An anticorrosive combination polyether and a method for preparing the same

Abstract

The present application relates to a kind of anticorrosion combination polyether and its preparation method, belong to combination polyether technical field, according to weight parts, the preparation raw material of the anticorrosion combination polyether includes:65-80 parts polyether polyol matrix composition, 15-25 parts barrier type composite nanofiller, 3-5 parts surface protective agent, 2.5-5 parts fluorine modified epoxy silane coupling agent, 4-8 parts polyether modified siloxane coupling agent, 2-4 parts chain extender, 1-1.5 parts benzotriazole-phosphite composite stabilizer, 10-15 parts cyclopentane foaming agent, 1-2 parts hardness strengthening agent.Barrier type composite nanofiller, surface protective agent, the polyether polyol matrix composition of the cooperation of the two by containing imidazole ring polyether, m-phenylenediamine base polyether, fluorine modified polyether, effectively improve the anticorrosion ability of combination polyether, satisfy the application demand of harsh environment such as wet, salt, acid and alkali.

Description

Technical Field

[0001] This invention belongs to the field of composite polyether technology, specifically relating to an anti-corrosion composite polyether and its preparation method. Background Technology

[0002] Polyether blends, as a high-performance polymer material, are widely used in many fields such as construction, chemical industry, electronics, and transportation. They have good foaming properties, thermal insulation properties, and processing adaptability, making them an indispensable basic material in many industries. However, in actual application scenarios, polyether blends often face complex and harsh environmental challenges. Moisture erosion in humid environments, chloride ion corrosion in saline media, and chemical damage in acid and alkali media can all lead to a decline in material performance.

[0003] These corrosive effects not only cause aging and damage to the surface of the polyether composite, but also gradually penetrate into the material's interior, leading to internal structural destruction, resulting in a decline in mechanical properties and a shortened service life. In severe cases, they can even affect the safety and stability of the entire application system. Existing conventional polyether composite corrosion-resistant designs often focus on single protective mechanisms, making it difficult to form a comprehensive, multi-layered corrosion-resistant system. This fails to meet the long-term use requirements of complex and harsh environments such as humid, saline, acidic, and alkaline conditions. Therefore, developing polyether composite materials with highly efficient corrosion resistance has become an important research direction in the industry. Summary of the Invention

[0004] The purpose of this invention is to provide an anti-corrosion composite polyether and its preparation method in order to solve the above-mentioned problems.

[0005] The present invention achieves the above objectives through the following technical solutions: This invention provides an anti-corrosion composite polyether, wherein the raw materials for preparing the anti-corrosion composite polyether, by weight, include: 65-80 parts of polyether polyol matrix composition, 15-25 parts of barrier-type composite nanofiller, 3-5 parts of surface protectant, 2.5-5 parts of fluorine-modified epoxy silane coupling agent, 4-8 parts of polyether-modified siloxane coupling agent, 2-4 parts of chain extender, 1-1.5 parts of benzotriazole-phosphite composite stabilizer, 10-15 parts of cyclopentane foaming agent, and 1-2 parts of hardness enhancer; The raw materials for preparing the polyether polyol matrix composition, by weight, include: 16.25-20 parts imidazole ring polyether, 26-32 parts m-phenylenediamine polyether, and 22.75-29 parts fluorine-modified polyether. The raw materials for preparing the barrier-type composite nanofiller, by weight, include: 0.5-1 parts of nano-graphene, 6-8 parts of fluorine-modified nano-SiO2, 8-13 parts of anhydrous ethanol, and 0.5-0.8 parts of γ-methacryloyloxypropyltrimethoxysilane coupling agent. The raw materials for preparing the surface protectant, by weight, include: 1.5-2 parts of fluorine-modified epoxy resin, 0.8-1.2 parts of aminosilane crosslinking agent, 0.2-0.3 parts of nano boron nitride, 0.15-0.2 parts of organically modified nano montmorillonite, 10-15 parts of ethyl acetate, and 0.5-1 parts of deionized water.

[0006] As a further optimization of the present invention, the preparation process of the surface protectant is as follows: (i) adding nano-boron nitride and organically modified nano-montmorillonite to ethyl acetate, placing it in a high-speed disperser, dispersing at 1950-2050 r / min for 20-40 min, and then using an ultrasonic disperser with a power of 295-305 W and a frequency of 17-39 kHz for 10-20 min to obtain a nanoparticle dispersion; (ii) adding fluorinated epoxy resin to the nanoparticle dispersion, adjusting the speed of the high-speed disperser to 900-1100 r / min, and stirring at 20-30℃ for 19-24 min to obtain an epoxy nanoparticle composite matrix; (iii) adding ethyl acetate dropwise to the epoxy nanoparticle composite matrix to adjust the viscosity of the system to 500-1000 mPa. s, to obtain the adjusted composite base material; (iv) add aminosilane crosslinking agent and deionized water to the adjusted composite base material, adjust the speed of the high-speed disperser to 780-820r / min, and continue stirring for 20-40min under constant temperature of 23-28℃ to obtain the pre-crosslinked base material; (v) after vacuum filtering the pre-crosslinked base material with 200 mesh nylon filter cloth, obtain the surface protectant.

[0007] As a further optimization of the present invention, the particle size of the organically modified nano-montmorillonite is 100-200 nm.

[0008] As a further optimization of the present invention, the preparation process of the barrier-type composite nanofiller is as follows: (i) Adding nano-graphene to anhydrous ethanol and ultrasonically exfoliating and dispersing for 20-40 min to obtain a graphene-ethanol dispersion, adding γ-methacryloxypropyltrimethoxysilane coupling agent to it, and stirring for 15-25 min to obtain a pre-activated material; (ii) Adding fluorine-modified nano-SiO2 to anhydrous ethanol and stirring for 8-12 min to obtain a fluorine-modified nano-SiO2 suspension; (iii) Slowly dripping the fluorine-modified nano-SiO2 suspension into the graphene-ethanol dispersion and stirring at high speed for 17-23 min to form a mixed dispersion; (iv) Adding distilled water to the mixed dispersion, adjusting the pH to 5-7, and stirring at a constant temperature of 50-60℃ for 1.5-2.5 h to obtain a grafted mixed system; (v) After vacuum drying the grafted mixed system by depressurization and distillation, obtaining the barrier-type composite nanofiller.

[0009] As a further optimization of the present invention, the preparation process of the polyether polyol matrix composition is as follows: (i) Imidazole ring polyether, m-phenylenediamine polyether, and fluorinated polyether are sequentially added to a vacuum constant temperature stirred reactor. After closing the reactor door, the vacuum degree is adjusted to -0.08--0.1MPa, the temperature is raised to 100-110℃, and vacuum dehydration is carried out at a speed of 300-400r / min for 1-1.5h to obtain a dehydrated mixture; (ii) Maintaining the above vacuum parameters, the temperature is lowered to 60-70℃, and first stirred at a low speed of 600-800r / min. (ii) Heat the mixture for 20-40 minutes, then increase the temperature to 1200-1500 r / min and stir at high speed for 40-50 minutes to obtain a preliminary mixture; (iii) Maintain a constant temperature of 60-70℃, a vacuum of -0.08--0.1MPa and a speed of 1200-1500 r / min, and continue stirring for 1-1.5 hours to obtain an activated product; (iv) Reduce the speed to 200-400 r / min, maintain a constant temperature and vacuum for 30-40 minutes to degas, and then allow it to cool naturally to 25-30℃. After filtration, the polyether polyol matrix composition is obtained.

[0010] As a further optimization of the present invention, the raw materials for preparing the hardness strengthening agent, by weight, include: 3-4 parts of nano-silicon carbide particles, 3-6 parts of composite fiber, 0.1-0.3 parts of bisaminosilane coupling agent, and 8-10 parts of isopropanol. The particle size of the nano-silicon carbide particles is 80-150 nm. The raw materials for the composite fiber filaments include: 2-4 parts basalt fiber filaments and 2-4 parts glass fiber filaments; The basalt fibers have a diameter of 1-3 μm and a length of 50-100 μm. The glass fiber filaments have a diameter of 0.5-2 μm and a length of 30-80 μm.

[0011] As a further optimization of the present invention, the preparation process of the hardness strengthening agent is as follows: (i) uniformly mixing basalt fiber filaments and glass fiber filaments to obtain composite fiber filaments, adding the composite fiber filaments to isopropanol, and using a CNC ultrasonic disperser with a power of 270-330W and a frequency of 27-29kHz for ultrasonic dispersion for 10-20 minutes to obtain a fiber filament dispersion; (ii) adding nano-silicon carbide particles to isopropanol, stirring for 5-15 minutes, and then adding a diaminosilane coupling agent dropwise, activating at room temperature for 10-30 minutes to obtain an activated silicon carbide dispersion; (iii) adding... The fiber dispersion was added dropwise to the activated silicon carbide dispersion at a rate of 1-2 mL / min, and then stirred at high speed of 1200-1500 r / min for 20-40 min to form a mixed composite system; (iv) the mixed composite system was distilled under reduced pressure at 55-65℃ and -0.08--0.1 MPa for 30-40 min to obtain a paste precursor; (v) the precursor was vacuum dried at 80℃ for 2 h, cooled, and then ground at 200 r / min using a planetary ball mill for 20 min, and then passed through a 200 mesh nylon sieve to obtain a hardness enhancer; The isopropanol is divided into two parts. One part, accounting for 70% of the total isopropanol, is used for the dispersion of composite fiber filaments, and the remaining isopropanol is used for the activation of nano-silicon carbide.

[0012] This invention also provides a method for preparing an anti-corrosion polyether, comprising the following steps: S1. Add the polyether polyol matrix composition to a vacuum constant temperature stirred reactor, maintain the vacuum degree of -0.08--0.1MPa and the temperature of 60-70℃, add the hardness strengthening agent and the barrier type composite nanofiller in sequence, adjust the speed to 1200-1500r / min, stir for 40-60min to form a basic mixed system. S2, add fluorine-modified epoxy silane coupling agent and polyether-modified siloxane coupling agent to the basic mixture system, maintain the above vacuum, temperature and speed, and continue stirring for 30-40 min. Then add chain extender, cool to 40-50℃, adjust the speed to 800-1000 r / min, stir for 20-30 min, then add benzotriazole-phosphite composite stabilizer and surface protectant, maintain vacuum of -0.08--0.1MPa and temperature of 40-50℃, stir at 600-800 r / min for 25-35 min, so that the surface protectant is uniformly coated on the surface of the mixture system to form a stable composite system; S3. Turn off the vacuum system, lower the temperature of the stable composite system to 25-30℃, add cyclopentane foaming agent, adjust the speed to 300-400r / min, stir for 15-20min, then inject the material into the mold, and cure at 25-30℃ and 0.1-0.3MPa pressure for 2-3h under constant temperature and pressure. After demolding, the corrosion-resistant composite polyether is obtained.

[0013] The beneficial effects of this invention are as follows: a barrier-type composite nanofiller is prepared by using nano-graphene, fluorine-modified nano-SiO2, anhydrous ethanol, and γ-methacryloyloxypropyltrimethoxysilane coupling agent in a specific ratio; a surface protectant is prepared by using fluorine-modified epoxy resin, aminosilane crosslinking agent, nano-boron nitride, organically modified nano-montmorillonite, ethyl acetate, and deionized water in a specific ratio; and the two are combined with a polyether polyol matrix composition composed of imidazole ring polyether, m-phenylenediamine polyether, and fluorine-modified polyether, which effectively improves the corrosion resistance of the combined polyether and meets the application requirements of harsh environments such as humid, salty, acidic, and alkaline environments. Composite fiber filaments, utilizing basalt fiber filaments and glass fiber filaments, nano-silicon carbide particles to fill the microscopic gaps between the fiber filaments and the polyether polyol matrix composition, barrier-type composite nanofillers, and other materials, significantly enhance the tensile, impact, and flexural fracture resistance of the corrosion-resistant composite polyether. This improved fracture resistance effectively ensures the mechanical integrity of the composite polyether during use in harsh environments, preventing surface protectant failures such as damage and detachment due to material fracture or cracking. This ensures the continuity and stability of the surface protective barrier, ultimately creating a synergistic effect with the anti-corrosion system and further extending the service life of the material under complex working conditions. Detailed Implementation

[0014] The present application will now be described in further detail. It should be noted that the following specific embodiments are only used to further illustrate the present application and should not be construed as limiting the scope of protection of the present application. Those skilled in the art can make some non-essential improvements and adjustments to the present application based on the above application content.

[0015] I. Materials

[0016] Unless otherwise specified, all methods used in this invention are conventional methods known to those skilled in the art, and all reagents and materials used are commercially available products.

[0017] (1) In this invention: Fluorine-modified epoxy silane coupling agents, such as model KH-560F produced by Hubei Xinlantian New Materials Co., Ltd., can be used. The polyether-modified siloxane coupling agent can be SILP-2633, manufactured by Jiangshan Xinna Technology Co., Ltd. The chain extender can be XYlinkHR-MOCA, manufactured by Suzhou Xiangyuan New Materials Co., Ltd. The benzotriazole-phosphite composite stabilizer can be Irganox B 225 manufactured by BASF (China) Co., Ltd. Cyclopentane foaming agent can be industrial grade cyclopentane, model CAS 287-92-3, produced by Xiamen Juda Chemical Equipment Co., Ltd. Fluorine-modified polyethers can be of the type HF-3000 produced by Sanming Haisifu Chemical Co., Ltd. Imidazole-containing polyethers can be made using model IME-46 produced by Hubei Hongjing Chemical Co., Ltd. Fluorine-modified nano-SiO2 can be produced by Hubei Huifu Nanomaterials Co., Ltd., using model HF-FS100. Nano boron nitride can be of model HN-B01 produced by Hubei Huifu Nanomaterials Co., Ltd.; The γ-methacryloxypropyltrimethoxysilane coupling agent can be KH-570 produced by the Institute of Chemistry, Chinese Academy of Sciences. The aminosilane crosslinking agent can be Dynasylan® SIVO203 manufactured by Evonik Industries AG; The bisaminosilane coupling agent can be Dynasylan 1146 manufactured by Evonik Industries AG.

[0018] II. Implementation Examples

[0019] Example 1

[0020] A corrosion-resistant polyether composition, by weight, comprises the following raw materials: 65 parts polyether polyol matrix composition, 15 parts barrier-type composite nanofiller, 3 parts surface protectant, 2.5 parts fluorine-modified epoxy silane coupling agent, 4 parts polyether-modified siloxane coupling agent, 2 parts chain extender, 1 part benzotriazole-phosphite composite stabilizer, 10 parts cyclopentane foaming agent, and 1 part hardness enhancer; The raw materials for preparing the polyether polyol matrix composition, by weight, include: 16.25 parts imidazole ring polyether, 26 parts m-phenylenediamine polyether, and 22.75 parts fluorine-modified polyether. The raw materials for preparing the barrier-type composite nanofiller, by weight, include: 0.5 parts of nano-graphene, 6 parts of fluorine-modified nano-SiO2, 8 parts of anhydrous ethanol, and 0.5 parts of γ-methacryloyloxypropyltrimethoxysilane coupling agent. The raw materials for preparing the surface protectant, by weight, include: 1.5 parts fluorine-modified epoxy resin, 0.8 parts aminosilane crosslinking agent, 0.2 parts nano boron nitride, 0.15 parts organically modified nano montmorillonite (the particle size of the organically modified nano montmorillonite is 100nm), 10 parts ethyl acetate, and 0.5 parts deionized water. The raw materials for preparing the hardness enhancer, by weight, include: 3 parts of nano-silicon carbide particles, 3 parts of composite fiber filaments, 0.1 parts of diaminosilane coupling agent, and 8 parts of isopropanol. Among them, the particle size of the nano-silicon carbide particles is 80nm; The raw materials for the composite fiber filaments include: 2 parts basalt fiber filaments and 2 parts glass fiber filaments; The basalt fibers have a diameter of 1 μm and a length of 50 μm. The glass fiber filaments have a diameter of 0.5 μm and a length of 30 μm. The preparation method of the above-mentioned anti-corrosion polyether includes the following steps: The preparation process of the surface protectant is as follows: (I) Add nano-boron nitride and organically modified nano-montmorillonite to ethyl acetate, place in a high-speed disperser, disperse at 1950 r / min for 20 min, and then use an ultrasonic disperser with a power of 295 W and a frequency of 17 kHz for 10 min to obtain a nanoparticle dispersion; (II) Add fluorine-modified epoxy resin to the nanoparticle dispersion, adjust the speed of the high-speed disperser to 900 r / min, and stir at 20℃ for 19 min to obtain an epoxy nanoparticle composite matrix; (III) Add ethyl acetate dropwise to the epoxy nanoparticle composite matrix to adjust the viscosity of the system to 500 mPa. s, to obtain the adjusted composite base material; (iv) add aminosilane crosslinking agent and deionized water to the adjusted composite base material, adjust the speed of the high-speed disperser to 780 r / min, and continue stirring for 20 min under constant temperature of 23℃ to obtain the pre-crosslinked base material; (v) after vacuum filtering the pre-crosslinked base material with 200 mesh nylon filter cloth, obtain the surface protectant. The preparation process of the barrier-type composite nanofiller is as follows: (i) Add nano-graphene to anhydrous ethanol, ultrasonically exfoliate and disperse for 20 min to obtain graphene ethanol dispersion, add γ-methacryloxypropyltrimethoxysilane coupling agent to it, stir for 15 min to obtain pre-activated material; (ii) Add fluorine-modified nano-SiO2 to anhydrous ethanol, stir for 8 min to obtain fluorine-modified nano-SiO2 suspension; (iii) Slowly drop the fluorine-modified nano-SiO2 suspension into the graphene ethanol dispersion, stir at high speed for 17 min to form a mixed dispersion; (iv) Add distilled water to the mixed dispersion, adjust the pH to 5, and stir at a constant temperature of 50℃ for 1.5 h to obtain a grafted mixed system; (v) After vacuum drying, the grafted mixed system is subjected to reduced pressure and distillation to obtain the barrier-type composite nanofiller. The preparation process of the polyether polyol matrix composition is as follows: (i) Imidazole ring polyether, m-phenylenediamine polyether and fluorinated polyether are added to a vacuum constant temperature stirred reactor in sequence. After closing the reactor door, the vacuum degree is adjusted to -0.08MPa, the temperature is raised to 100℃, and vacuum dehydration is carried out at 300r / min for 1h to obtain a dehydrated mixture; (ii) Maintaining the above vacuum parameters, the temperature is lowered to 60℃, and first stirred at a low speed of 600r / min for 20min, and then the temperature is raised to 1200r / min and stirred at a high speed for 40min to obtain a preliminary mixture; (iii) Maintaining a constant temperature of 60℃, a vacuum of -0.08MPa and a speed of 1200r / min, stirring is continued for 1h to obtain an activated product; (iv) The speed is reduced to 200r / min, the vacuum degree is maintained and the temperature is degassed for 30min, and then the mixture is naturally cooled to 25℃. After filtration, the polyether polyol matrix composition is obtained.

[0021] The preparation process of the hardness enhancer is as follows: (i) Basalt fiber and glass fiber are uniformly mixed to obtain composite fiber. The composite fiber is added to isopropanol and ultrasonically dispersed for 10 min using a CNC ultrasonic disperser with a power of 270W and a frequency of 27kHz to obtain a fiber dispersion; (ii) Nano silicon carbide particles are added to isopropanol and stirred for 5 min. Then, a diaminosilane coupling agent is added dropwise and activated at room temperature for 10 min to obtain an activated silicon carbide dispersion; (iii) The fiber dispersion is added dropwise to the activated silicon carbide dispersion at a rate of 1 mL / min. Then, the mixture is stirred at 1200 r / min for 20 min to form a mixed composite system; (iv) The mixed composite system is distilled under reduced pressure at 55℃ and -0.08MPa for 30 min to obtain a paste precursor; (v) The precursor is vacuum dried at 80℃ for 2 h. After cooling, it is ground for 20 min using a planetary ball mill with a speed of 200 r / min and then passed through a 200-mesh nylon sieve to obtain the hardness enhancer; The polyether polyol matrix composition was added to a vacuum constant temperature stirred reactor, maintaining a vacuum of -0.08 MPa and a temperature of 60°C. Hardness enhancer and barrier composite nanofiller were added sequentially, and the rotation speed was adjusted to 1200 r / min. The mixture was stirred for 40 min to form a basic mixed system. Add fluorinated epoxy silane coupling agent and polyether modified siloxane coupling agent to the basic mixture system, maintain the above vacuum, temperature and speed, and continue stirring for 30 min. Then add chain extender, cool down to 40℃, adjust the speed to 800 r / min, stir for 20 min, then add benzotriazole-phosphite composite stabilizer and surface protectant, maintain vacuum of -0.08 MPa and temperature of 40℃, stir at 600 r / min for 25 min, so that the surface protectant is uniformly coated on the surface of the mixture system to form a stable composite system. Turn off the vacuum system, lower the temperature of the stable composite system to 25°C, add cyclopentane foaming agent, adjust the speed to 300 r / min, stir for 15 min, then inject the material into the mold, and cure at 25°C and 0.1 MPa for 2 h under constant temperature and pressure. After demolding, the corrosion-resistant composite polyether is obtained.

[0022] Example 2

[0023] A corrosion-resistant polyether composition, comprising, by weight, the following raw materials: 72 parts polyether polyol matrix composition, 20 parts barrier-type composite nanofiller, 4 parts surface protectant, 3.75 parts fluorine-modified epoxy silane coupling agent, 6 parts polyether-modified siloxane coupling agent, 3 parts chain extender, 1.25 parts benzotriazole-phosphite composite stabilizer, 12.5 parts cyclopentane foaming agent, and 1.5 parts hardness enhancer; The raw materials for preparing the polyether polyol matrix composition, by weight, include: 18.125 parts imidazole ring polyether, 29 parts m-phenylenediamine polyether, and 25.875 parts fluorine-modified polyether. The raw materials for preparing the barrier-type composite nanofiller, by weight, include: 0.75 parts of nano-graphene, 7 parts of fluorine-modified nano-SiO2, 10.5 parts of anhydrous ethanol, and 0.65 parts of γ-methacryloyloxypropyltrimethoxysilane coupling agent. The raw materials for preparing the surface protectant, by weight, include: 1.75 parts of fluorine-modified epoxy resin, 1 part of aminosilane crosslinking agent, 0.25 parts of nano boron nitride, 0.175 parts of organically modified nano montmorillonite (the particle size of organically modified nano montmorillonite is 150 nm), 12.5 parts of ethyl acetate, and 0.75 parts of deionized water. The raw materials for preparing the hardness enhancer, by weight, include: 3.5 parts of nano-silicon carbide particles, 3.5 parts of composite fiber filaments, 0.2 parts of diaminosilane coupling agent, and 9 parts of isopropanol. Among them, the particle size of the nano-silicon carbide particles is 115nm; The raw materials for the composite fiber filaments include: 3 parts basalt fiber filaments and 3 parts glass fiber filaments; The basalt fibers have a diameter of 2μm and a length of 75μm. The glass fiber filaments have a diameter of 1.25 μm and a length of 55 μm. The preparation method of the above-mentioned anti-corrosion polyether includes the following steps: The preparation process of the surface protectant is as follows: (I) Add nano-boron nitride and organically modified nano-montmorillonite to ethyl acetate, place in a high-speed disperser, disperse at 2000 r / min for 30 min, and then use an ultrasonic disperser with a power of 300 W and a frequency of 28 kHz for 15 min to obtain a nanoparticle dispersion; (II) Add fluorine-modified epoxy resin to the nanoparticle dispersion, adjust the speed of the high-speed disperser to 1000 r / min, and stir at 25℃ for 22 min to obtain an epoxy nanoparticle composite matrix; (III) Add ethyl acetate dropwise to the epoxy nanoparticle composite matrix to adjust the viscosity of the system to 750 mPa. s, to obtain the adjusted composite base material; (iv) add aminosilane crosslinking agent and deionized water to the adjusted composite base material, adjust the speed of the high-speed disperser to 800 r / min, and continue stirring for 30 min under constant temperature of 25℃ to obtain the pre-crosslinked base material; (v) after vacuum filtering the pre-crosslinked base material with 200 mesh nylon filter cloth, obtain the surface protectant. The preparation process of the barrier-type composite nanofiller is as follows: (i) Add nano-graphene to anhydrous ethanol, ultrasonically exfoliate and disperse for 30 min to obtain graphene ethanol dispersion, add γ-methacryloxypropyltrimethoxysilane coupling agent to it, stir for 20 min to obtain pre-activated material; (ii) Add fluorine-modified nano-SiO2 to anhydrous ethanol, stir for 10 min to obtain fluorine-modified nano-SiO2 suspension; (iii) Slowly drop the fluorine-modified nano-SiO2 suspension into the graphene ethanol dispersion, stir at high speed for 20 min to form a mixed dispersion; (iv) Add distilled water to the mixed dispersion, adjust the pH to 6, and stir at a constant temperature of 55℃ for 2 h to obtain a grafted mixed system; (v) After vacuum drying, the grafted mixed system is subjected to reduced pressure and distillation to obtain the barrier-type composite nanofiller. The preparation process of the polyether polyol matrix composition is as follows: (i) Imidazole ring polyether, m-phenylenediamine polyether and fluorinated polyether are added to a vacuum constant temperature stirred reactor in sequence. After closing the reactor door, the vacuum degree is adjusted to -0.09MPa and the temperature is raised to 105℃. The mixture is vacuum dehydrated at 350r / min for 1.25h to obtain a dehydrated mixture; (ii) The above vacuum parameters are maintained and the temperature is lowered to 65℃. The mixture is first stirred at a low speed of 700r / min for 30min, and then the temperature is raised to 1350r / min and stirred at a high speed for 45min to obtain a preliminary mixture; (iii) The mixture is stirred for 1.25h while maintaining a constant temperature of 65℃, a vacuum of -0.09MPa and a speed of 1350r / min to obtain an activated product; (iv) The speed is reduced to 300r / min and the vacuum degree is maintained for constant temperature degassing for 35min. Then the mixture is naturally cooled to 27℃ and filtered to obtain the polyether polyol matrix composition.

[0024] The preparation process of the hardness enhancer is as follows: (i) Basalt fiber and glass fiber are uniformly mixed to obtain composite fiber. The composite fiber is added to isopropanol and ultrasonically dispersed for 15 min using a CNC ultrasonic disperser with a power of 300W and a frequency of 28kHz to obtain a fiber dispersion; (ii) Nano silicon carbide particles are added to isopropanol and stirred for 10 min. Then, a diaminosilane coupling agent is added dropwise and activated at room temperature for 20 min to obtain an activated silicon carbide dispersion; (iii) The fiber dispersion is added dropwise to the activated silicon carbide dispersion at a rate of 1.5 mL / min. Then, the mixture is stirred at a high speed of 1350 r / min for 30 min to form a mixed composite system; (iv) The mixed composite system is distilled under reduced pressure at 60℃ and -0.09 MPa for 35 min to obtain a paste precursor; (v) The precursor is vacuum dried at 80℃ for 2 h. After cooling, it is ground for 20 min using a planetary ball mill with a speed of 200 r / min and then passed through a 200-mesh nylon sieve to obtain the hardness enhancer; The polyether polyol matrix composition was added to a vacuum constant temperature stirred reactor, maintaining a vacuum of -0.09 MPa and a temperature of 65°C. Hardness enhancer and barrier composite nanofiller were added sequentially, and the rotation speed was adjusted to 1350 r / min. The mixture was stirred for 50 min to form a basic mixed system. Add fluorinated epoxy silane coupling agent and polyether modified siloxane coupling agent to the basic mixture system, maintain the above vacuum, temperature and speed, and continue stirring for 35 min. Then add chain extender, cool down to 45℃, adjust the speed to 900 r / min, stir for 25 min, then add benzotriazole-phosphite composite stabilizer and surface protectant, maintain vacuum of -0.09MPa and temperature of 45℃, stir at 700 r / min for 30 min, so that the surface protectant is uniformly coated on the surface of the mixture system to form a stable composite system. Turn off the vacuum system, lower the temperature of the stable composite system to 27°C, add cyclopentane foaming agent, adjust the speed to 350 r / min, stir for 17 min, then inject the material into the mold, and cure at 27°C and 0.2 MPa pressure for 2.5 h. After demolding, the corrosion-resistant composite polyether is obtained.

[0025] Example 3

[0026] An anti-corrosion polyether, by weight, comprises the following raw materials: 80 parts polyether polyol matrix composition, 25 parts barrier-type composite nanofiller, 5 parts surface protectant, 5 parts fluorine-modified epoxy silane coupling agent, 8 parts polyether-modified siloxane coupling agent, 4 parts chain extender, 1.5 parts benzotriazole-phosphite composite stabilizer, 15 parts cyclopentane foaming agent, and 2 parts hardness enhancer; The raw materials for preparing the polyether polyol matrix composition, by weight, include: 20 parts imidazole ring polyether, 32 parts m-phenylenediamine polyether, and 29 parts fluorine-modified polyether. The raw materials for preparing the barrier-type composite nanofiller, by weight, include: 1 part of nano-graphene, 8 parts of fluorine-modified nano-SiO2, 13 parts of anhydrous ethanol, and 0.8 parts of γ-methacryloyloxypropyltrimethoxysilane coupling agent. The raw materials for preparing the surface protectant, by weight, include: 2 parts fluorine-modified epoxy resin, 1.2 parts aminosilane crosslinking agent, 0.3 parts nano boron nitride, 0.2 parts organically modified nano montmorillonite (the particle size of the organically modified nano montmorillonite is 200 nm), 15 parts ethyl acetate, and 1 part deionized water. The raw materials for preparing the hardness strengthening agent, by weight, include: 4 parts of nano-silicon carbide particles, 6 parts of composite fiber filaments, 0.3 parts of diaminosilane coupling agent, and 10 parts of isopropanol. The particle size of the nano-silicon carbide particles is 150 nm. The raw materials for the composite fiber filaments include: 4 parts basalt fiber filaments and 4 parts glass fiber filaments; The basalt fiber has a diameter of 3 μm and a length of 100 μm. The glass fiber filament has a diameter of 2 μm and a length of 80 μm. The preparation method of the above-mentioned anti-corrosion polyether includes the following steps: The preparation process of the surface protectant is as follows: (i) Add nano-boron nitride and organically modified nano-montmorillonite to ethyl acetate, place in a high-speed disperser, disperse at 2050 r / min for 40 min, and then use an ultrasonic disperser with a power of 305 W and a frequency of 39 kHz for 20 min to obtain a nanoparticle dispersion; (ii) Add fluorine-modified epoxy resin to the nanoparticle dispersion, adjust the speed of the high-speed disperser to 1100 r / min, and stir at 30℃ for 24 min to obtain an epoxy nanoparticle composite matrix; (iii) Add ethyl acetate dropwise to the epoxy nanoparticle composite matrix to adjust the viscosity of the system to 1000 mPa. s, to obtain the adjusted composite base material; (iv) add aminosilane crosslinking agent and deionized water to the adjusted composite base material, adjust the speed of the high-speed disperser to 820 r / min, and continue stirring for 40 min under constant temperature of 28℃ to obtain the pre-crosslinked base material; (v) after vacuum filtering the pre-crosslinked base material with 200 mesh nylon filter cloth, obtain the surface protectant. The preparation process of the barrier-type composite nanofiller is as follows: (i) Add nano-graphene to anhydrous ethanol, ultrasonically exfoliate and disperse for 40 min to obtain graphene ethanol dispersion, add γ-methacryloxypropyltrimethoxysilane coupling agent to it, stir for 25 min to obtain pre-activated material; (ii) Add fluorine-modified nano-SiO2 to anhydrous ethanol, stir for 12 min to obtain fluorine-modified nano-SiO2 suspension; (iii) Slowly drop the fluorine-modified nano-SiO2 suspension into the graphene ethanol dispersion, stir at high speed for 23 min to form a mixed dispersion; (iv) Add distilled water to the mixed dispersion, adjust the pH to 7, and stir at a constant temperature of 60℃ for 2.5 h to obtain a grafted mixed system; (v) After vacuum drying, the grafted mixed system is subjected to reduced pressure and distillation to obtain the barrier-type composite nanofiller. The preparation process of the polyether polyol matrix composition is as follows: (i) Imidazole ring polyether, m-phenylenediamine polyether and fluorinated polyether are added to a vacuum constant temperature stirred reactor in sequence. After closing the reactor door, the vacuum degree is adjusted to -0.1MPa and the temperature is raised to 110℃. The mixture is dehydrated under vacuum at 400r / min for 1.5h to obtain a dehydrated mixture; (ii) The above vacuum parameters are maintained and the temperature is lowered to 70℃. The mixture is first stirred at a low speed of 800r / min for 40min, and then the temperature is raised to 1500r / min and stirred at a high speed for 50min to obtain a preliminary mixture; (iii) The mixture is stirred for 1.5h while maintaining a constant temperature of 70℃, a vacuum of -0.1MPa and a speed of 1500r / min to obtain an activated product; (iv) The speed is reduced to 400r / min and the vacuum degree is maintained for constant temperature degassing for 40min. Then the mixture is naturally cooled to 30℃ and filtered to obtain the polyether polyol matrix composition.

[0027] The preparation process of the hardness enhancer is as follows: (i) Basalt fiber and glass fiber are uniformly mixed to obtain composite fiber, the composite fiber is added to isopropanol, and ultrasonic dispersion is performed for 20 min using a CNC ultrasonic disperser with a power of 330W and a frequency of 29kHz to obtain fiber dispersion; (ii) Nano silicon carbide particles are added to isopropanol, stirred for 15 min, and then bisaminosilane coupling agent is added dropwise and activated at room temperature for 30 min to obtain activated silicon carbide dispersion; (iii) The fiber dispersion is added dropwise to the activated silicon carbide dispersion at a rate of 2 mL / min, and then stirred at high speed of 1500 r / min for 40 min to form a mixed composite system; (iv) The mixed composite system is distilled under reduced pressure at 65℃ and -0.1MPa for 40 min to obtain a paste precursor; (v) The precursor is vacuum dried at 80℃ for 2 h, cooled, and then ground for 20 min using a planetary ball mill with a speed of 200 r / min, and then passed through a 200-mesh nylon sieve to obtain the hardness enhancer; The polyether polyol matrix composition was added to a vacuum constant temperature stirred reactor, maintaining a vacuum of -0.1 MPa and a temperature of 70°C. Hardness enhancer and barrier composite nanofiller were added sequentially, and the rotation speed was adjusted to 1500 r / min. The mixture was stirred for 60 min to form a basic mixed system. Add fluorinated epoxy silane coupling agent and polyether modified siloxane coupling agent to the basic mixture system, maintain the above vacuum, temperature and speed, and continue stirring for 40 min. Then add chain extender, cool down to 50℃, adjust the speed to 1000 r / min, stir for 30 min, then add benzotriazole-phosphite composite stabilizer and surface protectant, maintain vacuum of -0.1 MPa and temperature of 50℃, stir at 800 r / min for 35 min, so that the surface protectant is uniformly coated on the surface of the mixture system to form a stable composite system. Turn off the vacuum system, lower the temperature of the stable composite system to 30°C, add cyclopentane foaming agent, adjust the speed to 400 r / min, stir for 20 min, then inject the material into the mold, and cure at 30°C and 0.3 MPa pressure for 3 h. After demolding, the corrosion-resistant composite polyether is obtained.

[0028] Comparative Example 1

[0029] A corrosion-resistant polyether composition, comprising, by weight, the following raw materials: 72 parts polyether polyol matrix composition, 24 parts surface protectant, 3.75 parts fluorine-modified epoxy silane coupling agent, 6 parts polyether-modified siloxane coupling agent, 3 parts chain extender, 1.25 parts benzotriazole-phosphite composite stabilizer, 12.5 parts cyclopentane foaming agent, and 1.5 parts hardness enhancer; The raw materials for preparing the polyether polyol matrix composition, by weight, include: 18.125 parts imidazole ring polyether, 29 parts m-phenylenediamine polyether, and 25.875 parts fluorine-modified polyether. The raw materials for preparing the surface protectant, by weight, include: 1.75 parts of fluorine-modified epoxy resin, 1 part of aminosilane crosslinking agent, 0.25 parts of nano boron nitride, 0.175 parts of organically modified nano montmorillonite (the particle size of organically modified nano montmorillonite is 150 nm), 12.5 parts of ethyl acetate, and 0.75 parts of deionized water. The raw materials for preparing the hardness enhancer, by weight, include: 3.5 parts of nano-silicon carbide particles, 3.5 parts of composite fiber filaments, 0.2 parts of diaminosilane coupling agent, and 9 parts of isopropanol. Among them, the particle size of the nano-silicon carbide particles is 115nm; The raw materials for the composite fiber filaments include: 3 parts basalt fiber filaments and 3 parts glass fiber filaments; The basalt fibers have a diameter of 2μm and a length of 75μm. The glass fiber filaments have a diameter of 1.25 μm and a length of 55 μm. The preparation method of the above-mentioned anti-corrosion polyether includes the following steps: The preparation process of the surface protectant is as follows: (I) Add nano-boron nitride and organically modified nano-montmorillonite to ethyl acetate, place in a high-speed disperser, disperse at 2000 r / min for 30 min, and then use an ultrasonic disperser with a power of 300 W and a frequency of 28 kHz for 15 min to obtain a nanoparticle dispersion; (II) Add fluorine-modified epoxy resin to the nanoparticle dispersion, adjust the speed of the high-speed disperser to 1000 r / min, and stir at 25℃ for 22 min to obtain an epoxy nanoparticle composite matrix; (III) Add ethyl acetate dropwise to the epoxy nanoparticle composite matrix to adjust the viscosity of the system to 750 mPa. s, to obtain the adjusted composite base material; (iv) add aminosilane crosslinking agent and deionized water to the adjusted composite base material, adjust the speed of the high-speed disperser to 800 r / min, and continue stirring for 30 min under constant temperature of 25℃ to obtain the pre-crosslinked base material; (v) after vacuum filtering the pre-crosslinked base material with 200 mesh nylon filter cloth, obtain the surface protectant. The preparation process of the polyether polyol matrix composition is as follows: (i) Imidazole ring polyether, m-phenylenediamine polyether and fluorinated polyether are added to a vacuum constant temperature stirred reactor in sequence. After closing the reactor door, the vacuum degree is adjusted to -0.09MPa and the temperature is raised to 105℃. The mixture is vacuum dehydrated at 350r / min for 1.25h to obtain a dehydrated mixture; (ii) The above vacuum parameters are maintained and the temperature is lowered to 65℃. The mixture is first stirred at a low speed of 700r / min for 30min, and then the temperature is raised to 1350r / min and stirred at a high speed for 45min to obtain a preliminary mixture; (iii) The mixture is stirred for 1.25h while maintaining a constant temperature of 65℃, a vacuum of -0.09MPa and a speed of 1350r / min to obtain an activated product; (iv) The speed is reduced to 300r / min and the vacuum degree is maintained for constant temperature degassing for 35min. Then the mixture is naturally cooled to 27℃ and filtered to obtain the polyether polyol matrix composition.

[0030] The preparation process of the hardness enhancer is as follows: (i) Basalt fiber and glass fiber are uniformly mixed to obtain composite fiber. The composite fiber is added to isopropanol and ultrasonically dispersed for 15 min using a CNC ultrasonic disperser with a power of 300W and a frequency of 28kHz to obtain a fiber dispersion; (ii) Nano silicon carbide particles are added to isopropanol and stirred for 10 min. Then, a diaminosilane coupling agent is added dropwise and activated at room temperature for 20 min to obtain an activated silicon carbide dispersion; (iii) The fiber dispersion is added dropwise to the activated silicon carbide dispersion at a rate of 1.5 mL / min. Then, the mixture is stirred at a high speed of 1350 r / min for 30 min to form a mixed composite system; (iv) The mixed composite system is distilled under reduced pressure at 60℃ and -0.09 MPa for 35 min to obtain a paste precursor; (v) The precursor is vacuum dried at 80℃ for 2 h. After cooling, it is ground for 20 min using a planetary ball mill with a speed of 200 r / min and then passed through a 200-mesh nylon sieve to obtain the hardness enhancer; The polyether polyol matrix composition was added to a vacuum constant temperature stirred reactor, maintaining a vacuum of -0.09 MPa and a temperature of 65°C. A hardness enhancer was added, the rotation speed was adjusted to 1350 r / min, and the mixture was stirred for 50 min to form a basic mixed system. Add fluorinated epoxy silane coupling agent and polyether modified siloxane coupling agent to the basic mixture system, maintain the above vacuum, temperature and speed, and continue stirring for 35 min. Then add chain extender, cool down to 45℃, adjust the speed to 900 r / min, stir for 25 min, then add benzotriazole-phosphite composite stabilizer and surface protectant, maintain vacuum of -0.09MPa and temperature of 45℃, stir at 700 r / min for 30 min, so that the surface protectant is uniformly coated on the surface of the mixture system to form a stable composite system. Turn off the vacuum system, lower the temperature of the stable composite system to 27°C, add cyclopentane foaming agent, adjust the speed to 350 r / min, stir for 17 min, then inject the material into the mold, and cure at 27°C and 0.2 MPa pressure for 2.5 h. After demolding, the corrosion-resistant composite polyether is obtained.

[0031] Comparative Example 2

[0032] A corrosion-resistant polyether composition, comprising, by weight, the following raw materials: 72 parts polyether polyol matrix composition, 24 parts barrier-type composite nanofiller, 3.75 parts fluorine-modified epoxy silane coupling agent, 6 parts polyether-modified siloxane coupling agent, 3 parts chain extender, 1.25 parts benzotriazole-phosphite composite stabilizer, 12.5 parts cyclopentane foaming agent, and 1.5 parts hardness reinforcing agent; The raw materials for preparing the polyether polyol matrix composition, by weight, include: 18.125 parts imidazole ring polyether, 29 parts m-phenylenediamine polyether, and 25.875 parts fluorine-modified polyether. The raw materials for preparing the barrier-type composite nanofiller, by weight, include: 0.75 parts of nano-graphene, 7 parts of fluorine-modified nano-SiO2, 10.5 parts of anhydrous ethanol, and 0.65 parts of γ-methacryloyloxypropyltrimethoxysilane coupling agent. The raw materials for preparing the hardness enhancer, by weight, include: 3.5 parts of nano-silicon carbide particles, 3.5 parts of composite fiber filaments, 0.2 parts of diaminosilane coupling agent, and 9 parts of isopropanol. Among them, the particle size of the nano-silicon carbide particles is 115nm; The raw materials for the composite fiber filaments include: 3 parts basalt fiber filaments and 3 parts glass fiber filaments; The basalt fibers have a diameter of 2μm and a length of 75μm. The glass fiber filaments have a diameter of 1.25 μm and a length of 55 μm. The preparation method of the above-mentioned anti-corrosion polyether includes the following steps: The preparation process of the barrier-type composite nanofiller is as follows: (i) Add nano-graphene to anhydrous ethanol, ultrasonically exfoliate and disperse for 30 min to obtain graphene ethanol dispersion, add γ-methacryloxypropyltrimethoxysilane coupling agent to it, stir for 20 min to obtain pre-activated material; (ii) Add fluorine-modified nano-SiO2 to anhydrous ethanol, stir for 10 min to obtain fluorine-modified nano-SiO2 suspension; (iii) Slowly drop the fluorine-modified nano-SiO2 suspension into the graphene ethanol dispersion, stir at high speed for 20 min to form a mixed dispersion; (iv) Add distilled water to the mixed dispersion, adjust the pH to 6, and stir at a constant temperature of 55℃ for 2 h to obtain a grafted mixed system; (v) After vacuum drying, the grafted mixed system is subjected to reduced pressure and distillation to obtain the barrier-type composite nanofiller. The preparation process of the polyether polyol matrix composition is as follows: (i) Imidazole ring polyether, m-phenylenediamine polyether and fluorinated polyether are added to a vacuum constant temperature stirred reactor in sequence. After closing the reactor door, the vacuum degree is adjusted to -0.09MPa and the temperature is raised to 105℃. The mixture is vacuum dehydrated at 350r / min for 1.25h to obtain a dehydrated mixture; (ii) The above vacuum parameters are maintained and the temperature is lowered to 65℃. The mixture is first stirred at a low speed of 700r / min for 30min, and then the temperature is raised to 1350r / min and stirred at a high speed for 45min to obtain a preliminary mixture; (iii) The mixture is stirred for 1.25h while maintaining a constant temperature of 65℃, a vacuum of -0.09MPa and a speed of 1350r / min to obtain an activated product; (iv) The speed is reduced to 300r / min and the vacuum degree is maintained for constant temperature degassing for 35min. Then the mixture is naturally cooled to 27℃ and filtered to obtain the polyether polyol matrix composition.

[0033] The preparation process of the hardness enhancer is as follows: (i) Basalt fiber and glass fiber are uniformly mixed to obtain composite fiber. The composite fiber is added to isopropanol and ultrasonically dispersed for 15 min using a CNC ultrasonic disperser with a power of 300W and a frequency of 28kHz to obtain a fiber dispersion; (ii) Nano silicon carbide particles are added to isopropanol and stirred for 10 min. Then, a diaminosilane coupling agent is added dropwise and activated at room temperature for 20 min to obtain an activated silicon carbide dispersion; (iii) The fiber dispersion is added dropwise to the activated silicon carbide dispersion at a rate of 1.5 mL / min. Then, the mixture is stirred at a high speed of 1350 r / min for 30 min to form a mixed composite system; (iv) The mixed composite system is distilled under reduced pressure at 60℃ and -0.09 MPa for 35 min to obtain a paste precursor; (v) The precursor is vacuum dried at 80℃ for 2 h. After cooling, it is ground for 20 min using a planetary ball mill with a speed of 200 r / min and then passed through a 200-mesh nylon sieve to obtain the hardness enhancer; The polyether polyol matrix composition was added to a vacuum constant temperature stirred reactor, maintaining a vacuum of -0.09 MPa and a temperature of 65°C. Hardness enhancer and barrier composite nanofiller were added sequentially, and the rotation speed was adjusted to 1350 r / min. The mixture was stirred for 50 min to form a basic mixed system. Add fluorinated epoxy silane coupling agent and polyether modified siloxane coupling agent to the basic mixture system, maintain the above vacuum, temperature and speed, and continue stirring for 35 min. Then add chain extender, cool down to 45℃, adjust the speed to 900 r / min, stir for 25 min, then add benzotriazole-phosphite composite stabilizer, maintain vacuum of -0.09 MPa and temperature of 45℃, and stir at 700 r / min for 30 min to form a stable composite system. Turn off the vacuum system, lower the temperature of the stable composite system to 27°C, add cyclopentane foaming agent, adjust the speed to 350 r / min, stir for 17 min, then inject the material into the mold, and cure at 27°C and 0.2 MPa pressure for 2.5 h. After demolding, the corrosion-resistant composite polyether is obtained.

[0034] Comparative Example 3

[0035] A corrosion-resistant polyether composition, wherein the raw materials for preparing the corrosion-resistant polyether composition include, by weight: 96 parts polyether polyol matrix composition, 3.75 parts fluorine-modified epoxy silane coupling agent, 6 parts polyether-modified siloxane coupling agent, 3 parts chain extender, 1.25 parts benzotriazole-phosphite composite stabilizer, 12.5 parts cyclopentane foaming agent, and 1.5 parts hardness reinforcing agent; The raw materials for preparing the polyether polyol matrix composition, by weight, include: 18.125 parts imidazole ring polyether, 29 parts m-phenylenediamine polyether, and 25.875 parts fluorine-modified polyether. The raw materials for preparing the hardness enhancer, by weight, include: 3.5 parts of nano-silicon carbide particles, 3.5 parts of composite fiber filaments, 0.2 parts of diaminosilane coupling agent, and 9 parts of isopropanol. Among them, the particle size of the nano-silicon carbide particles is 115nm; The raw materials for the composite fiber filaments include: 3 parts basalt fiber filaments and 3 parts glass fiber filaments; The basalt fibers have a diameter of 2μm and a length of 75μm. The glass fiber filaments have a diameter of 1.25 μm and a length of 55 μm. The preparation method of the above-mentioned anti-corrosion polyether includes the following steps: The preparation process of the polyether polyol matrix composition is as follows: (i) Imidazole ring polyether, m-phenylenediamine polyether and fluorinated polyether are added to a vacuum constant temperature stirred reactor in sequence. After closing the reactor door, the vacuum degree is adjusted to -0.09MPa and the temperature is raised to 105℃. The mixture is vacuum dehydrated at 350r / min for 1.25h to obtain a dehydrated mixture; (ii) The above vacuum parameters are maintained and the temperature is lowered to 65℃. The mixture is first stirred at a low speed of 700r / min for 30min, and then the temperature is raised to 1350r / min and stirred at a high speed for 45min to obtain a preliminary mixture; (iii) The mixture is stirred for 1.25h while maintaining a constant temperature of 65℃, a vacuum of -0.09MPa and a speed of 1350r / min to obtain an activated product; (iv) The speed is reduced to 300r / min and the vacuum degree is maintained for constant temperature degassing for 35min. Then the mixture is naturally cooled to 27℃ and filtered to obtain the polyether polyol matrix composition.

[0036] The preparation process of the hardness enhancer is as follows: (i) Basalt fiber and glass fiber are uniformly mixed to obtain composite fiber. The composite fiber is added to isopropanol and ultrasonically dispersed for 15 min using a CNC ultrasonic disperser with a power of 300W and a frequency of 28kHz to obtain a fiber dispersion; (ii) Nano silicon carbide particles are added to isopropanol and stirred for 10 min. Then, a diaminosilane coupling agent is added dropwise and activated at room temperature for 20 min to obtain an activated silicon carbide dispersion; (iii) The fiber dispersion is added dropwise to the activated silicon carbide dispersion at a rate of 1.5 mL / min. Then, the mixture is stirred at a high speed of 1350 r / min for 30 min to form a mixed composite system; (iv) The mixed composite system is distilled under reduced pressure at 60℃ and -0.09 MPa for 35 min to obtain a paste precursor; (v) The precursor is vacuum dried at 80℃ for 2 h. After cooling, it is ground for 20 min using a planetary ball mill with a speed of 200 r / min and then passed through a 200-mesh nylon sieve to obtain the hardness enhancer; The polyether polyol matrix composition was added to a vacuum constant temperature stirred reactor, maintaining a vacuum of -0.09 MPa and a temperature of 65°C. The hardness strengthening agent was added sequentially, the rotation speed was adjusted to 1350 r / min, and the mixture was stirred for 50 min to form a basic mixture system. Add fluorinated epoxy silane coupling agent and polyether modified siloxane coupling agent to the basic mixture system, maintain the above vacuum, temperature and speed, and continue stirring for 35 min. Then add chain extender, cool down to 45℃, adjust the speed to 900 r / min, stir for 25 min, then add benzotriazole-phosphite composite stabilizer, maintain vacuum of -0.09 MPa and temperature of 45℃, and stir at 700 r / min for 30 min to form a stable composite system. Turn off the vacuum system, lower the temperature of the stable composite system to 27°C, add cyclopentane foaming agent, adjust the speed to 350 r / min, stir for 17 min, then inject the material into the mold, and cure at 27°C and 0.2 MPa pressure for 2.5 h. After demolding, the corrosion-resistant composite polyether is obtained.

[0037] Comparative Example 4

[0038] A corrosion-resistant polyether composition, comprising, by weight, the following raw materials: 72 parts polyether polyol matrix composition, 20 parts barrier-type composite nanofiller, 4 parts surface protectant, 3.75 parts fluorine-modified epoxy silane coupling agent, 6 parts polyether-modified siloxane coupling agent, 3 parts chain extender, 1.25 parts benzotriazole-phosphite composite stabilizer, 12.5 parts cyclopentane foaming agent, and 1.5 parts hardness enhancer; The raw materials for preparing the polyether polyol matrix composition, by weight, include: 18.125 parts imidazole ring polyether, 29 parts m-phenylenediamine polyether, and 25.875 parts fluorine-modified polyether. The raw materials for preparing the barrier-type composite nanofiller, by weight, include: 0.75 parts of nano-graphene, 7 parts of fluorine-modified nano-SiO2, 10.5 parts of anhydrous ethanol, and 0.65 parts of γ-methacryloyloxypropyltrimethoxysilane coupling agent. The raw materials for preparing the surface protectant, by weight, include: 1.75 parts of fluorine-modified epoxy resin, 1 part of aminosilane crosslinking agent, 0.25 parts of nano boron nitride, 0.175 parts of organically modified nano montmorillonite (the particle size of organically modified nano montmorillonite is 150 nm), 12.5 parts of ethyl acetate, and 0.75 parts of deionized water. The raw materials for preparing the hardness enhancer, by weight, include: 3.5 parts of nano-silicon carbide particles, 3.5 parts of composite fiber filaments, 0.2 parts of diaminosilane coupling agent, and 9 parts of isopropanol. Among them, the particle size of the nano-silicon carbide particles is 115nm; Specifically, the composite fiber filament is a glass fiber filament; The basalt fibers have a diameter of 2μm and a length of 75μm. The glass fiber filaments have a diameter of 1.25 μm and a length of 55 μm. The preparation method of the above-mentioned anti-corrosion polyether includes the following steps: The preparation process of the surface protectant is as follows: (I) Add nano-boron nitride and organically modified nano-montmorillonite to ethyl acetate, place in a high-speed disperser, disperse at 2000 r / min for 30 min, and then use an ultrasonic disperser with a power of 300 W and a frequency of 28 kHz for 15 min to obtain a nanoparticle dispersion; (II) Add fluorine-modified epoxy resin to the nanoparticle dispersion, adjust the speed of the high-speed disperser to 1000 r / min, and stir at 25℃ for 22 min to obtain an epoxy nanoparticle composite matrix; (III) Add ethyl acetate dropwise to the epoxy nanoparticle composite matrix to adjust the viscosity of the system to 750 mPa. s, to obtain the adjusted composite base material; (iv) add aminosilane crosslinking agent and deionized water to the adjusted composite base material, adjust the speed of the high-speed disperser to 800 r / min, and continue stirring for 30 min under constant temperature of 25℃ to obtain the pre-crosslinked base material; (v) after vacuum filtering the pre-crosslinked base material with 200 mesh nylon filter cloth, obtain the surface protectant. The preparation process of the barrier-type composite nanofiller is as follows: (i) Add nano-graphene to anhydrous ethanol, ultrasonically exfoliate and disperse for 30 min to obtain graphene ethanol dispersion, add γ-methacryloxypropyltrimethoxysilane coupling agent to it, stir for 20 min to obtain pre-activated material; (ii) Add fluorine-modified nano-SiO2 to anhydrous ethanol, stir for 10 min to obtain fluorine-modified nano-SiO2 suspension; (iii) Slowly drop the fluorine-modified nano-SiO2 suspension into the graphene ethanol dispersion, stir at high speed for 20 min to form a mixed dispersion; (iv) Add distilled water to the mixed dispersion, adjust the pH to 6, and stir at a constant temperature of 55℃ for 2 h to obtain a grafted mixed system; (v) After vacuum drying, the grafted mixed system is subjected to reduced pressure and distillation to obtain the barrier-type composite nanofiller. The preparation process of the polyether polyol matrix composition is as follows: (i) Imidazole ring polyether, m-phenylenediamine polyether and fluorinated polyether are added to a vacuum constant temperature stirred reactor in sequence. After closing the reactor door, the vacuum degree is adjusted to -0.09MPa and the temperature is raised to 105℃. The mixture is vacuum dehydrated at 350r / min for 1.25h to obtain a dehydrated mixture; (ii) The above vacuum parameters are maintained and the temperature is lowered to 65℃. The mixture is first stirred at a low speed of 700r / min for 30min, and then the temperature is raised to 1350r / min and stirred at a high speed for 45min to obtain a preliminary mixture; (iii) The mixture is stirred for 1.25h while maintaining a constant temperature of 65℃, a vacuum of -0.09MPa and a speed of 1350r / min to obtain an activated product; (iv) The speed is reduced to 300r / min and the vacuum degree is maintained for constant temperature degassing for 35min. Then the mixture is naturally cooled to 27℃ and filtered to obtain the polyether polyol matrix composition.

[0039] The preparation process of the hardness enhancer is as follows: (i) The composite fiber filaments are added to isopropanol and ultrasonically dispersed for 15 min using a CNC ultrasonic disperser with a power of 300W and a frequency of 28kHz to obtain a fiber filament dispersion; (ii) Nano silicon carbide particles are added to isopropanol and stirred for 10 min, then a diaminosilane coupling agent is added dropwise and activated at room temperature for 20 min to obtain an activated silicon carbide dispersion; (iii) The fiber filament dispersion is added dropwise to the activated silicon carbide dispersion at a rate of 1.5 mL / min, and then stirred at a high speed of 1350 r / min for 30 min to form a mixed composite system; (iv) The mixed composite system is vacuum distilled at 60℃ and -0.09 MPa for 35 min to obtain a paste precursor; (v) The precursor is vacuum dried at 80℃ for 2 h, cooled, and then ground for 20 min using a planetary ball mill with a speed of 200 r / min. After passing through a 200-mesh nylon sieve, the hardness enhancer is obtained. The polyether polyol matrix composition was added to a vacuum constant temperature stirred reactor, maintaining a vacuum of -0.09 MPa and a temperature of 65°C. Hardness enhancer and barrier composite nanofiller were added sequentially, and the rotation speed was adjusted to 1350 r / min. The mixture was stirred for 50 min to form a basic mixed system. Add fluorinated epoxy silane coupling agent and polyether modified siloxane coupling agent to the basic mixture system, maintain the above vacuum, temperature and speed, and continue stirring for 35 min. Then add chain extender, cool down to 45℃, adjust the speed to 900 r / min, stir for 25 min, then add benzotriazole-phosphite composite stabilizer and surface protectant, maintain vacuum of -0.09MPa and temperature of 45℃, stir at 700 r / min for 30 min, so that the surface protectant is uniformly coated on the surface of the mixture system to form a stable composite system. Turn off the vacuum system, lower the temperature of the stable composite system to 27°C, add cyclopentane foaming agent, adjust the speed to 350 r / min, stir for 17 min, then inject the material into the mold, and cure at 27°C and 0.2 MPa pressure for 2.5 h. After demolding, the corrosion-resistant composite polyether is obtained.

[0040] Comparative Example 5

[0041] A corrosion-resistant polyether composition, comprising, by weight, the following raw materials: 72 parts polyether polyol matrix composition, 20 parts barrier-type composite nanofiller, 4 parts surface protectant, 3.75 parts fluorine-modified epoxy silane coupling agent, 6 parts polyether-modified siloxane coupling agent, 3 parts chain extender, 1.25 parts benzotriazole-phosphite composite stabilizer, 12.5 parts cyclopentane foaming agent, and 1.5 parts hardness enhancer; The raw materials for preparing the polyether polyol matrix composition, by weight, include: 18.125 parts imidazole ring polyether, 29 parts m-phenylenediamine polyether, and 25.875 parts fluorine-modified polyether. The raw materials for preparing the barrier-type composite nanofiller, by weight, include: 0.75 parts of nano-graphene, 7 parts of fluorine-modified nano-SiO2, 10.5 parts of anhydrous ethanol, and 0.65 parts of γ-methacryloyloxypropyltrimethoxysilane coupling agent. The raw materials for preparing the surface protectant, by weight, include: 1.75 parts of fluorine-modified epoxy resin, 1 part of aminosilane crosslinking agent, 0.25 parts of nano boron nitride, 0.175 parts of organically modified nano montmorillonite (the particle size of organically modified nano montmorillonite is 150 nm), 12.5 parts of ethyl acetate, and 0.75 parts of deionized water. The raw materials for preparing the hardness enhancer, by weight, include: 3.5 parts of nano-silicon carbide particles, 3.5 parts of composite fiber filaments, 0.2 parts of diaminosilane coupling agent, and 9 parts of isopropanol. Among them, the particle size of the nano-silicon carbide particles is 115nm; Specifically, the composite fiber filament is basalt fiber filament; The basalt fibers have a diameter of 2μm and a length of 75μm. The glass fiber filaments have a diameter of 1.25 μm and a length of 55 μm. The preparation method of the above-mentioned anti-corrosion polyether includes the following steps: The preparation process of the surface protectant is as follows: (I) Add nano-boron nitride and organically modified nano-montmorillonite to ethyl acetate, place in a high-speed disperser, disperse at 2000 r / min for 30 min, and then use an ultrasonic disperser with a power of 300 W and a frequency of 28 kHz for 15 min to obtain a nanoparticle dispersion; (II) Add fluorine-modified epoxy resin to the nanoparticle dispersion, adjust the speed of the high-speed disperser to 1000 r / min, and stir at 25℃ for 22 min to obtain an epoxy nanoparticle composite matrix; (III) Add ethyl acetate dropwise to the epoxy nanoparticle composite matrix to adjust the viscosity of the system to 750 mPa. s, to obtain the adjusted composite base material; (iv) add aminosilane crosslinking agent and deionized water to the adjusted composite base material, adjust the speed of the high-speed disperser to 800 r / min, and continue stirring for 30 min under constant temperature of 25℃ to obtain the pre-crosslinked base material; (v) after vacuum filtering the pre-crosslinked base material with 200 mesh nylon filter cloth, obtain the surface protectant. The preparation process of the barrier-type composite nanofiller is as follows: (i) Add nano-graphene to anhydrous ethanol, ultrasonically exfoliate and disperse for 30 min to obtain graphene ethanol dispersion, add γ-methacryloxypropyltrimethoxysilane coupling agent to it, stir for 20 min to obtain pre-activated material; (ii) Add fluorine-modified nano-SiO2 to anhydrous ethanol, stir for 10 min to obtain fluorine-modified nano-SiO2 suspension; (iii) Slowly drop the fluorine-modified nano-SiO2 suspension into the graphene ethanol dispersion, stir at high speed for 20 min to form a mixed dispersion; (iv) Add distilled water to the mixed dispersion, adjust the pH to 6, and stir at a constant temperature of 55℃ for 2 h to obtain a grafted mixed system; (v) After vacuum drying, the grafted mixed system is subjected to reduced pressure and distillation to obtain the barrier-type composite nanofiller. The preparation process of the polyether polyol matrix composition is as follows: (i) Imidazole ring polyether, m-phenylenediamine polyether and fluorinated polyether are added to a vacuum constant temperature stirred reactor in sequence. After closing the reactor door, the vacuum degree is adjusted to -0.09MPa and the temperature is raised to 105℃. The mixture is vacuum dehydrated at 350r / min for 1.25h to obtain a dehydrated mixture; (ii) The above vacuum parameters are maintained and the temperature is lowered to 65℃. The mixture is first stirred at a low speed of 700r / min for 30min, and then the temperature is raised to 1350r / min and stirred at a high speed for 45min to obtain a preliminary mixture; (iii) The mixture is stirred for 1.25h while maintaining a constant temperature of 65℃, a vacuum of -0.09MPa and a speed of 1350r / min to obtain an activated product; (iv) The speed is reduced to 300r / min and the vacuum degree is maintained for constant temperature degassing for 35min. Then the mixture is naturally cooled to 27℃ and filtered to obtain the polyether polyol matrix composition.

[0042] The preparation process of the hardness enhancer is as follows: (i) The composite fiber filaments are added to isopropanol and ultrasonically dispersed for 15 min using a CNC ultrasonic disperser with a power of 300W and a frequency of 28kHz to obtain a fiber filament dispersion; (ii) Nano silicon carbide particles are added to isopropanol and stirred for 10 min, then a diaminosilane coupling agent is added dropwise and activated at room temperature for 20 min to obtain an activated silicon carbide dispersion; (iii) The fiber filament dispersion is added dropwise to the activated silicon carbide dispersion at a rate of 1.5 mL / min, and then stirred at a high speed of 1350 r / min for 30 min to form a mixed composite system; (iv) The mixed composite system is vacuum distilled at 60℃ and -0.09 MPa for 35 min to obtain a paste precursor; (v) The precursor is vacuum dried at 80℃ for 2 h, cooled, and then ground for 20 min using a planetary ball mill with a speed of 200 r / min. After passing through a 200-mesh nylon sieve, the hardness enhancer is obtained. The polyether polyol matrix composition was added to a vacuum constant temperature stirred reactor, maintaining a vacuum of -0.09 MPa and a temperature of 65°C. Hardness enhancer and barrier composite nanofiller were added sequentially, and the rotation speed was adjusted to 1350 r / min. The mixture was stirred for 50 min to form a basic mixed system. Add fluorinated epoxy silane coupling agent and polyether modified siloxane coupling agent to the basic mixture system, maintain the above vacuum, temperature and speed, and continue stirring for 35 min. Then add chain extender, cool down to 45℃, adjust the speed to 900 r / min, stir for 25 min, then add benzotriazole-phosphite composite stabilizer and surface protectant, maintain vacuum of -0.09MPa and temperature of 45℃, stir at 700 r / min for 30 min, so that the surface protectant is uniformly coated on the surface of the mixture system to form a stable composite system. Turn off the vacuum system, lower the temperature of the stable composite system to 27°C, add cyclopentane foaming agent, adjust the speed to 350 r / min, stir for 17 min, then inject the material into the mold, and cure at 27°C and 0.2 MPa pressure for 2.5 h. After demolding, the corrosion-resistant composite polyether is obtained.

[0043] Comparative Example 6

[0044] A corrosion-resistant polyether composition, comprising, by weight, the following raw materials: 72.96 parts polyether polyol matrix composition, 20.2 parts barrier-type composite nanofiller, 4.04 parts surface protectant, 3.79 parts fluorine-modified epoxy silane coupling agent, 6.07 parts polyether-modified siloxane coupling agent, 3.03 parts chain extender, 1.26 parts benzotriazole-phosphite composite stabilizer, and 12.65 parts cyclopentane foaming agent; The raw materials for preparing the polyether polyol matrix composition, by weight, include: 18.125 parts imidazole ring polyether, 29 parts m-phenylenediamine polyether, and 25.875 parts fluorine-modified polyether. The raw materials for preparing the barrier-type composite nanofiller, by weight, include: 0.75 parts of nano-graphene, 7 parts of fluorine-modified nano-SiO2, 10.5 parts of anhydrous ethanol, and 0.65 parts of γ-methacryloyloxypropyltrimethoxysilane coupling agent. The raw materials for preparing the surface protectant, by weight, include: 1.75 parts of fluorine-modified epoxy resin, 1 part of aminosilane crosslinking agent, 0.25 parts of nano boron nitride, 0.175 parts of organically modified nano montmorillonite (the particle size of organically modified nano montmorillonite is 150 nm), 12.5 parts of ethyl acetate, and 0.75 parts of deionized water. The preparation method of the above-mentioned anti-corrosion polyether includes the following steps: The preparation process of the surface protectant is as follows: (I) Add nano-boron nitride and organically modified nano-montmorillonite to ethyl acetate, place in a high-speed disperser, disperse at 2000 r / min for 30 min, and then use an ultrasonic disperser with a power of 300 W and a frequency of 28 kHz for 15 min to obtain a nanoparticle dispersion; (II) Add fluorine-modified epoxy resin to the nanoparticle dispersion, adjust the speed of the high-speed disperser to 1000 r / min, and stir at 25℃ for 22 min to obtain an epoxy nanoparticle composite matrix; (III) Add ethyl acetate dropwise to the epoxy nanoparticle composite matrix to adjust the viscosity of the system to 750 mPa. s, to obtain the adjusted composite base material; (iv) add aminosilane crosslinking agent and deionized water to the adjusted composite base material, adjust the speed of the high-speed disperser to 800 r / min, and continue stirring for 30 min under constant temperature of 25℃ to obtain the pre-crosslinked base material; (v) after vacuum filtering the pre-crosslinked base material with 200 mesh nylon filter cloth, obtain the surface protectant. The preparation process of the barrier-type composite nanofiller is as follows: (i) Add nano-graphene to anhydrous ethanol, ultrasonically exfoliate and disperse for 30 min to obtain graphene ethanol dispersion, add γ-methacryloxypropyltrimethoxysilane coupling agent to it, stir for 20 min to obtain pre-activated material; (ii) Add fluorine-modified nano-SiO2 to anhydrous ethanol, stir for 10 min to obtain fluorine-modified nano-SiO2 suspension; (iii) Slowly drop the fluorine-modified nano-SiO2 suspension into the graphene ethanol dispersion, stir at high speed for 20 min to form a mixed dispersion; (iv) Add distilled water to the mixed dispersion, adjust the pH to 6, and stir at a constant temperature of 55℃ for 2 h to obtain a grafted mixed system; (v) After vacuum drying, the grafted mixed system is subjected to reduced pressure and distillation to obtain the barrier-type composite nanofiller. The preparation process of the polyether polyol matrix composition is as follows: (i) Imidazole ring polyether, m-phenylenediamine polyether and fluorinated polyether are added to a vacuum constant temperature stirred reactor in sequence. After closing the reactor door, the vacuum degree is adjusted to -0.09MPa and the temperature is raised to 105℃. The mixture is vacuum dehydrated at 350r / min for 1.25h to obtain a dehydrated mixture; (ii) The above vacuum parameters are maintained and the temperature is lowered to 65℃. The mixture is first stirred at a low speed of 700r / min for 30min, and then the temperature is raised to 1350r / min and stirred at a high speed for 45min to obtain a preliminary mixture; (iii) The mixture is stirred for 1.25h while maintaining a constant temperature of 65℃, a vacuum of -0.09MPa and a speed of 1350r / min to obtain an activated product; (iv) The speed is reduced to 300r / min and the vacuum degree is maintained for constant temperature degassing for 35min. Then the mixture is naturally cooled to 27℃ and filtered to obtain the polyether polyol matrix composition.

[0045] The polyether polyol matrix composition was added to a vacuum constant temperature stirred reactor, maintaining a vacuum of -0.09 MPa and a temperature of 65°C. Barrier-type composite nanofillers were added sequentially, the rotation speed was adjusted to 1350 r / min, and the mixture was stirred for 50 min to form a basic mixed system. Add fluorinated epoxy silane coupling agent and polyether modified siloxane coupling agent to the basic mixture system, maintain the above vacuum, temperature and speed, and continue stirring for 35 min. Then add chain extender, cool down to 45℃, adjust the speed to 900 r / min, stir for 25 min, then add benzotriazole-phosphite composite stabilizer and surface protectant, maintain vacuum of -0.09MPa and temperature of 45℃, stir at 700 r / min for 30 min, so that the surface protectant is uniformly coated on the surface of the mixture system to form a stable composite system. Turn off the vacuum system, lower the temperature of the stable composite system to 27°C, add cyclopentane foaming agent, adjust the speed to 350 r / min, stir for 17 min, then inject the material into the mold, and cure at 27°C and 0.2 MPa pressure for 2.5 h. After demolding, the corrosion-resistant composite polyether is obtained.

[0046] III. Experimental Testing

[0047] 3.1 Testing the corrosion resistance of the barrier-type composite nanofiller and surface protectant to the corrosion-resistant polyether combination

[0048] ①The salt spray corrosion resistance of the anti-corrosion polyether samples prepared in Examples 1-3 and Comparative Examples 1-3 was tested according to GB / T 10125-2021 "Artificial Atmosphere Corrosion Test - Salt Spray Test". The results are shown in Table 1 below. ②The acid and alkali corrosion resistance of the corrosion-resistant polyether samples prepared in Examples 1-3 and Comparative Examples 1-3 were tested according to GB / T 9274-1988 "Determination of resistance to liquid media for paints and varnishes". The results are shown in Table 2 below. ③ The water absorption properties of the corrosion-resistant polyether composite samples prepared in Examples 1-3 and Comparative Examples 1-3 were tested according to GB / T 2423.4-2008 "Environmental testing for electrical and electronic products - Part 2: Test methods - Test Db: Alternating damp heat (12h + 12h cycle)". The results are shown in Table 3 below. ④ The corrosion medium penetration rate of the corrosion-resistant polyether composite samples prepared in Examples 1-3 and Comparative Examples 1-3 was tested according to GB / T 19282-2014 "Test Method for Chemical Resistance of Thermoplastic Pipes for Fluid Transportation". The results are shown in Table 4 below.

[0049]

[0050] Table 1

[0051] Table 2

[0052] Table 3

[0053] Table 4

[0054] As can be seen from Tables 1-4 above, the anti-corrosion composite polyether prepared in Example 2 has the best resistance to salt spray corrosion, acid and alkali corrosion, water absorption, and corrosive media penetration rate compared to Examples 1, 3, and Comparative Examples 1-3. Therefore, the barrier-type composite nanofiller prepared by using nano-graphene, fluorine-modified nano-SiO2, anhydrous ethanol, and γ-methacryloyloxypropyltrimethoxysilane coupling agent in a specific ratio, and the surface protectant prepared by using fluorine-modified epoxy resin, aminosilane crosslinking agent, nano-boron nitride, organically modified nano-montmorillonite, ethyl acetate, and deionized water in a specific ratio, combined with a polyether polyol matrix composition composed of imidazole ring polyether, m-phenylenediamine polyether, and fluorine-modified polyether, effectively improves the corrosion resistance of the composite polyether and meets the application requirements of harsh environments such as humid, salty, acidic, and alkaline conditions.

[0055] 3.2 Testing of the effect of hardness enhancer on the crack resistance of corrosion-resistant polyether composites

[0056] ①The tensile strength and elongation at break of the corrosion-resistant polyether composite samples prepared in Example 2 and Comparative Examples 4-6 were tested according to GB / T 1040.2-2006 "Determination of tensile properties of plastics - Part 2: Test conditions for molded and extruded plastics". The results are shown in Table 5 below. ②The corrosion-resistant polyether composite samples prepared in Example 2 and Comparative Examples 4-6 were tested for simply supported beam impact strength according to GB / T 1843-2008 "Determination of impact strength of plastic cantilever beams". The results are shown in Table 6 below. ③ The bending strength and bending modulus of the corrosion-resistant polyether composite samples prepared in Example 2 and Comparative Examples 4-6 were tested according to GB / T 9341-2008 "Determination of Flexural Properties of Plastics". The results are shown in Table 7 below.

[0057]

[0058] Table 5

[0059] Table 6

[0060] Table 7

[0061] As can be seen from Tables 5-7 above, the anti-corrosion polyether composite prepared in Example 2 has better fracture resistance than that prepared in Comparative Examples 4-6. The composite fiber filaments, through the use of basalt fiber filaments and glass fiber filaments, nano-silicon carbide particles filling the microscopic gaps between the fiber filaments and the polyether polyol matrix composition, barrier composite nanofillers, etc., significantly enhance the tensile, impact and bending fracture resistance of the anti-corrosion polyether composite. This improvement in fracture resistance can effectively ensure the mechanical integrity of the composite polyether during use in harsh environments, avoid failure problems such as damage and detachment of surface protective agent due to material fracture and cracking, ensure the continuity and stability of the surface protective barrier, and ultimately form a synergistic effect with the anti-corrosion system, further extending the service life of the material under complex working conditions.

[0062] The embodiments described above are merely examples of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention.

Claims

1. A corrosion-resistant composite polyether, characterized in that, By weight, the raw materials for preparing the corrosion-resistant polyether complex include: 65-80 parts of polyether polyol matrix composition, 15-25 parts of barrier-type composite nanofiller, 3-5 parts of surface protectant, 2.5-5 parts of fluorine-modified epoxy silane coupling agent, 4-8 parts of polyether-modified siloxane coupling agent, 2-4 parts of chain extender, 1-1.5 parts of benzotriazole-phosphite composite stabilizer, 10-15 parts of cyclopentane foaming agent, and 1-2 parts of hardness enhancer; The raw materials for preparing the polyether polyol matrix composition, by weight, include: 16.25-20 parts imidazole ring polyether, 26-32 parts m-phenylenediamine polyether, and 22.75-29 parts fluorine-modified polyether. The raw materials for preparing the barrier-type composite nanofiller, by weight, include: 0.5-1 parts of nano-graphene, 6-8 parts of fluorine-modified nano-SiO2, 8-13 parts of anhydrous ethanol, and 0.5-0.8 parts of γ-methacryloyloxypropyltrimethoxysilane coupling agent. The raw materials for preparing the surface protectant, by weight, include: 1.5-2 parts of fluorine-modified epoxy resin, 0.8-1.2 parts of aminosilane crosslinking agent, 0.2-0.3 parts of nano boron nitride, 0.15-0.2 parts of organically modified nano montmorillonite, 10-15 parts of ethyl acetate, and 0.5-1 parts of deionized water.

2. The corrosion-resistant composite polyether according to claim 1, characterized in that, The preparation process of the surface protectant is as follows: (i) Add nano-boron nitride and organically modified nano-montmorillonite to ethyl acetate, place in a high-speed disperser, disperse at 1950-2050 r / min for 20-40 min, and then use an ultrasonic disperser with a power of 295-305 W and a frequency of 17-39 kHz for 10-20 min to obtain a nanoparticle dispersion; (ii) Add fluorine-modified epoxy resin to the nanoparticle dispersion, adjust the speed of the high-speed disperser to 900-1100 r / min, and stir at 20-30℃ for 19-24 min to obtain an epoxy nanoparticle composite matrix; (iii) Add ethyl acetate dropwise to the epoxy nanoparticle composite matrix to adjust the viscosity of the system to 500-1000 mPa. s, to obtain the adjusted composite base material; (iv) add aminosilane crosslinking agent and deionized water to the adjusted composite base material, adjust the speed of the high-speed disperser to 780-820r / min, and continue stirring for 20-40min under constant temperature of 23-28℃ to obtain the pre-crosslinked base material; (v) after vacuum filtering the pre-crosslinked base material with 200 mesh nylon filter cloth, obtain the surface protectant.

3. The corrosion-resistant composite polyether according to claim 1, characterized in that, The organically modified nano-montmorillonite has a particle size of 100-200 nm.

4. The corrosion-resistant composite polyether according to claim 1, characterized in that, The preparation process of the barrier-type composite nanofiller is as follows: (i) Add nano-graphene to anhydrous ethanol, ultrasonically exfoliate and disperse for 20-40 min to obtain graphene ethanol dispersion, add γ-methacryloxypropyltrimethoxysilane coupling agent to it, stir for 15-25 min to obtain pre-activated material; (ii) Add fluorine-modified nano-SiO2 to anhydrous ethanol, stir for 8-12 min to obtain fluorine-modified nano-SiO2 suspension; (iii) Slowly drop the fluorine-modified nano-SiO2 suspension into the graphene ethanol dispersion, stir at high speed for 17-23 min to form a mixed dispersion; (iv) Add distilled water to the mixed dispersion, adjust the pH to 5-7, and stir at a constant temperature of 50-60℃ for 1.5-2.5 h to obtain a grafted mixed system; (v) After depressurization and distillation, the grafted mixed system is dried under vacuum to obtain the barrier-type composite nanofiller.

5. The corrosion-resistant composite polyether according to claim 1, characterized in that, The preparation process of the polyether polyol matrix composition is as follows: (i) Imidazole ring polyether, m-phenylenediamine polyether, and fluorinated polyether are added sequentially to a vacuum constant temperature stirred reactor. After closing the reactor door, the vacuum degree is adjusted to -0.08--0.1 MPa, the temperature is raised to 100-110℃, and vacuum dehydration is carried out at a speed of 300-400 r / min for 1-1.5 h to obtain a dehydrated mixture; (ii) Maintaining the above vacuum parameters, the temperature is lowered to 60-70℃, and first stirred at a low speed of 600-800 r / min for 20-40 min. n, then raise the temperature to 1200-1500 r / min and stir at high speed for 40-50 min to obtain the initial mixture; (iii) maintain a constant temperature of 60-70℃, a vacuum of -0.08--0.1MPa and a speed of 1200-1500 r / min, and continue stirring for 1-1.5 h to obtain the activated product; (iv) reduce the speed to 200-400 r / min, maintain a constant temperature and vacuum for 30-40 min to degas, and then cool naturally to 25-30℃. After filtration, the polyether polyol matrix composition is obtained.

6. The corrosion-resistant composite polyether according to claim 1, characterized in that, The raw materials for preparing the hardness strengthening agent, by weight, include: 3-4 parts of nano-silicon carbide particles, 3-6 parts of composite fiber filaments, 0.1-0.3 parts of bisaminosilane coupling agent, and 8-10 parts of isopropanol. The particle size of the nano-silicon carbide particles is 80-150 nm. The raw materials for the composite fiber filaments include: 2-4 parts basalt fiber filaments and 2-4 parts glass fiber filaments; The basalt fibers have a diameter of 1-3 μm and a length of 50-100 μm. The glass fiber filaments have a diameter of 0.5-2 μm and a length of 30-80 μm.

7. The corrosion-resistant composite polyether according to claim 6, characterized in that, The preparation process of the hardness strengthening agent is as follows: (i) Basalt fiber filaments and glass fiber filaments are uniformly mixed to obtain composite fiber filaments. The composite fiber filaments are added to isopropanol and ultrasonically dispersed for 10-20 minutes using a CNC ultrasonic disperser with a power of 270-330W and a frequency of 27-29kHz to obtain a fiber filament dispersion; (ii) Nano-silicon carbide particles are added to isopropanol and stirred for 5-15 minutes. Then, a diaminosilane coupling agent is added dropwise and activated at room temperature for 10-30 minutes to obtain an activated silicon carbide dispersion; (iii) The fiber filament dispersion is then... Add the activated silicon carbide dispersion at a rate of 1-2 mL / min, and then stir at a high speed of 1200-1500 r / min for 20-40 min to form a mixed composite system; (iv) distill the mixed composite system under reduced pressure at 55-65℃ and -0.08--0.1 MPa for 30-40 min to obtain a paste-like precursor; (v) vacuum dry the precursor at 80℃ for 2 h, cool it, and then grind it for 20 min at a speed of 200 r / min using a planetary ball mill, and then pass it through a 200-mesh nylon sieve to obtain a hardness enhancer.

8. A method for preparing the anti-corrosion composite polyether according to any one of claims 1-7, characterized in that, Includes the following steps: S1. Add the polyether polyol matrix composition to a vacuum constant temperature stirred reactor, maintain the vacuum degree of -0.08--0.1MPa and the temperature of 60-70℃, add the hardness strengthening agent and the barrier type composite nanofiller in sequence, adjust the speed to 1200-1500r / min, stir for 40-60min to form a basic mixed system. S2, add fluorine-modified epoxy silane coupling agent and polyether-modified siloxane coupling agent to the basic mixture system, maintain the above vacuum, temperature and speed, and continue stirring for 30-40 min. Then add chain extender, cool to 40-50℃, adjust the speed to 800-1000 r / min, stir for 20-30 min, then add benzotriazole-phosphite composite stabilizer and surface protectant, maintain vacuum of -0.08--0.1MPa and temperature of 40-50℃, stir at 600-800 r / min for 25-35 min, so that the surface protectant is uniformly coated on the surface of the mixture system to form a stable composite system; S3. Turn off the vacuum system, lower the temperature of the stable composite system to 25-30℃, add cyclopentane foaming agent, adjust the speed to 300-400r / min, stir for 15-20min, then inject the material into the mold, and cure at 25-30℃ and 0.1-0.3MPa pressure for 2-3h under constant temperature and pressure. After demolding, the corrosion-resistant composite polyether is obtained.

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