxime group in a mass ratio of 10:2, the organosilicon monomer containing an oxime group is composed of tetrakis(4-methyl-2-pentanoneoxime)silane and vinyltributylanoneoximesilane in a mass ratio of 8:1, the mass ratio of the organosilicon monomer, the solvent, and the composite catalyst is 20:60:0.1, the solvent is compounded by dimethyl carbonate and propylene glycol methyl ether acetate in a volume ratio of 7:3, and the composite catalyst is composed of dibutyltin dilaurate and triethylamine in a mass ratio of 3:1; Step 3: Add modified nano-silica to the mixed solution at room temperature, raise the temperature to 40° C. under inert gas protection, stir and react for 1 hour, then add the organosilicon prepolymer, stir evenly, control the stirring speed to 100 rpm, raise the temperature to 60° C., copolymerize for 3 hours, and distill under reduced pressure to obtain a high-performance moisture-curing organosilicon resin, wherein the mass ratio of the mixed solution, modified nano-silica and organosilicon prepolymer is 30:10:50; The preparation method of modified nano-silica is as follows: dispersing nano-silica in a polyvinyl alcohol aqueous solution with a concentration of 5wt%, controlling the solid-liquid ratio to be 1:5, ultrasonically treating for 10 minutes, with an ultrasonic power of 100W and an ultrasonic frequency of 40KHz, magnetically stirring at 60°C for 1 hour, and drying to obtain a hydroxylated filler; adding the hydroxylated filler to a γ-mercaptopropyltrimethoxysilane ethanol solution with a concentration of 2wt%, controlling the solid-liquid ratio to be 3:10, adding acetic acid to adjust the pH to 4, heating to 50°C, stirring under nitrogen protection for 2 hours, and stirring at a speed of 200rpm, filtering, washing, and drying at 60°C for 4 hours to obtain modified nano-silica.

[0028] Comparative Example 3 A method for synthesizing a high-performance moisture-curing silicone resin comprises the following preparation steps: Step 1, adding an epoxy monomer and 2-vinylpyridine to a solvent, then adding azobisisobutyronitrile, and stirring evenly to obtain a mixed solution, wherein the mass ratio of the epoxy monomer, 2-vinylpyridine, solvent and azobisisobutyronitrile is 18:10:60:0.2, and the epoxy monomer is 3,4-epoxycyclohexyl methacrylate; Step 2: Add the organosilicon monomer to the solvent, stir evenly, heat to 30° C., add the composite catalyst, and stir to react for 2 hours to obtain an organosilicon prepolymer, wherein the organosilicon monomer is composed of methyltrimethoxysilane, perfluorooctyltriethoxysilane, and an oxime-containing organosilicon monomer in a mass ratio of 10:5:2, the oxime-containing organosilicon monomer is tetra(4-methyl-2-pentanoneoxime)silane, the mass ratio of the organosilicon monomer, the solvent, and the composite catalyst is 20:60:0.1, the solvent is compounded by dimethyl carbonate and propylene glycol methyl ether acetate in a volume ratio of 7:3, and the composite catalyst is composed of dibutyltin dilaurate and triethylamine in a mass ratio of 3:1; Step 3: Add modified nano-silica to the mixed solution at room temperature, raise the temperature to 40° C. under inert gas protection, stir and react for 1 hour, then add the organosilicon prepolymer, stir evenly, control the stirring speed to 100 rpm, raise the temperature to 60° C., copolymerize for 3 hours, and distill under reduced pressure to obtain a high-performance moisture-curing organosilicon resin, wherein the mass ratio of the mixed solution, modified nano-silica and organosilicon prepolymer is 30:10:50; The preparation method of modified nano-silica is as follows: dispersing nano-silica in a polyvinyl alcohol aqueous solution with a concentration of 5wt%, controlling the solid-liquid ratio to be 1:5, ultrasonically treating for 10 minutes, with an ultrasonic power of 100W and an ultrasonic frequency of 40KHz, at 60°C, magnetically stirring for 1 hour, and drying to obtain a hydroxylated filler; adding the hydroxylated filler to a γ-mercaptopropyltrimethoxysilane ethanol solution with a concentration of 2wt%, controlling the solid-liquid ratio to be 3:10, adding acetic acid to adjust the pH to 4, heating to 50°C, stirring under nitrogen protection for 2 hours, stirring at a speed of 200rpm, filtering, washing, and drying at 60°C for 4 hours to obtain modified nano-silica.

[0029] Comparative Example 4 A method for synthesizing a high-performance moisture-curing silicone resin comprises the following preparation steps: Step 1, adding an epoxy monomer and 2-vinylpyridine to a solvent, then adding azobisisobutyronitrile, and stirring evenly to obtain a mixed solution, wherein the mass ratio of the epoxy monomer, 2-vinylpyridine, solvent and azobisisobutyronitrile is 18:10:60:0.2, and the epoxy monomer is 3,4-epoxycyclohexyl methacrylate; Step 2: Add the organosilicon monomer to the solvent, stir evenly, heat to 30° C., add the composite catalyst, and stir to react for 2 hours to obtain an organosilicon prepolymer, wherein the organosilicon monomer is composed of methyltrimethoxysilane, perfluorooctyltriethoxysilane, and an oxime-containing organosilicon monomer in a mass ratio of 10:5:2, the oxime-containing organosilicon monomer is vinyltributylanoximesilane, the mass ratio of the organosilicon monomer, the solvent, and the composite catalyst is 20:60:0.1, the solvent is compounded of dimethyl carbonate and propylene glycol methyl ether acetate in a volume ratio of 7:3, and the composite catalyst is composed of dibutyltin dilaurate and triethylamine in a mass ratio of 3:1; Step 3: Add modified nano-silica to the mixed solution at room temperature, raise the temperature to 40° C. under inert gas protection, stir and react for 1 hour, then add the organosilicon prepolymer, stir evenly, control the stirring speed to 100 rpm, raise the temperature to 60° C., copolymerize for 3 hours, and distill under reduced pressure to obtain a high-performance moisture-curing organosilicon resin, wherein the mass ratio of the mixed solution, modified nano-silica and organosilicon prepolymer is 30:10:50; The preparation method of modified nano-silica is as follows: dispersing nano-silica in a polyvinyl alcohol aqueous solution with a concentration of 5wt%, controlling the solid-liquid ratio to be 1:5, ultrasonically treating for 10 minutes, with an ultrasonic power of 100W and an ultrasonic frequency of 40KHz, magnetically stirring at 60°C for 1 hour, and drying to obtain a hydroxylated filler; adding the hydroxylated filler to a γ-mercaptopropyltrimethoxysilane ethanol solution with a concentration of 2wt%, controlling the solid-liquid ratio to be 3:10, adding acetic acid to adjust the pH to 4, heating to 50°C, stirring under nitrogen protection for 2 hours, and stirring at a speed of 200rpm, filtering, washing, and drying at 60°C for 4 hours to obtain modified nano-silica.

[0030] Comparative Example 5 A method for synthesizing a high-performance moisture-curing silicone resin comprises the following preparation steps: Step 1, adding an epoxy monomer and 2-vinylpyridine to a solvent, then adding azobisisobutyronitrile, and stirring evenly to obtain a mixed solution, wherein the mass ratio of the epoxy monomer, 2-vinylpyridine, solvent and azobisisobutyronitrile is 18:10:60:0.2, and the epoxy monomer is 3,4-epoxycyclohexyl methacrylate; Step 2: Add the organosilicon monomer to the solvent, stir evenly, heat to 30° C., add the composite catalyst, and stir the mixture for 2 hours to obtain an organosilicon prepolymer, wherein the organosilicon monomer is composed of methyltrimethoxysilane, perfluorooctyltriethoxysilane, and an oxime-containing organosilicon monomer in a mass ratio of 10:5:2, the oxime-containing organosilicon monomer is composed of tetrakis(4-methyl-2-pentanoneoxime)silane and vinyltributylanoneoximesilane in a mass ratio of 8:1, the mass ratio of the organosilicon monomer, the solvent, and the composite catalyst is 20:60:0.1, the solvent is compounded of dimethyl carbonate and propylene glycol methyl ether acetate in a volume ratio of 7:3, and the composite catalyst is composed of dibutyltin dilaurate and triethylamine in a mass ratio of 3:1; Step 3: Add modified nano-silica to the mixed solution at room temperature, raise the temperature to 40° C. under inert gas protection, stir and react for 1 hour, then add the organosilicon prepolymer, stir evenly, control the stirring speed to 100 rpm, raise the temperature to 60° C., copolymerize for 3 hours, and distill under reduced pressure to obtain a high-performance moisture-curing organosilicon resin, wherein the mass ratio of the mixed solution, modified nano-silica and organosilicon prepolymer is 30:10:50; The preparation method of modified nano-silica is as follows: dispersing nano-silica in a polyvinyl alcohol aqueous solution with a concentration of 5wt%, controlling the solid-liquid ratio to be 1:5, ultrasonically treating for 10 minutes, with an ultrasonic power of 100W and an ultrasonic frequency of 40KHz, magnetically stirring at 60°C for 1 hour, and drying to obtain a hydroxylated filler; adding the hydroxylated filler to a γ-aminopropyltrimethoxysilane ethanol solution with a concentration of 2wt%, controlling the solid-liquid ratio to be 3:10, adding acetic acid to adjust the pH to 4, heating to 50°C, stirring under nitrogen protection for 2 hours, and stirring at a speed of 200rpm, filtering, washing, and drying at 60°C for 4 hours to obtain modified nano-silica.

[0031] Comparative Example 6 A method for synthesizing a high-performance moisture-curing silicone resin comprises the following preparation steps: Step 1, adding an epoxy monomer and 2-vinylpyridine to a solvent, then adding azobisisobutyronitrile, and stirring evenly to obtain a mixed solution, wherein the mass ratio of the epoxy monomer, 2-vinylpyridine, solvent and azobisisobutyronitrile is 18:10:60:0.2, and the epoxy monomer is 3,4-epoxycyclohexyl methacrylate; Step 2: Add the organosilicon monomer to the solvent, stir evenly, heat to 30° C., add the composite catalyst, and stir the mixture for 2 hours to obtain an organosilicon prepolymer, wherein the organosilicon monomer is composed of methyltrimethoxysilane, perfluorooctyltriethoxysilane, and an oxime-containing organosilicon monomer in a mass ratio of 10:5:2, the oxime-containing organosilicon monomer is composed of tetrakis(4-methyl-2-pentanoneoxime)silane and vinyltributylanoneoximesilane in a mass ratio of 8:1, the mass ratio of the organosilicon monomer, the solvent, and the composite catalyst is 20:60:0.1, the solvent is compounded of dimethyl carbonate and propylene glycol methyl ether acetate in a volume ratio of 7:3, and the composite catalyst is composed of dibutyltin dilaurate and triethylamine in a mass ratio of 3:1; Step 3: Add modified nano-silica and organosilicon prepolymer to the mixed solution at room temperature, raise the temperature to 40° C. under inert gas protection, stir and react for 1 hour, raise the temperature to 60° C., copolymerize for 3 hours, control the stirring speed to 100 rpm, and distill under reduced pressure to obtain a high-performance moisture-curing organosilicon resin, wherein the mass ratio of the mixed solution, modified nano-silica and organosilicon prepolymer is 30:10:50; The preparation method of modified nano-silica is as follows: dispersing nano-silica in a polyvinyl alcohol aqueous solution with a concentration of 5wt%, controlling the solid-liquid ratio to be 1:5, ultrasonically treating for 10 minutes, with an ultrasonic power of 100W and an ultrasonic frequency of 40KHz, magnetically stirring at 60°C for 1 hour, and drying to obtain a hydroxylated filler; adding the hydroxylated filler to a γ-mercaptopropyltrimethoxysilane ethanol solution with a concentration of 2wt%, controlling the solid-liquid ratio to be 3:10, adding acetic acid to adjust the pH to 4, heating to 50°C, stirring under nitrogen protection for 2 hours, and stirring at a speed of 200rpm, filtering, washing, and drying at 60°C for 4 hours to obtain modified nano-silica.

[0032] Performance Testing The high-performance moisture-curable silicone resins prepared in Examples 1-3 and Comparative Examples 1-6 were tested for tensile strength, elongation at break, water impermeability, bonding strength, and curing time in accordance with the requirements of the national standard GB / T16777-2008 "Test Methods for Building Waterproof Coatings"; The test results are shown in Table 1.

[0033] Table 1 Performance parameters of high performance moisture-curable silicone resins prepared in Examples 1-3 and Comparative Examples 1-6

[0034] As shown in Table 1, the high-performance moisture-curing silicone resin prepared by the present invention exhibits excellent mechanical properties. It exhibits high tensile strength, high elongation at break, excellent tear strength, water impermeability, good bonding strength, high curing efficiency, and short surface-free and through-cure times. Its well-balanced overall performance combines mechanical strength and flexibility with reliable water resistance and adhesion, and is easy to apply, making it suitable for applications requiring both high performance and high efficiency.

[0035] This specific embodiment is merely an explanation of the present invention and is not intended to limit the present invention. After reading this specification, those skilled in the art may make non-creative modifications to this embodiment as needed. However, as long as such modifications are within the scope of the claims of the present invention, they are protected by patent law.

Claims

1. A method for synthesizing a high-performance moisture-curing silicone resin, characterized in that: The method comprises the following preparation steps: Step 1: adding epoxy monomer and 2-vinyl pyridine to a solvent, then adding an initiator, and stirring evenly to obtain a mixed solution; Step 2: Add the organosilicon monomer to the solvent, stir evenly, heat to 30-40°C, add the composite catalyst, stir and react for 2-4 hours to obtain the organosilicon prepolymer; Step 3: Add the modified filler to the mixed liquid at room temperature, raise the temperature to 40-50°C under the protection of inert gas, stir and react for 1-2 hours, then add the silicone prepolymer, stir evenly, raise the temperature to 60-80°C, copolymerize for 3-4 hours, and distill under reduced pressure to obtain a high-performance moisture-curing silicone resin.

2. The method for synthesizing a high-performance moisture-curable silicone resin according to claim 1, wherein: The epoxy monomer is one or more of 3,4-epoxycyclohexyl methacrylate, allyl glycidyl ether, and glycidyl methacrylate.

3. The method for synthesizing a high-performance moisture-curable silicone resin according to claim 1, wherein: The mass ratio of the epoxy monomer to 2-vinyl pyridine is 18-25:10-12.

4. The method for synthesizing a high-performance moisture-curable silicone resin according to claim 1, wherein: The solvent is prepared by compounding dimethyl carbonate and propylene glycol methyl ether acetate in a volume ratio of 7-9:1-3.

5. The method for synthesizing a high-performance moisture-curable silicone resin according to claim 1, wherein: The organic silicon monomer consists of methyltrimethoxysilane, perfluorooctyltriethoxysilane and an organic silicon monomer containing an oxime group in a mass ratio of 10-15:5-8:2-5.

6. The method for synthesizing a high-performance moisture-curable silicone resin according to claim 5, characterized in that: The organic silicon monomer containing an oxime group is composed of tetrakis (4-methyl-2-pentanone oxime) silane and vinyltributylanone oxime silane in a mass ratio of 8-10:1-3.

7. The method for synthesizing a high-performance moisture-curable silicone resin according to claim 1, wherein: The mass ratio of the mixed liquid, the modified filler and the organosilicon prepolymer is 30-40:10-20:50-60.

8. The method for synthesizing a high-performance moisture-curable silicone resin according to claim 1, wherein: The preparation method of the modified filler is: The nanofiller is dispersed in a polyvinyl alcohol aqueous solution, ultrasonically treated for 10-30 minutes, magnetically stirred at 60-80°C for 1-2 hours, and dried to obtain a hydroxylated filler; the hydroxylated filler is added to an ethanol solution of a mercaptosilane coupling agent, acetic acid is added to adjust the pH to 4-6, the temperature is raised to 50-80°C, and under nitrogen protection, stirred for reaction for 2-4 hours, filtered, washed, and dried at 60-80°C for 4-6 hours to obtain a modified filler.

9. The method for synthesizing a high-performance moisture-curable silicone resin according to claim 8, wherein: The mercaptosilane coupling agent is one or more of γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane and γ-mercaptopropylmethyldimethoxysilane.

10. Use of a high-performance moisture-curing organosilicon resin synthesized by the method for synthesizing a high-performance moisture-curing organosilicon resin according to any one of claims 1 to 9 in coatings.

Images