Corrosion-resistant composite adhesive and preparation method thereof

Abstract

The invention provides a corrosion-resistant composite adhesive and a preparation method thereof, and the composite adhesive is prepared from the following components in parts by weight: 8 to 15 parts of chloroprene rubber, 6 to 10 parts of thermoplastic elastomer, 1 to 2 parts of C5 petroleum resin, 1 to 2 parts of C9 petroleum resin, 100 to 140 parts of 120 # solvent oil, 45 to 60 parts of ethyl acetate, 0.5 to 1 part of antioxidant and 4 to 8 parts of CoCrFeNiAl coated SiO2 particles. 2 to 3 parts of nano pH response chitosan / sodium alginate particles; wherein the CoCrFeNiAl (at) SiO2 particles are formed by compounding a high-entropy alloy CoCrFeNiAl and silicon dioxide, and the CoCrFeNiAl (at) SiO2 particles are formed by compounding the high-entropy alloy According to the adhesive disclosed by the invention, through the synergistic effect of multiple components, the corrosion resistance is remarkably improved.

Description

Technical Field

[0001] The present invention relates to the field of adhesives, and in particular to a corrosion-resistant composite adhesive and a preparation method thereof. Background Art

[0002] Neoprene rubber (CR) adhesives are widely used in industries such as footwear, construction, automotive interiors, and leather goods due to their excellent initial tack, flexibility, weather resistance, and good adhesion to a variety of substrates. The chlorine atoms in their molecular structure impart certain flame retardancy and oil resistance, making them a valuable alternative to traditional solvent-based adhesives. However, in applications involving harsh corrosive environments, the long-term corrosion resistance of conventional chloroprene rubber adhesives is still insufficient, becoming a key bottleneck restricting their wider application. This deficiency is mainly reflected in the following aspects: Limited resistance to chemical media: While chloroprene rubber has some resistance to non-polar solvents and oils, it has poor tolerance to strong acids, strong bases, oxidizing media, and certain polar solvents. Prolonged exposure to such environments can lead to degradation of the rubber molecular chains and destruction of the cross-linked network, causing the adhesive layer to soften, dissolve, swell, or become brittle, ultimately losing bond strength and sealing properties. In high temperature and high humidity environments, moisture and heat synergistically accelerate the hydrolysis and aging process of chloroprene rubber. This not only degrades the physical and mechanical properties of the adhesive layer but also significantly weakens its adhesion to the substrate interface, causing bond failure. Furthermore, moisture penetration provides a pathway for corrosive ions (such as Cl-) to migrate to the metal substrate / adhesive interface, inducing substrate corrosion or interfacial corrosion. Passive corrosion protection: Traditional corrosion protection strategies rely primarily on the limited barrier properties of chloroprene rubber itself or the addition of conventional inert fillers (such as talc and calcium carbonate) to physically block corrosive media. These methods lack active protection mechanisms and are unable to respond to changes in the corrosive environment (such as local pH fluctuations) or release corrosion inhibitors to suppress the initiation and development of corrosion. Filler-matrix interface issues: Even when anti-corrosion fillers are added, their compatibility and interfacial bonding strength with the chloroprene rubber matrix are often suboptimal. This can lead to uneven filler dispersion, defects at the interface, or micropores, which in turn provide a preferential path for the penetration of corrosive media, weakening the filler's anti-corrosion effect and even accelerating localized corrosion. Therefore, despite the numerous advantages of chloroprene rubber adhesives, they still have significant deficiencies in chemical resistance, resistance to moisture and heat aging, and long-term corrosion protection of substrates when dealing with complex, changing, and long-term corrosive environments. Developing new chloroprene rubber-based composite adhesives with significantly enhanced, especially active and intelligent, anti-corrosion capabilities to meet the stringent anti-corrosion needs of high-end manufacturing, marine engineering, new energy facilities, and other fields is a key direction of current technological development. Summary of the Invention

[0003] Technical problem to be solved: The purpose of the present invention is to provide a corrosion-resistant composite adhesive that significantly improves corrosion resistance through the synergistic effect of multiple components.

[0004] Technical solution: A corrosion-resistant composite adhesive, comprising the following components in parts by weight: 8-15 parts of chloroprene rubber 6-10 parts thermoplastic elastomer 1-2 parts of C5 petroleum resin 1-2 parts of C9 petroleum resin 100-140 parts of No. 120 solvent oil 45-60 parts of ethyl acetate 0.5-1 part antioxidant 4-8 parts of CoCrFeNiAl@SiO2 particles 2-3 parts of nano pH-responsive chitosan / sodium alginate particles; The CoCrFeNiAl@SiO2 particles are composed of a composite of high entropy alloy CoCrFeNiAl and silicon dioxide. Preferably, the antioxidant is one or more of antioxidant RD, antioxidant 4010NA, antioxidant 264, antioxidant SP, antioxidant TNPP or antioxidant TNP; and / or, The thermoplastic elastomer is a styrene-isoprene-styrene block copolymer. The preparation method of the above-mentioned corrosion-resistant composite adhesive comprises the following steps: S1. No. 120 solvent oil and ethyl acetate were mixed and added to the reactor, and heated and stirred under anaerobic conditions to uniformly disperse the two mixed solvents; S2. The chloroprene rubber, thermoplastic elastomer, C5 petroleum resin, C9 petroleum resin were added to the reactor and mixed and stirred until all the materials were dissolved; S3. Finally, the antioxidant, CoCrFeNiAl@SiO2 particles and nano pH-responsive chitosan / sodium alginate particles were added to the reactor and stirred to mix evenly to obtain a composite adhesive. Preferably, the heating temperature in step S1 is 45-60° C., and the stirring speed is 600-900 r / min; and / or the stirring time is 3-6 h, and the stirring speed is 600-900 r / min. Preferably, the preparation method of the CoCrFeNiAl@SiO2 particles comprises the following steps: S11. adding ethyl orthosilicate to a 0.15-0.2 mol / L hydrochloric acid solution for pre-hydrolysis to obtain a ethyl orthosilicate pre-hydrolyzed solution; S12. Equimolar amounts of CoCl2·6H2O, CrCl3·6H2O, FeCl3·6H2O, Ni(NO3)2·6H2O, Al(NO3)3·9H2O, and citric acid were mixed uniformly, and the mixture was added to the ethyl orthosilicate pre-hydrolyzed solution and stirred until completely dissolved to obtain a mixed hydrolyzed solution. S13. F127 was added to anhydrous ethanol and stirred until completely dissolved to obtain an F127 solution. S14. The mixed hydrolyzed solution was added to the F127 solution and stirred to mix uniformly to obtain a precursor solution; S15. The precursor solution is spray dried and granulated by a spray drying apparatus to obtain composite particles; S16. The composite particles are first dried in air, then heated to 550°C at a rate of 2-3°C / min, kept at this temperature for 2 hours, and finally sintered at 900-1050°C for 3 hours under nitrogen to obtain CoCrFeNiAl@SiO2 particles. Preferably, the method for preparing the nano pH-responsive chitosan / sodium alginate particles comprises the following steps: S21. Prepare sodium alginate solution and chitosan solution; S22. Calcium chloride was added to the sodium alginate solution, mixed and stirred, chitosan solution was added, the pH of the mixed solution was adjusted to 4 to 5, stirring was continued, and high-speed centrifugation was performed to obtain nano-hybrid particles; S23. Add the nano-hybrid particles to a 0.1 mol / L sodium bicarbonate aqueous solution, stir and mix, place the mixture in a vacuum box at 40-50 kPa for 10-20 min, and centrifuge and dry to obtain nano pH-responsive chitosan / sodium alginate particles. Preferably, in step S11, the mass ratio of tetraethyl orthosilicate to hydrochloric acid is 1.8-2.2:1; and / or, In step S12, the molar ratio of CoCl2·6H2O to ethyl orthosilicate is 0.03-0.05:1; and / or, The mass ratio of F127 to ethyl orthosilicate in the F127 solution in step S14 is 0.8-1:1; and / or the hot air flow rate in the spray granulation in step S15 is 220-240 L / min and the pressure is 0.3-0.4 kg / cm 2 . Preferably, in step S21, the concentration of the sodium alginate solution is 3-8 g / L, and the concentration of the chitosan solution is 3-8 g / L; and / or, The mass ratio of calcium chloride, sodium alginate and chitosan in the mixed solution in step S22 is 4-5:0.8-1:1.2-1.5; and / or the mass volume ratio of the nano-mixed particles to the sodium bicarbonate aqueous solution in step S23 is 1-2:50. Beneficial effects: The corrosion-resistant composite adhesive of the present invention has the following advantages: 1. The CoCrFeNiAl high-entropy alloy in the present invention has excellent corrosion resistance. Its surface preferentially forms dense oxides such as Cr2O3 in a corrosive environment. These oxides have good passivation ability and can effectively block further penetration of corrosive media. SiO2 forms a dense physical barrier in the composite particle structure, which can effectively reduce the penetration of corrosive media (such as Cl-), thereby reducing the corrosion rate. The introduction of SiO2 can slow down the corrosion current density and improve the corrosion resistance of the coating. The low surface energy characteristics of SiO2 also make it difficult for corrosive media to adhere, thereby further inhibiting the corrosion reaction. The synergistic effect of SiO2 and the high-entropy alloy not only improves the stability of the surface oxide film, but also enhances its ability to resist pitting corrosion and uniform corrosion. 2. The pH-responsive nano-chitosan / sodium alginate particles prepared in the present invention, under acidic conditions, the amino groups of chitosan are protonated, resulting in enhanced electrostatic repulsion, thereby inducing particle swelling; while under alkaline conditions, the carboxyl groups of alginate are ionized, thereby inducing particle swelling. The swollen chitosan / sodium alginate particles and CoCrFeNiAl@SiO2 particles combine to block the pores or defects in the adhesive layer, cutting off the diffusion path of the corrosive medium, thereby improving the anti-corrosion effect; 3. The pH-responsive nano-chitosan / sodium alginate particles prepared in the present invention also contain a trace amount of sodium bicarbonate. During the acid corrosion process, H + The pH-responsive nano-chitosan / sodium alginate particles enter the interior and generate CO2 with sodium bicarbonate. Under the action of the acidic solution, the chitosan / sodium alginate particles further expand due to the action of CO2, blocking pores or defects and improving the anti-corrosion effect. DETAILED DESCRIPTION The present invention will be further described below in conjunction with examples, which are provided to explain the present invention and are not limited to the following examples: Example 1 A method for preparing a corrosion-resistant composite adhesive comprises the following steps: S1. 100 parts of No. 120 solvent oil and 45 parts of ethyl acetate were mixed and added to the reactor, heated to 45 ° C under anaerobic conditions, and stirred at 900 r / min speed to disperse the two mixed solvents evenly; S2. 8 parts of chloroprene rubber CR232, 6 parts of styrene-isoprene-styrene block copolymer, 1 part of C5 petroleum resin Escorez TM 2101, 2 parts C9 petroleum resin Escorez TM 5380 was added to the reactor and mixed and stirred until all materials were dissolved; S3. Finally, 0.5 parts of antioxidant TNPP, 4 parts of CoCrFeNiAl@SiO2 particles and 2 parts of nano pH-responsive chitosan / sodium alginate particles were added to the reactor and stirred for 6 hours at a stirring speed of 600 r / min to obtain a composite adhesive; The preparation method of the CoCrFeNiAl@SiO2 particles comprises the following steps: S11. The ethyl orthosilicate was added to a 0.15 mol / L hydrochloric acid solution for pre-hydrolysis, the mass ratio of ethyl orthosilicate and hydrochloric acid being 1.8:1 to obtain a ethyl orthosilicate pre-hydrolyzed solution; S12. Equimolar amounts of CoCl2·6H2O, CrCl3·6H2O, FeCl3·6H2O, Ni(NO3)2·6H2O, Al(NO3)3·9H2O, and citric acid were mixed and added to the ethyl orthosilicate pre-hydrolyzed solution and stirred until completely dissolved to obtain a mixed hydrolyzed solution. The molar ratio of CoCl2·6H2O to ethyl orthosilicate in the mixed hydrolyzed solution was 0.03:1. S13. F127 was added to anhydrous ethanol and stirred until completely dissolved to obtain an F127 solution; S14. The mixed hydrolysis solution was added to the F127 solution, the mass ratio of F127 contained in the F127 solution to the mixed hydrolysis solution of ethyl orthosilicate was 0.8: 1, and stirred to mix uniformly to obtain a precursor solution; S15. The precursor solution is spray-dried and granulated by a spray drying device. The hot air flow rate during the spray granulation is 220 L / min and the pressure is 0.4 kg / cm 2 , obtaining composite particles; S16. The composite particles were dried in air, then heated to 550°C at a rate of 2°C / min, held for 2 h, and finally sintered at 900°C under nitrogen for 3 h to obtain CoCrFeNiAl@SiO2. The method for preparing the nano pH-responsive chitosan / sodium alginate particles comprises the following steps: S21. Prepare 8 g / L sodium alginate aqueous solution and 3 g / L chitosan acetic acid solution; S22. Calcium chloride was added to the sodium alginate solution, mixed and stirred, chitosan acetic acid solution was added, and the pH of the mixed solution was adjusted to 4. The mass ratio of calcium chloride, sodium alginate and chitosan in the mixed solution was 5:0.8:1.2, and stirring was continued. High-speed centrifugation was performed to obtain nano-hybrid particles; S23. Add the nano-hybrid particles to a 0.1 mol / L sodium bicarbonate aqueous solution at a mass volume ratio of the nano-hybrid particles to the sodium bicarbonate aqueous solution of 1:50. After stirring and mixing, place the mixture in a vacuum chamber at 50 kPa for 10 min, and centrifuge and dry to obtain pH-responsive chitosan / sodium alginate nanoparticles. Example 2 A method for preparing a corrosion-resistant composite adhesive comprises the following steps: S1. 140 parts of 120 solvent oil and 60 parts of ethyl acetate were mixed and added to the reactor, heated to 60 ° C under anaerobic conditions, and stirred at 600 r / min speed to disperse the two mixed solvents evenly; S2. 15 parts of chloroprene rubber CR232, 10 parts of styrene-isoprene-styrene block copolymer, 2 parts of C5 petroleum resin Escorez TM 2101, 1 part C9 petroleum resin Escorez TM 5380 was added to the reactor and mixed and stirred until all materials were dissolved; S3. Finally, 1 part of the antioxidant TNPP, 8 parts of CoCrFeNiAl@SiO2 particles and 3 parts of nano pH-responsive chitosan / sodium alginate particles were added to the reactor and stirred for 3 hours at a stirring speed of 900 r / min to obtain a composite adhesive; The preparation method of the CoCrFeNiAl@SiO2 particles comprises the following steps: S11. Ethyl orthosilicate was added to a 0.2 mol / L hydrochloric acid solution for pre-hydrolysis, the mass ratio of ethyl orthosilicate and hydrochloric acid being 2.2:1 to obtain a pre-hydrolyzed solution of ethyl orthosilicate; S12. Equimolar amounts of CoCl2·6H2O, CrCl3·6H2O, FeCl3·6H2O, Ni(NO3)2·6H2O, Al(NO3)3·9H2O, and citric acid were mixed and added to the ethyl orthosilicate pre-hydrolyzed solution and stirred until completely dissolved to obtain a mixed hydrolyzed solution. The molar ratio of CoCl2·6H2O to ethyl orthosilicate in the mixed hydrolyzed solution was 0.05:1. S13. F127 was added to anhydrous ethanol and stirred until completely dissolved to obtain an F127 solution; S14. The mixed hydrolysis solution was added to the F127 solution, the mass ratio of F127 contained in the F127 solution to the ethyl orthosilicate in the mixed hydrolysis solution was 1:1, and the mixture was stirred to obtain a precursor solution; S15. The precursor solution is spray dried and granulated by a spray drying device. The hot air flow rate during the spray granulation is 240 L / min and the pressure is 0.3 kg / cm 2 , obtaining composite particles; S16. The composite particles were dried in air, then heated to 550°C at a rate of 3°C / min, held for 2 h, and finally sintered at 1050°C under nitrogen for 3 h to obtain CoCrFeNiAl@SiO2. The method for preparing the nano pH-responsive chitosan / sodium alginate particles comprises the following steps: S21. Prepare 3g / L sodium alginate aqueous solution and 8g / L chitosan acetic acid solution; S22. Calcium chloride was added to the sodium alginate solution, mixed and stirred, chitosan acetic acid solution was added, and the pH of the mixed solution was adjusted to 5. The mass ratio of calcium chloride, sodium alginate and chitosan in the mixed solution was 4:1:1.5, and stirring was continued. High-speed centrifugation was performed to obtain nano-hybrid particles; S23. Add the nano-hybrid particles to a 0.1 mol / L sodium bicarbonate aqueous solution at a mass volume ratio of the nano-hybrid particles to the sodium bicarbonate aqueous solution of 1:25. After stirring and mixing, place the mixture in a vacuum chamber at 40 kPa for 20 min, and centrifuge and dry to obtain pH-responsive chitosan / sodium alginate nanoparticles. Example 3 A method for preparing a corrosion-resistant composite adhesive comprises the following steps: S1. 110 parts of 120 solvent oil and 50 parts of ethyl acetate were mixed and added to the reactor, heated to 50 ° C under anaerobic conditions, and stirred at 650r / min speed to uniformly disperse the two mixed solvents; S2. 10 parts of chloroprene rubber CR232, 8 parts of styrene-isoprene-styrene block copolymer, 1.5 parts of C5 petroleum resin Escorez TM 2101, 1.5 parts C9 petroleum resin Escorez TM 5380 was added to the reactor and mixed and stirred until all materials were dissolved; S3. Finally, 0.6 parts of antioxidant TNPP, 6 parts of CoCrFeNiAl@SiO2 particles and 2.2 parts of nano pH-responsive chitosan / sodium alginate particles were added to the reactor and stirred for 5 hours at a stirring speed of 700 r / min to obtain a composite adhesive; The preparation method of the CoCrFeNiAl@SiO2 particles comprises the following steps: S11. Ethyl orthosilicate was added to a 0.18 mol / L hydrochloric acid solution for pre-hydrolysis, the mass ratio of ethyl orthosilicate to hydrochloric acid being 2:1 to obtain a pre-hydrolyzed solution of ethyl orthosilicate; S12. Equimolar amounts of CoCl2·6H2O, CrCl3·6H2O, FeCl3·6H2O, Ni(NO3)2·6H2O, Al(NO3)3·9H2O, and citric acid were mixed and added to the ethyl orthosilicate pre-hydrolyzed solution and stirred until completely dissolved to obtain a mixed hydrolyzed solution. The molar ratio of CoCl2·6H2O to ethyl orthosilicate in the mixed hydrolyzed solution was 0.03:1. S13. F127 was added to anhydrous ethanol and stirred until completely dissolved to obtain an F127 solution; S14. The mixed hydrolysis solution was added to the F127 solution, the mass ratio of F127 contained in the F127 solution to the mixed hydrolysis solution of ethyl orthosilicate was 0.8: 1, and stirred to mix uniformly to obtain a precursor solution; S15. The precursor solution is spray-dried and granulated by a spray drying device. The hot air flow rate during the spray granulation is 225 L / min and the pressure is 0.3 kg / cm 2 , obtaining composite particles; S16. The composite particles were dried in air, then heated to 550°C at a rate of 2°C / min, held for 2 h, and finally sintered at 1020°C under nitrogen for 3 h to obtain CoCrFeNiAl@SiO2. The method for preparing the nano pH-responsive chitosan / sodium alginate particles comprises the following steps: S21. Prepare 4 g / L sodium alginate aqueous solution and 4 g / L chitosan acetic acid solution; S22. Calcium chloride was added to the sodium alginate solution, mixed and stirred, chitosan acetic acid solution was added, and the pH of the mixed solution was adjusted to 5. The mass ratio of calcium chloride, sodium alginate and chitosan in the mixed solution was 4.2:0.9:1.3, and stirring was continued. High-speed centrifugation was performed to obtain nano-hybrid particles; S23. The nano-hybrid particles were added to a 0.1 mol / L sodium bicarbonate aqueous solution at a mass volume ratio of the nano-hybrid particles to the sodium bicarbonate aqueous solution of 1.2:50. After stirring and mixing, the mixture was placed in a vacuum chamber at 40 kPa for 20 min and centrifuged to obtain pH-responsive chitosan / sodium alginate nanoparticles. Example 4 A method for preparing a corrosion-resistant composite adhesive comprises the following steps: S1. 120 parts of 120 solvent oil and 50 parts of ethyl acetate were mixed and added to the reactor, heated to 55 ° C under anaerobic conditions, and stirred at 700 r / min speed to uniformly disperse the two mixed solvents; S2. 9 parts of chloroprene rubber CR232, 6 parts of styrene-isoprene-styrene block copolymer, 1.5 parts of C5 petroleum resin EscorezTM 2101, 1.2 parts C9 petroleum resin Escorez TM 5380 was added to the reactor and mixed and stirred until all materials were dissolved; S3. Finally, 0.8 parts of antioxidant TNPP, 7 parts of CoCrFeNiAl@SiO2 particles and 2.4 parts of nano pH-responsive chitosan / sodium alginate particles were added to the reactor and stirred for 4.5h at a stirring speed of 800r / min to obtain a composite adhesive; The preparation method of the CoCrFeNiAl@SiO2 particles comprises the following steps: S11. Ethyl orthosilicate was added to a 0.2 mol / L hydrochloric acid solution for pre-hydrolysis, the mass ratio of ethyl orthosilicate and hydrochloric acid being 2.1:1 to obtain a pre-hydrolyzed solution of ethyl orthosilicate; S12. Equimolar amounts of CoCl2·6H2O, CrCl3·6H2O, FeCl3·6H2O, Ni(NO3)2·6H2O, Al(NO3)3·9H2O, and citric acid were mixed and added to the ethyl orthosilicate pre-hydrolyzed solution and stirred until completely dissolved to obtain a mixed hydrolyzed solution. The molar ratio of CoCl2·6H2O to ethyl orthosilicate in the mixed hydrolyzed solution was 0.05:1. S13. F127 was added to anhydrous ethanol and stirred until completely dissolved to obtain an F127 solution; S14. The mixed hydrolysis solution was added to the F127 solution, the mass ratio of F127 contained in the F127 solution to the ethyl orthosilicate in the mixed hydrolysis solution was 1:1, and the mixture was stirred to obtain a precursor solution; S15. The precursor solution is spray dried and granulated by a spray drying device. The hot air flow rate during the spray granulation is 235 L / min and the pressure is 0.36 kg / cm 2 , obtaining composite particles; S16. The composite particles were dried in air, then heated to 550°C at a rate of 2.5°C / min, held for 2 h, and finally sintered at 950°C under nitrogen for 3 h to obtain CoCrFeNiAl@SiO2. The method for preparing the nano pH-responsive chitosan / sodium alginate particles comprises the following steps: S21. Prepare 7g / L sodium alginate aqueous solution and 6g / L chitosan acetic acid solution; S22. Calcium chloride was added to the sodium alginate solution, mixed and stirred, chitosan acetic acid solution was added, and the pH of the mixed solution was adjusted to 5. The mass ratio of calcium chloride, sodium alginate and chitosan in the mixed solution was 4.8:0.8:1.4, and stirring was continued. High-speed centrifugation was performed to obtain nano-hybrid particles; S23. The nanohybrid particles were added to a 0.1 mol / L sodium bicarbonate aqueous solution at a mass volume ratio of the nanohybrid particles to the sodium bicarbonate aqueous solution of 1.7:50. After stirring and mixing, the mixture was placed in a vacuum chamber at 50 kPa for 10 min and centrifuged to obtain pH-responsive chitosan / sodium alginate nanoparticles. Example 5 A method for preparing a corrosion-resistant composite adhesive comprises the following steps: S1. 130 parts of 120 solvent oil and 55 parts of ethyl acetate were mixed and added to the reactor, heated to 55 ° C under anaerobic conditions, and stirred at 800 r / min speed to uniformly disperse the two mixed solvents; S2. 10 parts of chloroprene rubber CR232, 8 parts of styrene-isoprene-styrene block copolymer, 1.5 parts of C5 petroleum resin Escorez TM 2101, 1.2 parts C9 petroleum resin Escorez TM 5380 was added to the reactor and mixed and stirred until all materials were dissolved; S3. Finally, 0.8 parts of antioxidant TNPP, 5 parts of CoCrFeNiAl@SiO2 particles and 2.6 parts of nano pH-responsive chitosan / sodium alginate particles were added to the reactor and stirred for 4 hours at a stirring speed of 700 r / min to obtain a composite adhesive; The preparation method of the CoCrFeNiAl@SiO2 particles comprises the following steps: S11. Ethyl orthosilicate was added to a 0.15 mol / L hydrochloric acid solution for pre-hydrolysis, the mass ratio of ethyl orthosilicate to hydrochloric acid being 2:1 to obtain a pre-hydrolyzed solution of ethyl orthosilicate; S12. Equimolar amounts of CoCl2·6H2O, CrCl3·6H2O, FeCl3·6H2O, Ni(NO3)2·6H2O, Al(NO3)3·9H2O, and citric acid were mixed and added to the ethyl orthosilicate pre-hydrolyzed solution and stirred until completely dissolved to obtain a mixed hydrolyzed solution. The molar ratio of CoCl2·6H2O to ethyl orthosilicate in the mixed hydrolyzed solution was 0.04:1. S13. F127 was added to anhydrous ethanol and stirred until completely dissolved to obtain an F127 solution; S14. The mixed hydrolysis solution was added to the F127 solution, the mass ratio of F127 contained in the F127 solution to the mixed hydrolysis solution of ethyl orthosilicate was 0.9: 1, and stirred to mix uniformly to obtain a precursor solution; S15. The precursor solution is spray dried and granulated by a spray drying device. The hot air flow rate during the spray granulation is 230 L / min and the pressure is 0.35 kg / cm 2, obtaining composite particles; S16. The composite particles were dried in air, then heated to 550°C at a rate of 2°C / min, held for 2 h, and finally sintered at 1000°C for 3 h under nitrogen to obtain CoCrFeNiAl@SiO2. The method for preparing the nano pH-responsive chitosan / sodium alginate particles comprises the following steps: S21. Prepare 5g / L sodium alginate aqueous solution and 5g / L chitosan acetic acid solution; S22. Calcium chloride was added to the sodium alginate solution, mixed and stirred, chitosan acetic acid solution was added, and the pH of the mixed solution was adjusted to 4. The mass ratio of calcium chloride, sodium alginate and chitosan in the mixed solution was 4.5:0.8:1.4, and stirring was continued, and high-speed centrifugation was performed to obtain nano-hybrid particles; S23. The nanohybrid particles were added to a 0.1 mol / L sodium bicarbonate aqueous solution at a mass volume ratio of the nanohybrid particles to the sodium bicarbonate aqueous solution of 1.5:50. After stirring and mixing, the mixture was placed in a vacuum chamber at 45 kPa for 15 minutes and centrifuged to obtain pH-responsive chitosan / sodium alginate nanoparticles. Comparative Example 1 The difference between Comparative Example 1 and Example 5 is that the CoCrFeNiAl@SiO2 particles are not contained. Comparative Example 2 The difference between Comparative Example 2 and Example 5 is that the comparative example 2 does not contain nano pH-responsive chitosan / sodium alginate particles. Comparative Example 3 The difference between Comparative Example 3 and Example 5 is that the nano pH-responsive chitosan / sodium alginate particles are replaced by nano chitosan particles. Comparative Example 4 The difference between Comparative Example 4 and Example 5 is that the CoCrFeNiAl@SiO2 particles are replaced by micron SiO2 particles. Comparative Example 5 The difference between Comparative Example 5 and Example 5 is that the CoCrFeNiAl@SiO2 particles are replaced with Cr@SiO2; A method for preparing a corrosion-resistant composite adhesive comprises the following steps: S1. 130 parts of 120 solvent oil and 55 parts of ethyl acetate were mixed and added to the reactor, heated to 55 ° C under anaerobic conditions, and stirred at 800 r / min speed to uniformly disperse the two mixed solvents; S2. 10 parts of chloroprene rubber CR232, 8 parts of styrene-isoprene-styrene block copolymer, 1.5 parts of C5 petroleum resin Escorez TM 2101, 1.2 parts C9 petroleum resin EscorezTM 5380 was added to the reactor and mixed and stirred until all materials were dissolved; S3. Finally, 0.8 parts of antioxidant TNPP, 5 parts of CoCrFeNiAl@SiO2 particles and 2.6 parts of nano pH-responsive chitosan / sodium alginate particles were added to the reactor and stirred for 4 hours at a stirring speed of 700 r / min to obtain a composite adhesive; The preparation method of the Cr@SiO2 particles comprises the following steps: S11. Ethyl orthosilicate was added to a 0.15 mol / L hydrochloric acid solution for pre-hydrolysis, the mass ratio of ethyl orthosilicate to hydrochloric acid being 2:1 to obtain a pre-hydrolyzed solution of ethyl orthosilicate; S12. After CrCl3·6H2O and citric acid were mixed, they were added to the ethyl orthosilicate pre-hydrolyzed solution and stirred until completely dissolved to obtain a mixed hydrolyzed solution. The molar ratio of CrCl3·6H2O to ethyl orthosilicate in the mixed hydrolyzed solution was 0.2:1; S13. F127 was added to anhydrous ethanol and stirred until completely dissolved to obtain an F127 solution; S14. The mixed hydrolysis solution was added to the F127 solution, the mass ratio of F127 contained in the F127 solution to the mixed hydrolysis solution of ethyl orthosilicate was 0.9: 1, and stirred to mix uniformly to obtain a precursor solution; S15. The precursor solution is spray dried and granulated by a spray drying device. The hot air flow rate during the spray granulation is 230 L / min and the pressure is 0.35 kg / cm 2 , obtaining composite particles; S16. The composite particles were dried in air, then heated to 550°C at a rate of 2°C / min, held for 2 h, and finally sintered at 1000°C for 3 h under nitrogen to obtain Crl@SiO2. The method for preparing the nano pH-responsive chitosan / sodium alginate particles comprises the following steps: S21. Prepare 5g / L sodium alginate aqueous solution and 5g / L chitosan acetic acid solution; S22. Calcium chloride was added to the sodium alginate solution, mixed and stirred, chitosan acetic acid solution was added, and the pH of the mixed solution was adjusted to 4. The mass ratio of calcium chloride, sodium alginate and chitosan in the mixed solution was 4.5:0.8:1.4, and stirring was continued, and high-speed centrifugation was performed to obtain nano-hybrid particles; S23. The nanohybrid particles were added to a 0.1 mol / L sodium bicarbonate aqueous solution at a mass volume ratio of the nanohybrid particles to the sodium bicarbonate aqueous solution of 1.5:50. After stirring and mixing, the mixture was placed in a vacuum chamber at 45 kPa for 15 minutes and centrifuged to obtain pH-responsive chitosan / sodium alginate nanoparticles. The adhesives prepared in Examples 1-5 and Comparative Examples 1-5 were evenly applied to the surface of an aluminum plate (area 30×15 mm), allowed to dry, and then applied a second time. The adhesive layer was closed when it felt sticky but not sticky with the adhesive liquid when touched with a finger. After being cured at room temperature, the adhesive was placed on the upper and lower chucks of a test machine, and a load was applied at a constant speed of 20 mm / min until the joint was broken. After the adhesive is cured, it is placed in acid or alkali respectively. After being placed at room temperature for 24 hours, the sample is taken out and its shear strength is tested. The shear strength results under each condition are shown in Table 1 below: Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. A corrosion-resistant composite adhesive, characterized in that: The composite adhesive comprises the following components in parts by weight: 8-15 parts of chloroprene rubber 6-10 parts thermoplastic elastomer 1-2 parts of C5 petroleum resin 1-2 parts of C9 petroleum resin 100-140 parts of No. 120 solvent oil 45-60 parts of ethyl acetate 0.5-1 part antioxidant 4-8 parts of CoCrFeNiAl@SiO2 particles 2-3 parts of nano pH-responsive chitosan / sodium alginate particles; The CoCrFeNiAl@SiO2 particles are composed of a composite of high entropy alloy CoCrFeNiAl and silicon dioxide.

2. The corrosion-resistant composite adhesive according to claim 1, characterized in that: The antioxidant is one or more of antioxidant RD, antioxidant 4010NA, antioxidant 264, antioxidant SP, antioxidant TNPP or antioxidant TNP; and / or the thermoplastic elastomer is styrene-isoprene-styrene block copolymer.

3. The method for preparing the corrosion-resistant composite adhesive according to claim 1, wherein: The following steps are involved: S1. No. 120 solvent oil and ethyl acetate were mixed and added to the reactor, and heated and stirred under anaerobic conditions to uniformly disperse the two mixed solvents; S2. The chloroprene rubber, thermoplastic elastomer, C5 petroleum resin, C9 petroleum resin were added to the reactor and mixed and stirred until all the materials were dissolved; S3. Finally, the antioxidant, CoCrFeNiAl@SiO2 particles and nano pH-responsive chitosan / sodium alginate particles were added to the reactor and stirred to mix evenly to obtain a composite adhesive.

4. The method for preparing the corrosion-resistant composite adhesive according to claim 2, wherein: In step S1, the heating temperature is 45-60° C. and the stirring speed is 600-900 r / min; and / or, The stirring time is 3 to 6 hours, and the stirring speed is 600 to 900 r / min.

5. The corrosion-resistant composite adhesive according to claim 1, characterized in that: The preparation method of the CoCrFeNiAl@SiO2 particles comprises the following steps: S11. adding ethyl orthosilicate to a 0.15-0.2 mol / L hydrochloric acid solution for pre-hydrolysis to obtain a ethyl orthosilicate pre-hydrolyzed solution; S12. Equimolar amounts of CoCl2·6H2O, CrCl3·6H2O, FeCl3·6H2O, Ni(NO3)2·6H2O, Al(NO3)3·9H2O, and citric acid were mixed uniformly, and the mixture was added to the ethyl orthosilicate pre-hydrolyzed solution and stirred until completely dissolved to obtain a mixed hydrolyzed solution; S13. F127 was added to anhydrous ethanol and stirred until completely dissolved to obtain an F127 solution; S14. The mixed hydrolyzed solution was added to the F127 solution and stirred to mix uniformly to obtain a precursor solution; S15. The precursor solution is spray dried and granulated by a spray drying apparatus to obtain composite particles; S16. The composite particles are first dried in air, then heated to 550°C at a rate of 2-3°C / min, kept at this temperature for 2 hours, and finally sintered at 900-1050°C for 3 hours under nitrogen to obtain CoCrFeNiAl@SiO2 particles.

6. The corrosion-resistant composite adhesive according to claim 1, characterized in that: The method for preparing the nano pH-responsive chitosan / sodium alginate particles comprises the following steps: S21. Prepare sodium alginate solution and chitosan solution; S22. Calcium chloride was added to the sodium alginate solution, mixed and stirred, chitosan solution was added, the pH of the mixed solution was adjusted to 4 to 5, stirring was continued, and high-speed centrifugation was performed to obtain nano-hybrid particles; S23. Add the nano-hybrid particles to a 0.1 mol / L sodium bicarbonate aqueous solution, stir and mix, place the mixture in a vacuum box at 40-50 kPa for 10-20 min, and centrifuge and dry to obtain nano pH-responsive chitosan / sodium alginate particles.

7. The corrosion-resistant composite adhesive according to claim 5, characterized in that: In step S11, the mass ratio of tetraethyl orthosilicate to hydrochloric acid is 1.8 to 2.2:1; and / or, In step S12, the molar ratio of CoCl2·6H2O to ethyl orthosilicate is 0.03-0.05:1; and / or, The mass ratio of F127 to ethyl orthosilicate in the F127 solution in step S14 is 0.8 to 1:1; and / or, In the step S15, the hot air flow rate in the spray granulation is 220-240 L / min, and the pressure is 0.3-0.4 kg / cm 2 .

8. The corrosion-resistant composite adhesive according to claim 6, characterized in that: In step S21, the concentration of the sodium alginate solution is 3-8 g / L, and the concentration of the chitosan solution is 3-8 g / L; and / or, The mass ratio of calcium chloride, sodium alginate and chitosan in the mixed solution in step S22 is 4-5:0.8-1:1.2-1.5; and / or the mass volume ratio of the nano-mixed particles to the sodium bicarbonate aqueous solution in step S23 is 1-2:50.

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