CN-122011941-A - Multi-layer cross-linked impact-resistant wear-resistant organic silicon and preparation method and application thereof

CN122011941ACN 122011941 ACN122011941 ACN 122011941ACN-122011941-A

Abstract

The invention discloses multi-layer cross-linked impact-resistant wear-resistant organic silicon and a preparation method and application thereof, and belongs to the technical field of organic silicon. The multi-layer cross-linked impact-resistant wear-resistant organic silicon comprises, by weight, a component A and a component B, wherein the component A comprises 80-100 parts of hybridized branched-chain organic silicon resin and 0.01-0.1 part of catalyst, the component B comprises 20-30 parts of cross-linking agent and 10-30 parts of filler, and the mass ratio of the component A to the component B is 1 (0.2-0.5). The fluorine-containing groups introduced by the invention endow the material with low surface energy characteristics, can reduce adhesion resistance and friction loss during water flow impact, can adapt to complex water body environment and temperature change in hydraulic and hydroelectric engineering, and has the performance advantage of long-term stable use.

Inventors

DONG SHIHUA
LIN WEI
XU YINJIE
YIN XUEWU
Mo Longyi
LIU YAHUI

Assignees

杭州伽源科技有限公司

Dates

Publication Date: 20260512
Application Date: 20260414

Claims (12)

1. The multilayer cross-linked impact-resistant wear-resistant organic silicon is characterized by comprising the following components in parts by weight, namely a component A and a component B; the component A comprises 80-100 parts of hybridized branched-chain type organic silicon resin and 0.01-0.1 part of catalyst; the component B comprises 20-30 parts of cross-linking agent and 10-30 parts of filler; The mass ratio of the component A to the component B is 1 (0.2-0.5).
2. The multi-level cross-linked impact and abrasion resistant silicone according to claim 1 wherein the catalyst in component a is one or more of bismuth octoate, zinc octoate and butyltin mercaptide.
3. The multi-stage cross-linked impact and abrasion resistant silicone according to claim 1, wherein the cross-linking agent in component B is one or more of diphenylmethane diisocyanate, KH-560, isophorone diisocyanate.
4. The multi-level cross-linked impact and abrasion resistant silicone according to claim 1, wherein the multi-level cross-linked impact and abrasion resistant silicone comprises the following components in parts by weight, component a and component B; The component A comprises 90 parts of hybridized branched-chain type organic silicon resin and 0.05 part of catalyst; the component B comprises 25 parts of cross-linking agent and 20 parts of filler; The catalyst is bismuth octoate; The cross-linking agent is a mixture of diphenylmethane diisocyanate and KH-560, The filler in the component B is fumed silica.
5. The multi-stage cross-linked impact and abrasion resistant silicone of claim 4 wherein said filler fumed silica has a primary particle size of 5-20nm; the mass ratio of the component A to the component B is 1:0.3; The mass ratio of the diphenylmethane diisocyanate to KH-560 is 2:1.
6. The multi-layer cross-linked impact-resistant wear-resistant organic silicon according to any one of claims 1 to 5, wherein the preparation method of the hybridized branched organic silicon resin in the component A comprises the following steps of raw material pretreatment, namely respectively adding tetraethyl orthosilicate, triethoxysilyl-isophthalic anhydride, polyether modified bisphenol A diethoxysilane and borate-phosphonate disubstituted ethoxysilane into a three-neck flask, adding a 5-part molecular sieve, stirring and dehydrating for 4 hours under the vacuum condition of 40 ℃ and minus 0.09MPa, wherein the water content detected by sampling is less than or equal to 0.05% and the water content can be used after sampling, purifying by distillation, collecting middle fractions, adding anhydrous magnesium sulfate, drying for 24 hours, and filtering for later use; Adding pretreated toluene into a three-neck flask, sequentially adding pretreated tetraethyl orthosilicate, triethoxysilyl-isophthalic anhydride, polyether modified bisphenol A diethoxysilane and borate-phosphonate disubstituted ethoxysilane under the protection of nitrogen atmosphere, stirring until materials are uniformly mixed, and then dropwise adding a catalyst, heating the system to 85 ℃, preserving heat, performing copolycondensation reaction for 6h, and adding toluene after the reaction is finished to realize the solid content of 45-50%; And (3) side chain grafting reaction, namely keeping the temperature of a reaction system at 85 ℃, adding perfluorooctyl-triazine triethoxysilane and hydroxyl-terminated polydimethylsiloxane, stirring uniformly, heating to 95 ℃, and carrying out heat preservation reaction for 4 hours to obtain the hybrid branched-chain type organic silicon resin.
7. The multi-stage cross-linked impact and abrasion resistant silicone of claim 6 wherein the step of preparing the triethoxysilyl-isophthalic anhydride required for the hybrid branched silicone resin of component a is as follows: The raw material pretreatment, namely placing isophthalic anhydride into a vacuum oven, drying for 4 hours under the vacuum condition of 80 ℃ to minus 0.09MPa to remove trace moisture, cooling and transferring into a dry three-neck flask, soaking anhydrous dichloromethane for 24 hours through a 5A molecular sieve, and collecting through distillation; The preparation of the isophthaloyl dichloride comprises the steps of dissolving isophthalic anhydride in dichloromethane after drying treatment, slowly dropwise adding thionyl chloride, controlling the reaction temperature to be less than or equal to 25 ℃ in the dropwise adding process, heating a reaction system to 40 ℃ after the dropwise adding is finished, preserving heat and reacting for 6 hours, introducing nitrogen to purge for 30 minutes after the reaction is finished, and removing residual SO 2 and HCl gas in the system to obtain a dichloromethane solution of the isophthaloyl dichloride; The preparation of triethoxysilyl-isophthalic acid anhydride includes maintaining the temperature of the reaction system at 40 deg.c, mixing triethylamine and isophthalic acid chloride solution, dropping the mixture slowly into the dichloromethane solution of isophthalic acid chloride, controlling the pH value of the system between 7 and 8, heating to 55 deg.c, maintaining the temperature for reaction for 8 hr, rotating evaporation, chromatographic separation and rotating evaporation to obtain white triethoxysilyl-isophthalic acid anhydride powder.
8. The multi-level cross-linked impact abrasion resistant silicone of claim 6 wherein the step of preparing polyether modified bisphenol a diethoxysilane for the hybrid branched silicone resin of component a comprises: Raw material pretreatment, namely vacuum drying 2, 2-bis-p-hydroxyphenyl propane at 100 ℃ and minus 0.09MPa for 6 hours, purifying ethylene oxide/propylene oxide by a 5A molecular sieve, and drying toluene by distillation; Adding dry bisphenol A and KOH into a high-pressure reaction kettle, heating to 120 ℃ for melting after nitrogen replacement, introducing propylene oxide at 10g/h, maintaining the kettle pressure at 0.3-0.5MPa, introducing ethylene oxide at 15g/h, heating to 130 ℃, and carrying out heat preservation reaction for 4 hours, cooling to 60 ℃ after the reaction is finished, and adding triphenyl phosphite for termination to obtain hydroxyl-terminated polyether modified bisphenol A; Polyether modified bisphenol A diethoxy silane is prepared through adding polyether bisphenol A and anhydrous toluene into a three-neck flask, introducing nitrogen gas, heating to 80 deg.c for dissolving, adding anhydrous sodium carbonate, slowly dropping gamma-chloropropyl diethoxy silane, heating to 95 deg.c for heat preservation reaction for 6 hr, and decompression and desolventizing.
9. The multi-stage cross-linked impact and abrasion resistant silicone according to claim 6, wherein the preparation steps of the borate-phosphonate disubstituted ethoxysilane required for the hybrid branched silicone resin in component a are as follows: pretreating raw materials, namely adding KH-550 into a 5A molecular sieve, dehydrating for 3 hours at 40 ℃ under the vacuum of minus 0.09MPa, respectively adding tributyl borate and diethyl phosphite into anhydrous magnesium sulfate, drying for 12 hours, filtering, distilling, adding 5A molecular sieve after distilling absolute ethyl alcohol, and standing for 24 hours; Adding absolute ethyl alcohol into a three-neck flask, introducing nitrogen for inertization, then adding dehydrated KH-550, heating to 55 ℃, adding p-toluenesulfonic acid, dropwise adding tributyl borate, heating to 70 ℃ after dropwise adding, and reacting for 4 hours to obtain an amino-borate intermediate; And adding anhydrous magnesium sulfate after the reaction is finished, stirring for 6 hours, filtering, extracting with petroleum ether twice, and carrying out reduced pressure desolventizing at 50 ℃ and minus 0.09MPa to obtain the final product boric acid ester-phosphonic acid ester-disubstituted ethoxysilane.
10. The multi-stage cross-linked impact and abrasion resistant silicone according to claim 6, wherein the preparation steps of the perfluorooctyl-triazinyl triethoxysilane required for the hybrid branched silicone resin in component a are as follows: Pretreating raw materials, namely taking cyanuric chloride, vacuum drying at 60 ℃ and minus 0.095MPa for 4 hours, adding a 5A molecular sieve into KH-550, vacuum dehydrating at 40 ℃ for 3 hours, adding calcium chloride for drying after methylene dichloride distillation, adding magnesium sulfate into 1H, 1H-perfluoro octyl amine for drying, and distilling and purifying with triethylamine; Adding dichloromethane into a three-neck flask, introducing nitrogen for inertization, cooling to 0-5 ℃, adding cyanuric chloride and triethylamine, stirring and dissolving, then dropwise adding KH-550, heating to 25 ℃ after dropwise adding, reacting for 4 hours, filtering triethylamine hydrochloride to obtain monosilane substituted intermediate, adding residual triethylamine into filtrate, heating to 35 ℃ and dropwise adding perfluorooctylamine, heating to 50 ℃ after dropwise adding, reacting for 6 hours, cooling, and adding 2, 6-di-tert-butyl-p-cresol to obtain crude product solution; Filtering the crude product solution by a filter membrane to remove salt, washing with deionized water for 3 times until the pH value is=7, adding calcium chloride, drying for 8 hours, then decompressing and desolventizing at 40 ℃ and 0.09MPa until the solid content is more than or equal to 99%, cooling to 10 ℃ and adding normal hexane for dissolving, standing at-5 ℃ for 12 hours to separate out crystals, washing with cold normal hexane for 2 times, and drying at 30 ℃ in vacuum for 6 hours to obtain white powder product, namely the prepared perfluorooctyl-triazine triethoxysilane.
11. The preparation method of the multi-level cross-linked impact-resistant and wear-resistant organic silicon, which is disclosed in claim 1, is characterized by comprising the following steps of firstly adding the hybridized branched organic silicon and a catalyst into a dispersing machine, stirring for 10min at the speed of 500r/min, and uniformly mixing to obtain a component A; Step two, adding a cross-linking agent and a filler into a dispersing machine, and stirring for 15min at a speed of 500r/min to obtain a component B; and step three, mixing the component A and the component B in proportion and then curing to obtain the multi-layer cross-linked impact-resistant wear-resistant organosilicon.
12. An application of the prepared multi-level cross-linked impact-resistant wear-resistant organic silicon in the field of high-speed water flow impact abrasion resistance of hydraulic and hydroelectric engineering concrete.

Description

Multi-layer cross-linked impact-resistant wear-resistant organic silicon and preparation method and application thereof Technical Field The invention belongs to the technical field of organic silicon, and particularly relates to a multi-layer cross-linked impact-resistant wear-resistant organic silicon, and a preparation method and application thereof. Background Overcurrent buildings in water conservancy and hydropower engineering, such as dam overflow surfaces, flood discharge holes, gate piers and the like, bear the severe test of high-speed water flow for a long time. The high-speed water flow can generate huge impact force and shearing force, and suspended particles such as sand, stones and the like which are wrapped by the high-speed water flow can cause serious abrasion damage to the surface of concrete. In addition, when the flow velocity of water flow is suddenly changed on an uneven overflowing surface, cavitation is extremely easy to occur, and the instantaneous high pressure generated when cavitation bubbles collapse can cause erosive damage, namely cavitation damage, to concrete. The synergistic effect of these scour, abrasion and cavitation severely threatens the safe operation and long-term durability of the building and results in costly and technically difficult maintenance work. To address the challenges described above, the prior art has developed a variety of protective materials. For example, chinese patent publication No. CN109180109A discloses a high-scouring-resistance waterproof inorganic coating and a preparation method thereof. The high-scouring-resistance waterproof inorganic paint comprises, by weight, 120-260 parts of ultrafine silicon carbide with an average particle size of 68-125 mu m, 150-280 parts of cement with strength not lower than 32.5MPa, 110-260 parts of admixture with an average particle size of 5-30 mu m, 5-10 parts of high-performance additive, 5-20 parts of redispersible emulsion powder with a water-gel ratio of 0.2-0.4, 2-5 parts of defoamer, 2-4 parts of dispersant and 10-20 parts of water repellent. According to the technical scheme, cement is mainly used as a main cementing material, superfine carborundum is compounded to be used as wear-resistant aggregate, and various additives such as latex powder and a water repellent are added. It is desirable to resist flushing by water currents by increasing its own solidity and surface hardness. However, in practical applications, as a rigid inorganic material, the toughness and deformation adaptability are limited. The problems of cracking, falling and the like caused by incapability of coordinated deformation are easy, and the long-term protection requirement under the complex working condition is difficult to meet. Also in the prior art, as disclosed in Chinese patent publication No. CN120484630A, a general epoxy sealing coating for concrete surface and a preparation method thereof are disclosed. The technical scheme is that the coating comprises a component A and a component B, wherein the weight ratio of the component A to the component B is (2-4) 1, the component A comprises epoxy resin, an active diluent, pigment filler, a defoaming agent, a dispersing agent, a leveling agent and an anti-settling agent, and the component B comprises a curing agent, an accelerator and a coupling agent. The coating is formed by reacting bisphenol A type or bisphenol F type epoxy resin with polyamine curing agent, a compact crosslinked network is formed, and invasion of water and corrosive medium can be effectively isolated, but the traditional epoxy resin coating also has the defects that a molecular chain structure of the traditional epoxy resin coating contains a large amount of benzene rings, the traditional epoxy resin coating is strong in rigidity and insufficient in flexibility, the texture of the traditional epoxy resin coating is relatively brittle, the toughness of the traditional epoxy resin coating is further reduced under a low-temperature environment, and the anti-impact performance of the traditional epoxy resin coating is poor. Also in the prior art, as disclosed in Chinese patent publication No. CN120082273A, a modified single-component polyurea waterproof coating, a preparation method and application thereof and a hydraulic concrete protective coating structure are disclosed. The technical scheme is that the modified single-component polyurea waterproof coating comprises the following preparation raw materials by mass, namely polytetrahydrofuran polyol, polyether triol, fluorine-containing polyether polyol, FEVE type fluorocarbon resin, organosilicon polyether diol, a hydrophobic agent, isocyanate, a defoaming agent, a diluent, a dispersing agent, a catalyst, a latent curing agent, a coupling agent, a water removing agent, pigment and filler, a thixotropic agent and a plasticizer. According to the technical scheme, the fluorine-containing polyether and the organic silicon polyether are introduced to modify the p