Multi-level cross-linked impact-resistant wear-resistant organic silicon as well as preparation method and application thereof

Abstract

The invention discloses multi-level cross-linked impact-resistant and wear-resistant organic silicon as well as a preparation method and application thereof, and belongs to the technical field of organic silicon. The multi-level cross-linked impact-resistant and wear-resistant organic silicon is prepared from the following components in parts by weight: a component A and a component B, the component A is prepared from 80 to 100 parts of hybrid branched chain type organic silicon resin and 0.01 to 0.1 part of catalyst; the component B is prepared from 20 to 30 parts of cross-linking agent and 10 to 30 parts of filler; the mass ratio of the component A to the component B is 1: (0.2-0.5). The introduced fluorine-containing group endows the material with the characteristic of low surface energy, and the adhesion resistance and friction loss during water flow impact can be reduced; the organic silicon resin can adapt to complex water environment and temperature change in water conservancy and hydropower engineering, and has the performance advantage of long-term stable use.

Description

Technical Field

[0001] This invention belongs to the field of organosilicon technology, specifically relating to a multi-level cross-linked impact-resistant and wear-resistant organosilicon, its preparation method, and its application. Background Technology

[0002] Structures in hydraulic and hydropower projects, such as dam spillways, spillways, and sluice gates, are subjected to the severe stress of high-speed water flow over extended periods. This high-speed flow not only generates enormous impact and shear forces, but the suspended particles such as silt and rocks it carries also cause severe abrasive damage to the concrete surface. Furthermore, when the flow velocity changes abruptly on uneven surfaces, cavitation is easily triggered. The instantaneous high pressure generated when cavitation bubbles collapse causes erosive damage to the concrete, known as cavitation erosion. These combined effects of scouring, abrasion, and cavitation severely threaten the safe operation and long-term durability of these structures, leading to costly and technically challenging maintenance work.

[0003] To address the aforementioned challenges, various protective materials have been developed in the prior art. For example, Chinese invention patent CN109180109A discloses a highly erosion-resistant and waterproof inorganic coating and its preparation method. The technical solution is as follows: the main components of the highly erosion-resistant and waterproof inorganic coating are as follows: 120-260 parts of ultrafine corundum with an average particle size of 68-125 μm, 150-280 parts of cement with a strength of not less than 32.5 MPa, 110-260 parts of admixture with an average particle size of 5-30 μm, 5-10 parts of high-performance additives, a water-cement ratio of 0.2-0.4, 5-20 parts of redispersible latex powder, 2-5 parts of defoamer, 2-4 parts of dispersant, and 10-20 parts of water-repellent agent.

[0004] The aforementioned technical solution primarily uses cement as the main binder, compounded with ultrafine corundum as wear-resistant aggregate, and also adds various admixtures such as latex powder and water-repellent agents. The aim is to resist water erosion by increasing its density and surface hardness. However, in practical applications, as a rigid inorganic material, its toughness and deformation adaptability are limited. It is prone to cracking and detachment due to its inability to coordinate deformation, making it difficult to meet the long-term protection requirements under complex working conditions.

[0005] There is also existing technology, such as Chinese invention patent with publication number CN120484630A, which discloses a general-purpose epoxy sealing coating for concrete surfaces and its preparation method. The technical solution is as follows: the coating comprises component A and component B, with a weight ratio of component A to component B of (2-4):1. Component A includes epoxy resin, reactive diluent, pigments and fillers, defoamer, dispersant, leveling agent, and anti-settling agent; component B includes curing agent, accelerator, and coupling agent.

[0006] The coating of the above-mentioned technical solution is formed by reacting bisphenol A or bisphenol F type epoxy resin with polyamine curing agent to form a dense cross-linked network, which can effectively isolate the intrusion of water and corrosive media; however, this traditional epoxy resin coating also has defects: its molecular chain structure contains a large number of benzene rings, which are rigid but lack flexibility, the material is brittle, and its toughness will further decrease at low temperature, resulting in poor impact resistance.

[0007] There are also existing technologies, such as Chinese invention patent with publication number CN120082273A, which discloses a modified one-component polyurea waterproof coating, its preparation method, and its application in hydraulic concrete protective coating structures. Its technical solution is as follows: a modified one-component polyurea waterproof coating is provided, comprising the following raw materials by weight: polytetrahydrofuran polyol, polyether triol, fluorinated polyether polyol, FEVE-type fluorocarbon resin, organosilicon polyether diol, hydrophobic agent, isocyanate, defoamer, diluent, dispersant, catalyst, latent curing agent, coupling agent, dehydrating agent, pigments and fillers, thixotropic agent, and plasticizer.

[0008] The aforementioned technical solution modifies the polyurea molecular chain by introducing fluorinated polyethers and organosilicon polyethers to improve the hydrophobicity and weather resistance of the coating. While this results in excellent elasticity and some weather resistance, it primarily relies on the network formed by the reaction of isocyanate with polyols / amines. When faced with the intense impact and repeated abrasion from high-speed, sand-laden water flow, its wear resistance and strength are insufficient. Although fluorine and silicon modification improves surface properties, it does not fundamentally solve the problem of structural stability and durability under intense impact and abrasion conditions.

[0009] In summary, existing hydraulic concrete protective materials often face contradictions between multiple properties such as rigidity and flexibility, abrasion resistance and toughness, and adhesion, making it difficult to fully meet the long-term protection requirements of modern water conservancy and hydropower projects in complex and harsh environments. Therefore, this application proposes a multi-layered cross-linked impact-resistant and abrasion-resistant organosilicon, its preparation method, and its application to solve the above problems. Summary of the Invention

[0010] To address the deficiencies in the aforementioned technical solutions, the present invention aims to provide a multi-layered cross-linked impact-resistant and wear-resistant organosilicon, its preparation method, and its application. This objective is achieved through the following technical solution: A multi-layered cross-linked impact-resistant and wear-resistant organosilicon, by weight, comprises the following components: component A and component B. Component A comprises 80-100 parts of hybrid branched organosilicon resin and 0.01-0.1 parts of catalyst; Component B includes 20-30 parts of crosslinking agent and 10-30 parts of filler.

[0011] The mass ratio of component A to component B is 1:(0.2-0.5). The catalyst in component A is one or more of bismuth octoate, zinc octoate, and butyltin thiolate.

[0012] The crosslinking agent in component B is one or more of diphenylmethane diisocyanate, KH-560, and isophorone diisocyanate.

[0013] The filler in component B is fumed silica. The preparation method of the hybrid branched organosilicon resin in component A includes the following steps: Step (1) Raw material pretreatment: Tetraethyl orthosilicate, triethoxysilyl-isophthalic anhydride, polyether-modified bisphenol A diethoxysilane, and borate-phosphonate-disubstituted ethoxysilane are respectively added to a three-necked flask, 5Å molecular sieve is added, and the mixture is stirred and dehydrated for 4h under vacuum conditions of 40℃ and -0.09MPa. The sample is tested and the moisture content is ≤0.05% before it can be used; anhydrous toluene is purified by distillation, the middle fraction is collected, anhydrous magnesium sulfate is added and dried for 24h, and then filtered for later use; Step (2) Preparation of main chain prepolymer: Add pretreated toluene to a three-necked flask, and under nitrogen atmosphere protection, add pretreated tetraethyl orthosilicate, triethoxysilyl-isophthalic anhydride, polyether-modified bisphenol A diethoxysilane, and borate-phosphonate-disubstituted ethoxysilane in sequence. Stir until the materials are mixed evenly, and then add catalyst dropwise. Then heat the system to 85°C and keep it at this temperature for 6 hours for co-condensation reaction. After the reaction is completed, add toluene to achieve a solid content of 45%-50%. Step (3) Side-linking reaction: Keep the reaction system temperature at 85°C, add perfluorooctyl-triazine cyclotriethoxysilane and hydroxyl-terminated polydimethylsiloxane, stir until uniform, then raise the temperature to 95°C and keep the reaction at this temperature for 4 hours to obtain hybrid branched organosilicon resin.

[0014] The viscosity of the hydroxyl-terminated polydimethylsiloxane used in step (3) of the preparation of the hybrid branched organosilicon resin in component A is 5000-50000 mPa•s. Preferably, the viscosity of the hydroxyl-terminated polydimethylsiloxane is 5000 mPa•s.

[0015] The preparation method of triethoxysilyl-isophthalic anhydride in step (1) of the preparation of the hybrid branched organosilicon resin in component A includes the following steps: Step (1) Raw material pretreatment: Isophthalic anhydride was placed in a vacuum oven and dried at 80℃ and -0.09MPa vacuum for 4h to remove trace moisture. After cooling, it was transferred to a dry three-necked flask. Anhydrous dichloromethane was soaked in 5Å molecular sieve for 24h and then collected by distillation. Step (2) Preparation of isophthaloyl chloride: Isophthalic anhydride was dissolved in dried dichloromethane, and then thionyl chloride was slowly added dropwise, with the reaction temperature controlled at ≤25℃ during the addition. After the addition was completed, the reaction system was heated to 40℃ and kept at this temperature for 6 hours. After the reaction was completed, nitrogen gas was purged for 30 minutes to remove residual SO2 and HCl gas from the system, resulting in a dichloromethane solution of isophthaloyl chloride.

[0016] Step (3) Preparation of triethoxysilyl-isophthalic anhydride: Maintain the reaction system temperature at 40℃, and slowly add triethylamine and a homogeneous mixture to a dichloromethane solution of isophthaloyl chloride. Control the pH of the system between 7 and 8 during the addition process. After the addition is complete, raise the temperature to 55℃ and keep the reaction at this temperature for 8 hours. The obtained product is then subjected to rotary evaporation, chromatography, and a second rotary evaporation to obtain the final white powdered triethoxysilyl-isophthalic anhydride.

[0017] The isophthalic anhydride is 2,2'-biphenyl anhydride.

[0018] The preparation steps of the polyether-modified bisphenol A diethoxysilane in step (1) of the preparation of the hybrid branched organosilicon resin in component A are as follows: (1) Raw material pretreatment: 2,2-bis(p-hydroxyphenyl)propane was dried under vacuum at 100℃ and -0.09MPa for 6h; ethylene oxide (EO) / propylene oxide (PO) was purified by 5Å molecular sieve and dried by toluene distillation; (2) Bisphenol A polyetherification: In a high-pressure reactor, dry bisphenol A and KOH were added, and after nitrogen purging, the temperature was raised to 120°C to melt. PO was first introduced at 10 g / h, and the reactor pressure was maintained at 0.3-0.5 MPa. Then EO was introduced at 15 g / h and the temperature was raised to 130°C. The reaction was kept at this temperature for 4 h. After the reaction was completed, the temperature was lowered to 60°C and triphenyl phosphite was added to terminate the reaction, resulting in hydroxyl-terminated polyether modified bisphenol A. (3) Polyether-modified bisphenol A diethoxysilane: Add polyether bisphenol A and anhydrous toluene to a three-necked flask, purge with nitrogen and heat to 80°C to dissolve, add anhydrous sodium carbonate, and slowly add γ-chloropropyl diethoxysilane; after adding, heat to 95°C and keep the reaction for 6 hours. After the reaction is completed, desolvate under reduced pressure to obtain the target product polyether-modified bisphenol A diethoxysilane.

[0019] The preparation steps of the borate ester-phosphonate bis-substituted ethoxysilane in step (1) of the preparation of the hybrid branched organosilicon resin in component A are as follows: Step (1) Raw material pretreatment: KH-550 was added to 5Å molecular sieve and dehydrated under vacuum at 40℃ and -0.09MPa for 3h; Tributyl borate and diethyl phosphite were each dried with anhydrous magnesium sulfate for 12h, filtered and then distilled; Anhydrous ethanol was distilled and then added to 5Å molecular sieve and allowed to stand for 24h. Step (2): Add anhydrous ethanol to a three-necked flask, inertize with nitrogen, add dehydration KH-550, heat to 55℃ and add p-toluenesulfonic acid, then add tributyl borate dropwise. After the addition is complete, heat to 70℃ and react for 4 hours to obtain an amino-boron ester intermediate; cool to 50℃ and add hydroquinone, then add diethyl phosphite dropwise. After the addition is complete, heat to 65℃ and react for 5 hours. Step (3): After the reaction is complete, add anhydrous magnesium sulfate and stir for 6 hours. After filtration, extract twice with petroleum ether. After desolvation under reduced pressure at 50℃ and -0.09MPa, the final product boronic acid ester-phosphonic acid ester disubstituted ethoxysilane is obtained.

[0020] The preparation steps of perfluorooctyl-triazine cyclotriethoxysilane in step (3) of the preparation of the hybrid branched organosilicon resin in component A are as follows: Step (1) Raw material pretreatment: Take cyanuric chloride and dry it under vacuum at 60℃ and -0.095MPa for 4h; add 5Å molecular sieve to KH-550 and dehydrate under vacuum at 40℃ for 3h; after distilling dichloromethane, add calcium chloride and dry; add magnesium sulfate to 1H,1H-perfluorooctylamine and dry; and purify by distillation of triethylamine. Step (2) Preparation of perfluorooctyl-triazine cyclotriethoxysilane: Dichloromethane was added to a three-necked flask, and after inertization by purging with nitrogen, the temperature was lowered to 0-5℃. Cyanurium chloride and triethylamine were added, and after stirring to dissolve, KH-550 was added dropwise. After the addition was completed, the temperature was raised to 25℃ and reacted for 4 hours. The triethylamine hydrochloride was removed by filtration to obtain a monosilane-substituted intermediate. The remaining triethylamine was added to the filtrate, and the temperature was raised to 35℃. Perfluorooctylamine was added dropwise. After the addition was completed, the temperature was raised to 50℃ and reacted for 6 hours. The temperature was lowered and 2,6-di-tert-butyl-p-cresol was added to obtain a crude product solution. Step (3): The crude product solution was filtered through a filter membrane to remove salt, washed three times with deionized water until pH=7, dried with calcium chloride for 8 hours, and then desoluble under reduced pressure at 40℃ and -0.09MPa until the solid content was ≥99%; cooled to 10℃ and dissolved in n-hexane, and allowed to stand at -5℃ for 12 hours to precipitate crystals. After washing twice with cold n-hexane, the product was dried under vacuum at 30℃ for 6 hours to obtain a white powder product, which is the prepared perfluorooctyl-triazine cyclotriethoxysilane.

[0021] Preferably, the multi-layered cross-linked impact-resistant and abrasion-resistant silicone has the following composition by weight, including component A and component B; Component A comprises 90 parts of hybrid branched silicone resin and 0.05 parts of catalyst; Component B comprises 25 parts of crosslinking agent and 20 parts of filler; The mass ratio of component A to component B is 1:0.3.

[0022] Preferably, the catalyst is bismuth octanoate; Preferably, the primary particle size of the fumed silica filler is 5-20 nm; Preferably, the crosslinking agent is a mixture of diphenylmethane diisocyanate and KH-560, wherein the mass ratio of diphenylmethane diisocyanate to KH-560 is 2:1; The KH-550 is γ-aminopropyltriethoxysilane; KH-560 is γ-glycidoxypropyltriethoxysilane.

[0023] The preparation method of the multi-level cross-linked impact-resistant and wear-resistant organosilicon is as follows: Step 1: Add the hybrid branched organosilicon and catalyst to a disperser and stir at a rate of 500 r / min for 10 min until they are mixed evenly to obtain component A; Step 2: Add the crosslinking agent and filler to the disperser and stir at a rate of 500 r / min for 15 min to obtain component B. Step 3: Mix component A and component B in proportion, degas under vacuum for 8 minutes, coat the mixture onto the surface of the test block, and cure it completely at 50°C to obtain multi-layered cross-linked impact-resistant and wear-resistant organosilicon.

[0024] An application of a multi-level cross-linked impact-resistant and abrasion-resistant silicone resin, which can be widely used in the field of concrete resistance to high-speed water flow abrasion in water conservancy and hydropower projects.

[0025] The beneficial effects of this invention are as follows: (1) The technical solution of the present invention uses a multi-level cross-linking structure design. The borate ester group and phosphonate ester group in the hybrid branched organosilicon resin molecular chain provide hybrid atoms B and P for the main chain. The first level of intramolecular cross-linking structure is constructed by interaction forces such as coordination bond and hydrogen bond. The cross-linking agent constructed by diisocyanate and KH-560 can form the second level of intermolecular cross-linking structure through chemical cross-linking. The silanol group on the surface of the fumed nano silica filler forms a chemical bond with the active sites of the resin molecule, such as hydroxyl and siloxane groups, to form the third level of organic-inorganic hybrid cross-linking. The balance between rigidity and flexibility is achieved. The rigid groups in the main chain of the hybrid branched organosilicon resin enhance the hardness and deformation resistance of the material. The flexible segments of the side chain can alleviate impact stress and reduce brittle fracture. At the same time, the fumed nano silica filler is uniformly dispersed in the cross-linking network, which further disperses the impact energy and significantly improves the material's resistance to high-speed water flow abrasion. This solves the problem of easy wear and short life of traditional organosilicon materials under strong impact. (2) The fluorine-containing groups introduced in the technical solution of the present invention endow the material with low surface energy characteristics, which can reduce the adhesion resistance and friction loss during water flow impact; it also enhances the intermolecular forces and corrosion resistance through heteroatom groups such as borate ester group and phosphonate ester group; and the organosilicon main chain itself has excellent high and low temperature resistance and aging resistance; making the organosilicon resin adaptable to the complex water environment and temperature changes in water conservancy and hydropower projects, and has the performance advantage of long-term stable use; (3) The technical solution of the present invention uses a bismuth-based catalyst, which has good tolerance to P, B and other substances, and can ensure reaction efficiency and product quality; and it also adopts a two-component design, which can be mixed in proportion and then cured. The curing process can be carried out at room temperature without high temperature and high pressure conditions, which can fully meet the needs of on-site construction. Attached Figure Description

[0026] Figure 1 This is a top view of the multi-level cross-linked impact-resistant and abrasion-resistant silicone cured sample prepared in Example 1 of the present invention; Figure 2 To be Figure 1 The diagram shows the structure of the test sample obtained after coating the sample onto a concrete block. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments and accompanying drawings. The illustrative embodiments and descriptions of this invention are for explanation only and are not intended to limit the invention. Furthermore, regarding numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0028] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0029] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0030] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0031] In the following examples, "parts" refers to parts by weight.

[0032] Example 1 A multi-layered cross-linked impact-resistant and abrasion-resistant silicone, by weight, comprises the following components: component A and component B; Component A comprises: 90 parts of hybrid branched silicone resin and 0.05 parts of catalyst; Component B comprises: 25 parts of crosslinking agent and 20 parts of filler; The mass ratio of component A to component B is 1:0.3.

[0033] The preparation method of the multi-level cross-linked impact-resistant and wear-resistant organosilicon is as follows: Step 1: Add the hybrid branched organosilicon and catalyst to a disperser and stir at a rate of 500 r / min for 10 min until they are mixed evenly to obtain component A; Step 2: Add the crosslinking agent and filler to the disperser and stir at a rate of 500 r / min for 15 min to obtain component B. Step 3: Mix component A and component B in proportion, degas under vacuum for 8 minutes, apply the mixture to the surface of a concrete test block, and cure it completely at 50°C to obtain a multi-layered cross-linked impact-resistant and wear-resistant organosilicon.

[0034] A top view of the multi-level cross-linked impact-resistant and abrasion-resistant silicone cured sample prepared in Example 1 is shown below. Figure 1 As shown.

[0035] Will Figure 1 The schematic diagram of the test sample prepared by coating the sample onto a concrete specimen is shown below. Figure 2 As shown.

[0036] The catalyst in component A is bismuth octanoate; The filler in component B is fumed silica with a native particle size of 5-20 nm. The crosslinking agent in component B is a mixture of KH-560 and isophorone diisocyanate.

[0037] The mass ratio of KH-560 to isophorone diisocyanate is 1:2.

[0038] The preparation steps of the hybrid branched organosilicon resin are as follows: Raw material pretreatment: 28g of tetraethyl orthosilicate, 22g of triethoxysilyl-isophthalic anhydride, 18g of polyether-modified bisphenol A diethoxysilane, and 12g of monomer borate-phosphonate disubstituted ethoxysilane were added to a 500mL three-necked flask, and 5Å molecular sieves were added. The mixture was stirred and dehydrated for 4h under vacuum conditions of 40℃ and -0.09MPa. The sample was tested and the moisture content was ≤0.05% before it could be used. Anhydrous toluene was purified by distillation, the middle fraction was collected, anhydrous magnesium sulfate was added and dried for 24h, and then filtered for later use.

[0039] Preparation of main chain prepolymer: 400 mL of pretreated toluene was added to a three-necked flask. Under nitrogen atmosphere, pretreated tetraethyl orthosilicate, triethoxysilyl-isophthalic anhydride, polyether-modified bisphenol A diethoxysilane, and borate-phosphonate-disubstituted ethoxysilane were added sequentially. The mixture was stirred until homogeneous, and then 10 μL of catalyst was added dropwise. The system was then heated to 85 °C and kept at this temperature for 6 h for co-condensation reaction. After the reaction was completed, toluene was added to achieve a solid content of 50%.

[0040] Side-linking reaction: Keep the reaction system temperature at 85℃, add 9g of perfluorooctyl-triazine cyclotriethoxysilane and 3g of terminal hydroxyl polydimethylsiloxane, stir until uniform, then raise the temperature to 95℃ and keep the reaction at this temperature for 4 hours to obtain hybrid branched organosilicon resin.

[0041] Furthermore, the viscosity of the hydroxyl-terminated polydimethylsiloxane is 5000-50000 mPa•s.

[0042] Furthermore, the 10 μL of catalyst added is an acid catalyst, specifically acetic acid.

[0043] The preparation steps of the triethoxysilyl-isophthalic anhydride are as follows: (1) Raw material pretreatment: 14.81 g of 2,2'-biphenyl dicarboxylic anhydride was placed in a vacuum oven and dried at 80℃ and -0.09 MPa vacuum for 4 h to remove trace moisture. After cooling, it was transferred to a dry three-necked flask. Anhydrous dichloromethane was soaked in 5Å molecular sieve for 24 h and then collected by distillation. (2) Preparation of isophthaloyl chloride: 14.81 g of isophthalic anhydride was dissolved in 400 mL of dried dichloromethane, and then 15.3 g of thionyl chloride was slowly added dropwise, with the reaction temperature controlled at ≤25℃ during the dropwise addition; after the dropwise addition was completed, the reaction system was heated to 40℃ and kept at this temperature for 6 h; after the reaction was completed, nitrogen gas was purged for 30 min to remove residual SO2 and HCl gas in the system, and a dichloromethane solution of isophthaloyl chloride was obtained. (3) Preparation of triethoxysilyl-isophthalic anhydride: Keep the reaction system temperature at 40℃, slowly add 10.1g of triethylamine to a dichloromethane solution of isophthaloyl chloride after mixing evenly; control the pH of the system between 7 and 8 during the addition process, raise the temperature to 55℃ after the addition is completed, and keep the temperature for 8h; the obtained product is obtained by rotary evaporation, chromatography, and rotary evaporation again to obtain the final white powder triethoxysilyl-isophthalic anhydride.

[0044] Furthermore, the isophthalic anhydride is 2,2'-biphenyl anhydride.

[0045] The preparation steps of the polyether-modified bisphenol A diethoxysilane are as follows: (1) Raw material pretreatment: 22.8 g of 2,2-bis(p-hydroxyphenyl)propane was dried under vacuum at 100 °C and -0.09 MPa for 6 h; ethylene oxide (EO) / propylene oxide (PO) was purified by 5 Å molecular sieve and dried by toluene distillation; (2) Bisphenol A polyetherification: In a high-pressure reactor, dry bisphenol A and 8g of KOH were added, and after nitrogen purging, the temperature was raised to 120℃ to melt. First, 24g of PO was introduced at 10g / h, and the reactor pressure was maintained at 0.3-0.5MPa. Then, 36g of EO was introduced at 15g / h and the temperature was raised to 130℃. The reaction was kept at this temperature for 4h. After the reaction was completed, the temperature was lowered to 60℃ and 0.5g of triphenyl phosphite was added to terminate the reaction, and hydroxyl-terminated polyether modified bisphenol A was obtained. (3) Polyether modified bisphenol A diethoxysilane: Add 82.8g of polyether bisphenol A and 400mL of anhydrous toluene to a three-necked flask, purge with nitrogen and heat to 80℃ to dissolve, add 4g of anhydrous sodium carbonate, and then slowly add 38g of γ-chloropropyl diethoxysilane; after the addition is complete, heat to 95℃ and keep the reaction for 6h. After the reaction is completed, the target product is obtained by desolvation under reduced pressure.

[0046] The preparation steps of the borate-phosphonate disubstituted ethoxysilane are as follows: (1) Raw material pretreatment: 42g KH-550 was added to 5Å molecular sieve and dehydrated under vacuum at 40℃ and -0.09MPa for 3h; 10g of anhydrous magnesium sulfate was added to each of tributyl borate and diethyl phosphite and dried for 12h, filtered and then distilled; after distillation of anhydrous ethanol, 5Å molecular sieve was added and allowed to stand for 24h. (2) Add anhydrous ethanol to a three-necked flask, inertize it with nitrogen gas, add dehydration KH-550, heat to 55℃ and add 0.3g p-toluenesulfonic acid, then add 28g tributyl borate dropwise. After the addition is complete, heat to 70℃ and react for 4h to obtain an amino-boron ester intermediate; cool to 50℃ and add 0.1g hydroquinone, then add 22g diethyl phosphite dropwise. After the addition is complete, heat to 65℃ and react for 5h. (3) After the reaction was completed, 10g of anhydrous magnesium sulfate was added and stirred for 6h. After filtration, it was extracted twice with petroleum ether and desolvated under reduced pressure at 50℃ and -0.09MPa to obtain the final product.

[0047] The preparation steps of the perfluorooctyl-triazine cyclotriethoxysilane are as follows: (1) Raw material pretreatment: 23.2g of cyanuric chloride was dried under vacuum at 60℃ and -0.095MPa for 4h; 38g of KH-550 was dehydrated under vacuum at 40℃ for 3h with 5Å molecular sieve; after distillation of dichloromethane, calcium chloride was added for drying; 1H,1H-perfluorooctylamine was added for drying with magnesium sulfate; and triethylamine was purified by distillation. (2) Preparation of perfluorooctyl-triazine cyclotriethoxysilane: Add 400 mL of dichloromethane to a three-necked flask, inertize with nitrogen gas, and cool to 0-5 °C. Add 23.2 g of cyanuric chloride and 10.1 g of triethylamine, stir to dissolve, and then add 38 g of KH-550 dropwise. After the addition is complete, heat to 25 °C and react for 4 h. Filter to remove triethylamine hydrochloride to obtain a monosilane-substituted intermediate. Add the remaining triethylamine (10.1 g) to the filtrate, heat to 35 °C and add 32 g of perfluorooctylamine dropwise. After the addition is complete, heat to 50 °C and react for 6 h. Cool down and add 0.2 g of 2,6-di-tert-butyl-p-cresol to obtain a crude product solution. (3) The crude product solution was filtered through a filter membrane to remove salt, washed three times with deionized water until pH=7, dried with calcium chloride for 8 hours, and then desoluble under reduced pressure at 40℃ and -0.09MPa until the solid content was ≥99%. It was cooled to 10℃ and dissolved in n-hexane, and allowed to stand at -5℃ for 12 hours to precipitate crystals. After washing twice with cold n-hexane, it was dried under vacuum at 30℃ for 6 hours to obtain a white powder product, which is perfluorooctyl-triazine cyclotriethoxysilane.

[0048] Example 2 A multi-layered cross-linked impact-resistant and abrasion-resistant silicone, by weight, comprises the following components: component A and component B; Component A comprises: 80 parts of hybrid branched organosilicon resin and 0.01 parts of catalyst; Component B comprises: 20 parts of crosslinking agent and 10 parts of filler; The mass ratio of component A to component B is 1:0.2.

[0049] The catalyst in component A is a mixture of bismuth octanoate and butyltin mercaptan. The crosslinking agent in component B is a mixture of diphenylmethane diisocyanate and KH-560.

[0050] The mass ratio of diphenylmethane diisocyanate to KH-560 is 2:1.

[0051] Example 3 A multi-layered cross-linked impact-resistant and abrasion-resistant silicone, by weight, comprises the following components: component A and component B; Component A comprises: 100 parts of hybrid branched organosilicon resin and 1 part of catalyst; Component B comprises: 30 parts of crosslinking agent and 30 parts of filler; The mass ratio of component A to component B is 1:0.5.

[0052] The catalyst in component A is a mixture of bismuth octanoate and zinc octanoate.

[0053] The crosslinking agent in component B is a mixture of isophorone diisocyanate and KH-560.

[0054] The mass ratio of isophorone diisocyanate to KH-560 is 2:1.

[0055] Example 4 A multi-layered cross-linked impact-resistant and abrasion-resistant silicone, by weight, comprises the following components: component A and component B; Component A comprises: 90 parts of hybrid branched silicone resin and 0.05 parts of catalyst; Component B comprises: 25 parts of crosslinking agent and 20 parts of filler; The mass ratio of component A to component B is 1:0.3; The catalyst in component A is bismuth octanoate. The crosslinking agent used in component B is only diphenylmethane diisocyanate.

[0056] Example 5 A multi-layered cross-linked impact-resistant and abrasion-resistant silicone, by weight, comprises the following components: component A and component B; Component A comprises: 90 parts of hybrid branched silicone resin and 0.05 parts of catalyst; Component B comprises: 25 parts of crosslinking agent and 20 parts of filler; The mass ratio of component A to component B is 1:0.3; The catalyst used in component A is only butyltin mercaptan. The crosslinking agent in component B is a mixture of KH-560 and isophorone diisocyanate.

[0057] The mass ratio of KH-560 to isophorone diisocyanate is 1:2.

[0058] Comparative Example 1 The hybrid branched organosilicon of Comparative Example 1 was prepared by the following method: (1) Raw material pretreatment: 40g tetraethyl orthosilicate, 22g triethoxysilyl-isophthalic anhydride and 18g polyether modified bisphenol A diethoxysilane were added to a 500mL three-necked flask, 5Å molecular sieve was added, and the mixture was stirred and dehydrated for 4h under vacuum conditions of 40℃ and -0.09MPa. The sample was tested and the moisture content was ≤0.05% before it could be used. Anhydrous toluene was purified by distillation, the middle fraction was collected, anhydrous magnesium sulfate was added and dried for 24h, and then filtered for later use.

[0059] (2) Preparation of main chain prepolymer: Add 400 mL of pretreated toluene to a three-necked flask. Under nitrogen atmosphere protection, add 40 g of pretreated tetraethyl orthosilicate, 22 g of triethoxysilyl-isophthalic anhydride, and 18 g of polyether modified bisphenol A diethoxysilane in sequence, but do not add the monomer borate ester-phosphonate ester disubstituted ethoxysilane. Stir until the materials are mixed evenly, and then add 10 μL of catalyst. Then heat the system to 85 °C and keep it at the temperature for 6 h for co-condensation reaction. After the reaction is completed, add toluene to achieve a solid content of 50%.

[0060] (3) Side-linking reaction: Keep the reaction system temperature at 85℃, add 9g of perfluorooctyl-triazine cyclotriethoxysilane and 3g of terminal hydroxyl polydimethylsiloxane, stir until uniform, raise the temperature to 95℃, and keep the reaction at the temperature for 4h to prepare organosilicon resin.

[0061] The difference between Comparative Example 1 and Example 1 is that the borate ester-phosphonate bissubstituted ethoxysilane was removed and replaced with an equal amount of tetraethyl orthosilicate. Except for the differences in components mentioned above, the preparation methods of triethoxysilyl-isophthalic anhydride, polyether-modified bisphenol A diethoxysilane, perfluorooctyl-triazine cyclotriethoxysilane, and multi-layer crosslinked impact-resistant and abrasion-resistant organosilicon in Comparative Example 1 are all the same as those in Example 1.

[0062] Comparative Example 2 The hybrid branched organosilicon of Comparative Example 1 was prepared by the following method: (1) Raw material pretreatment: 28g tetraethyl orthosilicate, 40g triethoxysilyl-isophthalic anhydride, and 12g borate-phosphonate-disubstituted ethoxysilane were added to a 500mL three-necked flask, and 5Å molecular sieves were added. The mixture was stirred and dehydrated for 4h under vacuum conditions of 40℃ and -0.09MPa. The sample was tested and the moisture content was ≤0.05% before it could be used. Anhydrous toluene was purified by distillation, and the middle fraction was collected. Anhydrous magnesium sulfate was added and dried for 24h. After filtration, it was ready for use.

[0063] (2) Preparation of main chain prepolymer: Add 400 mL of pretreated toluene to a three-necked flask. Under nitrogen atmosphere protection, add 28 g of pretreated tetraethyl orthosilicate, 40 g of triethoxysilyl-isophthalic anhydride, and 12 g of borate-phosphonate-disubstituted ethoxysilane in sequence, but do not add polyether-modified bisphenol A diethoxysilane. Stir until the materials are mixed evenly, and then add 10 μL of catalyst. Then heat the system to 85 °C and keep it at the temperature for 6 h for co-condensation reaction. After the reaction is completed, add toluene to achieve a solid content of 50%.

[0064] (3) Side-linking reaction: Keep the reaction system temperature at 85℃, add 9g of perfluorooctyl-triazine cyclotriethoxysilane and 3g of terminal hydroxyl polydimethylsiloxane, stir until uniform, raise the temperature to 95℃, and keep the reaction at the temperature for 4h to prepare organosilicon resin.

[0065] The difference between Comparative Example 2 and Example 1 is that the polyether-modified bisphenol A diethoxysilane was removed and replaced with an equal amount of triethoxysilyl-isophthalic anhydride.

[0066] Except for the differences in components mentioned above, the preparation methods of triethoxysilyl-isophthalic anhydride, borate-phosphonate-disubstituted ethoxysilane, perfluorooctyl-triazine-cyclotriethoxysilane, and multi-layered crosslinked impact-resistant and abrasion-resistant organosilicon in Comparative Example 2 are all the same as those in Example 1.

[0067] Comparative Example 3 The hybrid branched organosilicon of Comparative Example 1 was prepared by the following method: (1) Raw material pretreatment: 28g tetraethyl orthosilicate, 22g triethoxysilyl-isophthalic anhydride, 18g polyether modified bisphenol A diethoxysilane, and 12g borate-phosphonate disubstituted ethoxysilane were added to a 500mL three-necked flask, and 5Å molecular sieves were added. The mixture was stirred and dehydrated for 4h under vacuum conditions of 40℃ and -0.09MPa. The sample was tested and the moisture content was ≤0.05% before it could be used. Anhydrous toluene was purified by distillation, the middle fraction was collected, anhydrous magnesium sulfate was added and dried for 24h, and then filtered for later use.

[0068] (2) Preparation of main chain prepolymer: Add 400 mL of pretreated toluene to a three-necked flask. Under nitrogen atmosphere protection, add pretreated tetraethyl orthosilicate, triethoxysilyl-isophthalic anhydride, polyether modified bisphenol A diethoxysilane, and borate ester-phosphonate disubstituted ethoxysilane in sequence. Stir until the materials are mixed evenly, and then add 10 μL of catalyst. Then heat the system to 85 °C and keep it at the temperature for 6 h for co-condensation reaction. After the reaction is completed, add toluene to achieve a solid content of 50%.

[0069] (3) Side-linking reaction: Keep the reaction system temperature at 85°C, do not add perfluorooctyl-triazine cyclotriethoxysilane, but add 12g of terminal hydroxyl polydimethylsiloxane; stir until uniform, then raise the temperature to 95°C and keep the reaction for 4h to obtain organosilicon resin.

[0070] The difference between Comparative Example 3 and Example 1 is that perfluorooctyl-triazine cyclotriethoxysilane was completely removed; Except for the differences in components mentioned above, the preparation methods of triethoxysilyl-isophthalic anhydride, polyether-modified bisphenol A diethoxysilane, borate-phosphonate-disubstituted ethoxysilane, and multi-layer crosslinked impact-resistant and wear-resistant organosilicon in Comparative Example 3 are all the same as those in Example 1.

[0071] Comparative Example 4 The hybrid branched organosilicon of Comparative Example 1 was prepared by the following method: (1) Raw material pretreatment: 28g tetraethyl orthosilicate, 22g triethoxysilyl-isophthalic anhydride, 18g polyether modified bisphenol A diethoxysilane, and 12g monomer borate-phosphonate disubstituted ethoxysilane were added to a 500mL three-necked flask, and 5Å molecular sieves were added. The mixture was stirred and dehydrated for 4h under vacuum conditions of 40℃ and -0.09MPa. The sample was tested and the moisture content was ≤0.05% before it could be used. Anhydrous toluene was purified by distillation, the middle fraction was collected, anhydrous magnesium sulfate was added and dried for 24h, and then filtered for later use.

[0072] (2) Preparation of main chain prepolymer: Add 400 mL of pretreated toluene to a three-necked flask. Under nitrogen atmosphere protection, add pretreated tetraethyl orthosilicate, triethoxysilyl-isophthalic anhydride, polyether modified bisphenol A diethoxysilane, and borate ester-phosphonate disubstituted ethoxysilane in sequence. Stir until the materials are mixed evenly, and then add 10 μL of catalyst. Then heat the system to 85 °C and keep it at the temperature for 6 h for co-condensation reaction. After the reaction is completed, add toluene to achieve a solid content of 50%.

[0073] (3) Side-linking reaction: Keep the reaction system temperature at 85°C, do not add terminal hydroxyl polydimethylsiloxane, but add a total of 12g of perfluorooctyl-triazine cyclotriethoxysilane; stir until uniform, then raise the temperature to 95°C and keep the reaction for 4h to obtain organosilicon resin.

[0074] The difference between Comparative Example 4 and Example 1 is that the hydroxyl-terminated polydimethylsiloxane was completely removed and replaced with an equal amount of perfluorooctyl-triazine cyclotriethoxysilane. Except for the differences in components mentioned above, the preparation methods of triethoxysilyl-isophthalic anhydride, polyether-modified bisphenol A diethoxysilane, borate ester-phosphonate ester disubstituted ethoxysilane, perfluorooctyl-triazine cyclotriethoxysilane, and multi-layer crosslinked impact-resistant and abrasion-resistant organosilicon in Comparative Example 1 are all the same as those in Example 1.

[0075] Comparative Example 5 A multi-layered cross-linked impact-resistant and abrasion-resistant silicone, by weight, comprises the following components: component A and component B; Component A comprises: 90 parts of hybrid branched silicone resin and 0.05 parts of catalyst; Component B comprises: 25 parts of a crosslinking agent; The mass ratio of component A to component B is 1:0.3; The difference between Comparative Example 5 and Example 1 is that the filler fumed silica was removed from component B; apart from the above-mentioned component differences, all other items in Comparative Example 5 are the same as those in Example 1.

[0076] Comparative Example 6 The specific preparation steps of the hybrid branched organosilicon resin are as follows: (1) Raw material pretreatment: 28g tetraethyl orthosilicate, 32g triethoxysilyl-isophthalic anhydride, 8g polyether modified bisphenol A diethoxysilane, and 12g monomer borate-phosphonate disubstituted ethoxysilane were added to a 500mL three-necked flask, and 5Å molecular sieves were added. The mixture was stirred and dehydrated for 4h under vacuum conditions of 40℃ and -0.09MPa. The sample was tested and the moisture content was ≤0.05% before it could be used. Anhydrous toluene was purified by distillation, and the middle fraction was collected. Anhydrous magnesium sulfate was added and dried for 24h. After filtration, it was ready for use.

[0077] (2) Preparation of main chain prepolymer: Add 400 mL of pretreated toluene to a three-necked flask. Under nitrogen atmosphere protection, add 28 g of pretreated tetraethyl orthosilicate, 32 g of triethoxysilyl-isophthalic anhydride, 8 g of polyether modified bisphenol A diethoxysilane, and 12 g of borate-phosphonate disubstituted ethoxysilane in sequence. Stir until the materials are mixed evenly, and then add 10 μL of catalyst. Then heat the system to 85 °C and keep it at the temperature for 6 h for co-condensation reaction. After the reaction is completed, add toluene to achieve a solid content of 50%.

[0078] (3) Side-linking reaction: Keep the reaction system temperature at 85℃, add 9g of perfluorooctyl-triazine cyclotriethoxysilane and 3g of terminal hydroxyl polydimethylsiloxane, stir until uniform, raise the temperature to 95℃, and keep the reaction at the temperature for 4h to prepare organosilicon resin.

[0079] The difference between Comparative Example 6 and Example 1 is that, in the preparation process of the hybrid branched organosilicon resin, the amount of triethoxysilyl-isophthalic anhydride was increased and the amount of polyether-modified bisphenol A diethoxysilane was reduced. Except for the preparation method of the hybrid branched silicone resin, which is different from that in Example 1, the other preparation methods are the same as those in Example 1.

[0080] Comparative Example 7 The specific preparation steps of the hybrid branched organosilicon resin are as follows: (1) Raw material pretreatment: 28g tetraethyl orthosilicate, 12g triethoxysilyl-isophthalic anhydride, 28g polyether modified bisphenol A diethoxysilane, and 12g borate-phosphonate disubstituted ethoxysilane were added to a 500mL three-necked flask, and 5Å molecular sieves were added. The mixture was stirred and dehydrated for 4h under vacuum conditions of 40℃ and -0.09MPa. The sample was tested and the moisture content was ≤0.05% before it could be used. Anhydrous toluene was purified by distillation, the middle fraction was collected, anhydrous magnesium sulfate was added and dried for 24h, and then filtered for later use.

[0081] (2) Preparation of main chain prepolymer: Add 400 mL of pretreated toluene to a three-necked flask. Under nitrogen atmosphere protection, add 28 g of pretreated tetraethyl orthosilicate, 12 g of triethoxysilyl-isophthalic anhydride, 28 g of polyether modified bisphenol A diethoxysilane, and 12 g of borate-phosphonate disubstituted ethoxysilane in sequence. Stir until the materials are mixed evenly, and then add 10 μL of catalyst. Then heat the system to 85 °C and keep it at the temperature for 6 h for co-condensation reaction. After the reaction is completed, add toluene to achieve a solid content of 50%.

[0082] (3) Side-linking reaction: Keep the reaction system temperature at 85℃, add 9g of perfluorooctyl-triazine cyclotriethoxysilane and 3g of terminal hydroxyl polydimethylsiloxane, stir until uniform, raise the temperature to 95℃, and keep the reaction at the temperature for 4h to prepare organosilicon resin.

[0083] The difference between Comparative Example 7 and Example 1 is that, in the preparation process of the hybrid branched organosilicon resin, the amount of triethoxysilyl-isophthalic anhydride was reduced and the amount of polyether-modified bisphenol A diethoxysilane was increased. Except for the preparation method of the hybrid branched silicone resin, which is different from that in Example 1, the other preparation methods are the same as those in Example 1.

[0084] Comparative Example 8 Referring to the prior art, an organosilicon resin, by weight, has the following composition, including: component A and component B; Component A comprises: 100 parts vinyl silicone oil and 20 parts filler; Component B comprises: 100 parts of hydrogen-containing silicone oil and 0.1 parts of organotin catalyst.

[0085] The mass ratio of component A to component B is 1:0.03.

[0086] The viscosity of the vinyl silicone oil in component A is 1000 mPa•s; The filler in component A is fumed nano-silica; The viscosity of the hydrogen-containing silicone oil in component B is 200 mPa•s.

[0087] The preparation method of the organosilicon resin is as follows: Step 1: Add vinyl silicone oil and filler to a disperser and stir at a rate of 500 r / min for 10 min until homogeneous to obtain component A; Step 2: Stir the hydrogen-containing silicone oil and organotin catalyst at a rate of 500 r / min for 15 min to obtain component B; Step 3: Mix component A and component B in a certain proportion, degas under vacuum for 8 minutes, apply the mixture to the surface of a concrete test block, and cure it completely at 50°C to obtain the silicone resin.

[0088] Experimental example: Impact resistance test: Referring to section 5.21 of SL / T352-2020 "Test Procedure for Hydraulic Concrete" (underwater steel ball method), the impact resistance of the silicone coating against high-speed water flow was calculated using formula (1): (1) In the formula: The strength to withstand the impact of high-speed water flow, i.e., the mass worn per unit area per unit time, is expressed as h / (g / cm²). 2 ); T The cumulative test time is in hours (h). A The area of ​​the specimen subjected to impact and abrasion is in cm². 2 ; M , for T The cumulative mass loss of the specimen after the period of impact grinding, in g.

[0089] Adhesion strength test: The silicone prepared in Examples 1-5 and Comparative Examples 1-7 were applied to dry concrete surfaces and allowed to cure completely. Five different areas on the silicone surface were then treated with epoxy resin adhesive to adhere aluminum ingots with a diameter of 20 mm. The adhesion strength of the silicone coating on the concrete was measured using a DeFelsko pull-out tester according to ASTM D4541, with a pull-out rate of 0.2 MPa·s. -1 The average value of the measurements from five different regions was taken as the test result.

[0090] Surface contact angle test: Place the flat, clean, and fully cured samples prepared in Examples 1-5 and Comparative Examples 1-7 horizontally on the sample stage of the contact angle measuring instrument. Using a micro-syringe, gently drop a 5 μL drop of deionized water onto the sample surface; calculate the angle between the edge of the droplet and the sample surface, which is the surface contact angle.

[0091] Flexibility test: Refer to GB / T6742 "Bending test of paints and varnishes (cylindrical shaft)" to complete the flexibility test of the organosilicon samples prepared in Examples 1-5 and Comparative Examples 1-7.

[0092] Water absorption rate test: Referring to GB / T1034 "Determination of water absorption of plastics", the water absorption rate of the samples prepared in Examples 1-5 and Comparative Examples 1-7 was tested; the initial dry weight after drying was m1, and after fully soaking and absorbing water, the surface water was wiped dry and the weight was m2. The water absorption rate (%) was calculated as [(m2-m1) / m1]*100%.

[0093] The performance test results of Examples 1-5 and Comparative Examples 1-7 are shown in Table 1: Table 1:

[0094] Performance testing and analysis: The multi-layered cross-linked impact-resistant and abrasion-resistant silicone of the present invention, namely Example 1, exhibits excellent impact and abrasion resistance. Furthermore, while maintaining excellent adhesion, it also possesses good flexibility and water resistance, with significant performance indicators. The only difference between Example 1 and Comparative Example 5 is the presence or absence of filler. Although Comparative Example 5 showed slightly higher bonding strength after removing the filler than Example 1, its impact and abrasion resistance deteriorated rapidly, indicating that high bonding strength does not necessarily equate to high abrasion resistance. A possible reason for this is the use of fumed silica filler. The filler binds to the active sites of resin molecules, such as hydroxyl and siloxane groups, through surface silanol groups, embedding itself in the cross-linked network. This not only enhances the network density through a nano-reinforcement effect but also disperses external impact stress.

[0095] Those skilled in the art generally believe that increased flexibility is beneficial for stress dispersion, thereby improving bond strength. By comparing the performance test data of Example 1, Comparative Example 2, Comparative Example 6, and Comparative Example 7, it can be found that Comparative Example 2 removed polyether-modified bisphenol A diethoxysilane; Comparative Examples 6 and 7 adjusted the amounts of triethoxysilyl-isophthalic anhydride and polyether-modified bisphenol A diethoxysilane, respectively. However, all of these resulted in a significant decrease in bond strength and impact resistance, indicating that in the multi-level crosslinking system of this application, there exists an extremely narrow, synergistic window. Within this window, moderate rigidity not only provides a basis for wear resistance, but its regular molecular chain structure also contributes positively to interfacial forces.

[0096] Similarly, compared to Comparative Example 1, the impact and abrasion resistance of Comparative Example 1 decreased significantly after the removal of the borate-phosphonate disubstituted ethoxysilane. A possible reason is that the technical solution of this application constructs a hybrid branched organosilicon resin main chain structure using tetraethyl orthosilicate, triethoxysilyl-isophthalic anhydride, polyether-modified bisphenol A diethoxysilane, and borate-phosphonate disubstituted ethoxysilane. The triethoxysilyl-isophthalic anhydride provides a large number of benzene ring structures to the main chain molecule, increasing the rigidity of the main chain and enhancing the material's resistance to deformation; the polyether-modified bisphenol A diethoxysilane breaks the rigid aggregation of the main chain, giving the molecular chain a certain degree of mobility and alleviating stress concentration caused by external impact; the borate-phosphonate disubstituted ethoxysilane provides hybrid atoms to the main chain, which can enhance intermolecular interactions through coordination, hydrogen bonding, and other interactions, collectively improving the material's wear resistance.

[0097] Compared with Example 1, Comparative Example 3 completely removed perfluorooctyl-triazine cyclotriethoxysilane, causing the material surface to change abruptly from strongly hydrophobic to hydrophilic.

[0098] The difference between Comparative Example 4 and Example 1 is that the hydroxyl-terminated polydimethylsiloxane was completely removed and replaced with an equal amount of perfluorooctyl-triazine cyclotriethoxysilane. The flexibility and bonding strength of Comparative Example 4 both decreased. The possible reasons are as follows: the triethoxy group of perfluorooctyl-triazine-triethoxysilane reacts with the residual hydroxyl and siloxane groups in the main chain to graft fluorine-containing branches onto the main chain. The low surface energy of the fluorine-containing groups can reduce the adhesion resistance during water flow impact, while the triazine ring structure enhances the rigidity of the branches. On the other hand, the hydroxyl groups of terminal hydroxyl polydimethylsiloxane combine with the active sites of the main chain to graft flexible siloxane segments onto the side ends of the main chain, further improving the flexibility of the molecular chain and alleviating impact stress. Moreover, the weather resistance and water resistance of the siloxane segments can improve the overall environmental adaptability of the resin.

[0099] Furthermore, based on a comparison of Examples 1, 4, and 5, it can be found that the selection of the crosslinking system and catalyst is also crucial. Example 4, using a single crosslinking agent, and Example 5, using a conventional tin catalyst, both resulted in a comprehensive deterioration of adhesion, bond strength, and water resistance. This demonstrates a unique and irreplaceable synergistic matching relationship between the composite crosslinking system and bismuth-based catalyst of the present invention and the resin host containing B and P atoms.

[0100] The crosslinking agent formulation used in Example 1 can chemically react with the active groups of hybrid branched resins, such as hydroxyl and amino groups, to form a high-density crosslinked network. In contrast, using only diphenylmethane diisocyanate as a crosslinking agent results in insufficient internal chemical crosslinking, leading to decreased system rigidity and making the coating prone to cracking and wear under external forces. Furthermore, the catalyst exhibits significantly better tolerance to phosphorus and phosphorus (P and B) in the hybrid branched silicone resin molecular chain structure than conventional tin-based catalysts, ensuring reaction efficiency and product quality stability.

[0101] The remarkable performance leaps achieved by these inventions demonstrate that the molecular design of this invention is not a simple patchwork of existing technologies, but rather a solution to the technical challenges existing in the prior art by constructing a novel synergistic mechanism.

[0102] Comparative Example 8 is a conventional organosilicon material system in the prior art. Although it has excellent flexibility, its impact and abrasion resistance and bonding strength obviously cannot meet the requirements of high-performance protection. In addition, it has poor adhesion, high water absorption, and significant physical limitations.

[0103] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A multi-layered cross-linked impact-resistant and wear-resistant organosilicon, characterized in that, Its composition by weight is as follows, including component A and component B; Component A comprises 80-100 parts of hybrid branched organosilicon resin and 0.01-0.1 parts of catalyst; Component B comprises 20-30 parts of crosslinking agent and 10-30 parts of filler; The mass ratio of component A to component B is 1:(0.2-0.5).

2. The multi-layered cross-linked impact-resistant and wear-resistant organosilicon according to claim 1, characterized in that, The catalyst in component A is one or more of bismuth octoate, zinc octoate, and butyltin thiolate.

3. The multi-layered cross-linked impact-resistant and wear-resistant organosilicon according to claim 1, characterized in that, The crosslinking agent in component B is one or more of diphenylmethane diisocyanate, KH-560, and isophorone diisocyanate.

4. The multi-layered cross-linked impact-resistant and wear-resistant organosilicon according to claim 1, characterized in that, The multi-layered cross-linked impact-resistant and wear-resistant silicone, by weight, has the following composition, including component A and component B; Component A comprises 90 parts of hybrid branched silicone resin and 0.05 parts of catalyst; Component B comprises 25 parts of crosslinking agent and 20 parts of filler; The catalyst is bismuth octanoate; The crosslinking agent is a mixture of diphenylmethane diisocyanate and KH-560. The filler in component B is fumed silica.

5. The multi-layered cross-linked impact-resistant and wear-resistant organosilicon according to claim 4, characterized in that, The primary particle size of the fumed silica filler is 5-20 nm. The mass ratio of component A to component B is 1:0.3; The mass ratio of diphenylmethane diisocyanate to KH-560 is 2:

1.

6. A multi-layered cross-linked impact-resistant and wear-resistant organosilicon according to any one of claims 1-5, characterized in that, The preparation method of the hybrid branched organosilicon resin in component A includes the following steps: raw material pretreatment: tetraethyl orthosilicate, triethoxysilyl-isophthalic anhydride, polyether-modified bisphenol A diethoxysilane, and borate-phosphonate-disubstituted ethoxysilane are respectively added to a three-necked flask, 5 Å molecular sieve is added, and the mixture is stirred and dehydrated for 4 h under vacuum conditions of 40 °C and -0.09 MPa. The sample is tested and the moisture content is ≤0.05% before it can be used; anhydrous toluene is purified by distillation, the middle fraction is collected, anhydrous magnesium sulfate is added and dried for 24 h, and then filtered for later use; Preparation of the main chain prepolymer: Pretreated toluene was added to a three-necked flask. Under a nitrogen atmosphere, pretreated tetraethyl orthosilicate, triethoxysilyl-isophthalic anhydride, polyether-modified bisphenol A diethoxysilane, and borate-phosphonate-disubstituted ethoxysilane were added sequentially. The mixture was stirred until homogeneous, and then the catalyst was added dropwise. The system was then heated to 85°C and kept at this temperature for 6 hours for a copolymerization reaction. After the reaction was completed, toluene was added to achieve a solid content of 45%-50%. Side-linking reaction: Keep the reaction system temperature at 85℃, add perfluorooctyl-triazine cyclotriethoxysilane and hydroxyl-terminated polydimethylsiloxane, stir until uniform, then raise the temperature to 95℃ and keep the reaction at this temperature for 4 hours to obtain hybrid branched organosilicon resin.

7. The multi-layered cross-linked impact-resistant and wear-resistant organosilicon according to claim 6, characterized in that, The preparation steps for the triethoxysilyl-isophthalic anhydride required for the hybrid branched organosilicon resin in component A are as follows: Raw material pretreatment: Isophthalic anhydride was placed in a vacuum oven and dried at 80℃ and -0.09MPa vacuum for 4 hours to remove trace amounts of moisture. After cooling, it was transferred to a dry three-necked flask. Anhydrous dichloromethane was soaked in a 5Å molecular sieve for 24 hours and then collected by distillation. Preparation of isophthaloyl chloride: Isophthalic anhydride was dissolved in dried dichloromethane, and then thionyl chloride was slowly added dropwise, with the reaction temperature controlled at ≤25℃ during the addition. After the addition was completed, the reaction system was heated to 40℃ and kept at this temperature for 6 hours. After the reaction was completed, nitrogen gas was purged for 30 minutes to remove residual SO2 and HCl gas from the system, resulting in a dichloromethane solution of isophthaloyl chloride. Preparation of triethoxysilyl-isophthalic anhydride: The reaction system temperature was maintained at 40℃. Triethylamine was mixed evenly and slowly added dropwise to a dichloromethane solution of isophthaloyl chloride. During the dropwise addition, the pH of the system was controlled between 7 and 8. After the dropwise addition was completed, the temperature was raised to 55℃ and the reaction was maintained at this temperature for 8 hours. The obtained product was subjected to rotary evaporation, chromatography, and rotary evaporation again to obtain the final white powdered triethoxysilyl-isophthalic anhydride.

8. The multi-layered cross-linked impact-resistant and wear-resistant organosilicon according to claim 6, characterized in that, The preparation steps of the polyether-modified bisphenol A diethoxysilane required for the hybrid branched organosilicon resin in component A are as follows: Raw material pretreatment: 2,2-bis(p-hydroxyphenylpropane) was dried under vacuum at 100℃ and -0.09MPa for 6 h; ethylene oxide / propylene oxide was purified by 5Å molecular sieve and dried by toluene distillation; Bisphenol A polyetherification: In a high-pressure reactor, dry bisphenol A and KOH were added, and after nitrogen purging, the temperature was raised to 120°C for melting. First, propylene oxide was introduced at a rate of 10 g / h, and the reactor pressure was maintained at 0.3-0.5 MPa. Then, ethylene oxide was introduced at a rate of 15 g / h and the temperature was raised to 130°C. The reaction was maintained at this temperature for 4 h. After the reaction was completed, the temperature was lowered to 60°C and triphenyl phosphite was added to terminate the reaction, resulting in hydroxyl-terminated polyether modified bisphenol A. Polyether-modified bisphenol A diethoxysilane: Polyether bisphenol A and anhydrous toluene were added to a three-necked flask, and the mixture was heated to 80°C under nitrogen to dissolve. After adding anhydrous sodium carbonate, γ-chloropropyl diethoxysilane was slowly added dropwise. After the addition was complete, the temperature was raised to 95°C and the reaction was maintained for 6 hours. After the reaction was completed, the target product, polyether-modified bisphenol A diethoxysilane, was obtained by desolvation under reduced pressure.

9. The multi-layered cross-linked impact-resistant and wear-resistant organosilicon according to claim 6, characterized in that, The preparation steps for the borate-phosphonate disubstituted ethoxysilane required for the hybrid branched organosilicon resin in component A are as follows: Raw material pretreatment: KH-550 was added to 5Å molecular sieve and dehydrated under vacuum at 40℃ and -0.09MPa for 3 hours; tributyl borate and diethyl phosphite were each dried with anhydrous magnesium sulfate for 12 hours, filtered, and then distilled; anhydrous ethanol was distilled and then added to 5Å molecular sieve and allowed to stand for 24 hours. Anhydrous ethanol was added to a three-necked flask, and after inertization by purging with nitrogen, dehydration KH-550 was added. The temperature was raised to 55°C and p-toluenesulfonic acid was added, followed by the dropwise addition of tributyl borate. After the addition was complete, the temperature was raised to 70°C and the reaction was carried out for 4 hours to obtain an amino-boron ester intermediate. The temperature was lowered to 50°C and hydroquinone was added, followed by the dropwise addition of diethyl phosphite. After the addition was complete, the temperature was raised to 65°C and the reaction was carried out for 5 hours. After the reaction was complete, anhydrous magnesium sulfate was added and stirred for 6 hours. After filtration, the mixture was extracted twice with petroleum ether. After desolvation under reduced pressure at 50°C and -0.09 MPa, the final product, borate ester-phosphonate ester disubstituted ethoxysilane, was obtained.

10. The multi-layered cross-linked impact-resistant and wear-resistant organosilicon according to claim 6, characterized in that, The preparation steps for the perfluorooctyl-triazine cyclotriethoxysilane required for the hybrid branched organosilicon resin in component A are as follows: Raw material pretreatment: Cyanurium chloride was dried under vacuum at 60℃ and -0.095MPa for 4h; KH-550 was added with 5Å molecular sieve and dehydrated under vacuum at 40℃ for 3h; dichloromethane was distilled and dried with calcium chloride; 1H,1H-perfluorooctylamine was dried with magnesium sulfate; and triethylamine was purified by distillation. Preparation of perfluorooctyl-triazine cyclotriethoxysilane: Dichloromethane was added to a three-necked flask, and after inertization by purging with nitrogen, the temperature was lowered to 0-5℃. Cyanurium chloride and triethylamine were added, and after stirring to dissolve, KH-550 was added dropwise. After the addition was complete, the temperature was raised to 25℃ and reacted for 4 hours. The triethylamine hydrochloride was removed by filtration to obtain a monosilane-substituted intermediate. The remaining triethylamine was added to the filtrate, and the temperature was raised to 35℃. Perfluorooctylamine was added dropwise. After the addition was complete, the temperature was raised to 50℃ and reacted for 6 hours. The temperature was lowered and 2,6-di-tert-butyl-p-cresol was added to obtain a crude product solution. The crude product solution was filtered through a filter membrane to remove salt, washed three times with deionized water until pH=7, dried with calcium chloride for 8 hours, and then desoluble under reduced pressure at 40℃ and -0.09MPa until the solid content was ≥99%. After cooling to 10℃, it was dissolved in n-hexane, allowed to stand at -5℃ for 12 hours to precipitate crystals, washed twice with cold n-hexane, and then dried under vacuum at 30℃ for 6 hours to obtain a white powder product, which is the prepared perfluorooctyl-triazine cyclotriethoxysilane.

11. The method for preparing a multi-layered crosslinked impact-resistant and wear-resistant organosilicon according to claim 1, characterized in that, The preparation method of the multi-level cross-linked impact-resistant and wear-resistant organosilicon includes the following steps: Step 1: Add hybrid branched organosilicon and catalyst to a disperser and stir at a rate of 500 r / min for 10 min to mix evenly, and obtain component A; Step 2: Add the crosslinking agent and filler to the disperser and stir at a rate of 500 r / min for 15 min to obtain component B; Step 3: Mix component A and component B in a certain proportion and then cure to obtain multi-layered cross-linked impact-resistant and wear-resistant organosilicon.

12. The application of a multi-level cross-linked impact-resistant and wear-resistant organosilicon prepared according to claim 11 in the field of concrete resistance to high-speed water flow abrasion in water conservancy and hydropower engineering.

Images