Method for preparing anti-permeation anticorrosive filler by using waste rubber and anticorrosive coating

Abstract

The application provides a method for preparing anti-permeation anticorrosive filler from waste rubber and anticorrosive paint, and belongs to the technical field of paint, which comprises the following steps: crushing and sieving waste rubber to obtain rubber particles, then sequentially performing acid pickling, alkali washing and water washing, and drying, then adding the rubber particles into tetrachloroethylene for chlorination, then removing flocculent products by using a blast rotary furnace, then adding the rubber particles into tetrachloroethylene again for chlorination and performing bubbling operation, and then draining to obtain the anti-permeation anticorrosive filler. The anti-permeation anticorrosive filler prepared by the method has improved chlorine content and enhanced corrosion resistance, the anticorrosive coating prepared by using the filler can effectively solve the diffusion problem of water molecules, can effectively inhibit the permeation and migration of corrosion medium chloride ions, and can greatly improve the anti-permeation performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of coatings, in particular to a method for preparing anti-permeation anticorrosive fillers from waste rubber and anticorrosive coatings. BACKGROUND

[0002] At present, offshore wind power is accelerating the expansion to the deep sea area. However, the synergistic effect of high salinity, high humidity, strong ultraviolet rays, wave impact, marine organism attachment and dissolved oxygen and other complex marine environments leads to corrosion threat to offshore wind power structures, which seriously restricts the economy and safety thereof. In order to slow down the corrosion and prolong the service life of offshore wind power structures, protective coatings are often coated on offshore wind power structures, and the anti-permeation anticorrosive fillers in the protective coatings are very crucial to resist corrosion.

[0003] However, the protective coating is prone to failure after being used for a long time. Among them, chloride ion is one of the most destructive environmental factors leading to the failure of the protective coating, and the failure mechanism is that chloride ion diffuses through the intermolecular chain gap of the coating (especially in the water-swollen state) by virtue of small ion radius (0.181 nm) and high migration rate, and the penetration rate is jointly affected by the crosslinking density of the coating (low crosslinking degree resin is more prone to penetration), the type of filler (flaky fillers such as glass flake can extend the path) and the environmental temperature (the diffusion rate doubles every 10℃ of temperature rise). The penetration process is that water molecules first penetrate into the coating to form a "water channel", and chloride ions migrate along the hydration path (ion conductivity is greatly improved), and the penetration coefficient is 1-2 orders of magnitude higher than that of oxygen, and finally corrosion points appear in the coating, which continuously spreads around the corrosion points, resulting in the failure of the protective coating, and the whole coating falls off. In order to overcome the problem of diffusion of chloride ion in the swelling state of the coating, we propose a method for preparing anti-permeation anticorrosive fillers from waste rubber and anticorrosive coatings. SUMMARY

[0004] The purpose of the present application is to provide a method for preparing anti-permeation anticorrosive fillers from waste rubber and anticorrosive coatings to solve the problems raised in the background art.

[0005] To achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0006] The present application provides a method for preparing anti-permeation anticorrosive fillers from waste rubber, comprising the following steps:

[0007] S1: crushing and sieving the waste rubber to obtain rubber particles, and then sequentially performing acid washing, alkali washing and water washing on the rubber particles, and removing the surface residual moisture;

[0008] S2: adding the rubber particles treated in step S1 into tetrachloroethylene, stirring, then transferring into a sealed container, heating to 130℃ and constant temperature reaction, and then transferring into a filter screen after flocculent products appear on the surface of the rubber particles;

[0009] S3: drying the flocculated product, and then removing the flocculated product on the surface of the rubber particles by using a blast rotary furnace;

[0010] S4: adding the rubber particles treated in step S3 into tetrachloroethylene again, stirring again, heating to 130℃ and continuously stirring, and performing bubbling during the stirring;

[0011] S5: draining the rubber particles treated in step S4 to obtain a rubber-based anti-permeation anticorrosive filler.

[0012] Preferably, in step S1, the particle size of the rubber particles is 30-220 μm.

[0013] Preferably, in step S1, the rubber particles are subjected to acid pickling treatment by using hydrochloric acid with pH < 2.

[0014] Preferably, in step S1, the rubber particles are subjected to alkali pickling treatment by using sodium hydroxide solution with pH > 12.

[0015] Preferably, in step S2 or step S4, the mass concentration of the tetrachloroethylene is not less than 90%.

[0016] Preferably, in step S2, the stirring time is 3-24 h.

[0017] Preferably, in step S3, the drying method is blast drying, vacuum drying or freeze drying.

[0018] Preferably, in step S4, the stirring time is at least 1 h.

[0019] Preferably, in step S4, bubbling operation is performed by using chlorine during the stirring, the bubbling rate is 1-3 bubbles per second, and the continuous bubbling operation is performed for 6-12 h.

[0020] The present application also provides an anticorrosive coating, which comprises the anti-permeation anticorrosive filler prepared by using the above method and an epoxy-based coating, and the diluent used in the epoxy-based coating is ethyl acetate diluent.

[0021] Compared with the prior art, the present application has the following technical effects:

[0022] The method for preparing anti-permeation anticorrosive fillers based on waste rubber according to the present application, after the waste rubber is treated, the waste rubber is added into tetrachloroethylene with a mass concentration of not less than 90% twice, in the first time, the tetrachloroethylene is used for fully wetting and chlorinating the rubber particles, in the second time, the chlorine gas is added for bubbling operation, the hydrogen atoms in the rubber molecules are replaced by the chlorine gas in the tetrachloroethylene solvent, the chlorine content of the anti-permeation anticorrosive fillers prepared by the method is improved, and the corrosion resistance is enhanced, the anticorrosive coating prepared by using the fillers can effectively solve the diffusion problem of water molecules, and can effectively inhibit the permeation and migration of the corrosion medium chlorine ions, and the anti-permeation performance can be greatly improved. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 It is a top view of the anti-permeation anticorrosive fillers of the embodiment 1 of the present application;

[0024] Figure 2 It is a top view of the anti-permeation anticorrosive fillers of the embodiment 1 of the present application;

[0025] Figure 3 It is a top view of the anti-permeation anticorrosive fillers of the embodiment 1 of the present application;

[0026] Figure 4 It is a top view of the anti-permeation anticorrosive fillers of the embodiment 1 of the present application;

[0027] Figure 5 It is a top view of the anti-permeation anticorrosive fillers of the embodiment 1 of the present application;

[0028] Figure 6 It is a top view of the anti-permeation anticorrosive fillers of the embodiment 1 of the present application;

[0029] Figure 7 It is a top view of the anti-permeation anticorrosive fillers of the embodiment 1 of the present application;

[0030] Figure 8 It is a top view of the anti-permeation anticorrosive fillers of the embodiment 1 of the present application;

[0031] Figure 9 It is a top view of the anti-permeation anticorrosive fillers of the embodiment 1 of the present application;

[0032] Figure 10 Top view of the corrosion protective coating formed by mixing the anti-osmotic corrosion filler of the present application embodiment 2 with epoxy-based coating in a mass ratio of 1:1;

[0033] Figure 11 Contact angle test diagram of the corrosion protective coating formed by mixing the anti-osmotic corrosion filler of the present application embodiment 2 with epoxy-based coating in a mass ratio of 1:1;

[0034] Figure 12 Tensile strength diagram of the corrosion protective coating formed by mixing the anti-osmotic corrosion filler of the present application embodiment 2 with epoxy-based coating in a mass ratio of 1:1;

[0035] Figure 13 Top view of the corrosion protective coating formed by mixing the anti-osmotic corrosion filler of the present application embodiment 2 with epoxy-based coating in a mass ratio of 1:3;

[0036] Figure 14 Contact angle test diagram of the corrosion protective coating formed by mixing the anti-osmotic corrosion filler of the present application embodiment 2 with epoxy-based coating in a mass ratio of 1:3;

[0037] Figure 15 Tensile strength diagram of the corrosion protective coating formed by mixing the anti-osmotic corrosion filler of the present application embodiment 2 with epoxy-based coating in a mass ratio of 1:3;

[0038] Figure 16 Top view of the corrosion protective coating formed by mixing the anti-osmotic corrosion filler of the present application embodiment 3 with epoxy-based coating in a mass ratio of 1:1;

[0039] Figure 17 Contact angle test diagram of the corrosion protective coating formed by mixing the anti-osmotic corrosion filler of the present application embodiment 3 with epoxy-based coating in a mass ratio of 1:1;

[0040] Figure 18 Tensile strength diagram of the corrosion protective coating formed by mixing the anti-osmotic corrosion filler of the present application embodiment 3 with epoxy-based coating in a mass ratio of 1:1;

[0041] Figure 19 Top view of the corrosion protective coating formed by mixing the anti-osmotic corrosion filler of the present application embodiment 3 with epoxy-based coating in a mass ratio of 1:3;

[0042] Figure 20 Contact angle test diagram of the corrosion protective coating formed by mixing the anti-osmotic corrosion filler of the present application embodiment 3 with epoxy-based coating in a mass ratio of 1:3;

[0043] Figure 21 Tensile strength diagram of the corrosion protective coating formed by mixing the anti-osmotic corrosion filler of the present application embodiment 3 with epoxy-based coating in a mass ratio of 1:3;

[0044] Figure 22 A top view of the anti-corrosion coating formed by mixing the anti-permeation anti-corrosion filler of the present application embodiment 4 and the epoxy-based coating in a mass ratio of 1:1;

[0045] Figure 23 A contact angle test diagram of the anti-corrosion coating formed by mixing the anti-permeation anti-corrosion filler of the present application embodiment 4 and the epoxy-based coating in a mass ratio of 1:1;

[0046] Figure 24 A tensile strength diagram of the anti-corrosion coating formed by mixing the anti-permeation anti-corrosion filler of the present application embodiment 4 and the epoxy-based coating in a mass ratio of 1:1;

[0047] Figure 25 A top view of the anti-corrosion coating formed by mixing the anti-permeation anti-corrosion filler of the present application embodiment 4 and the epoxy-based coating in a mass ratio of 1:3;

[0048] Figure 26 A contact angle test diagram of the anti-corrosion coating formed by mixing the anti-permeation anti-corrosion filler of the present application embodiment 4 and the epoxy-based coating in a mass ratio of 1:3;

[0049] Figure 27 A tensile strength diagram of the anti-corrosion coating formed by mixing the anti-permeation anti-corrosion filler of the present application embodiment 4 and the epoxy-based coating in a mass ratio of 1:3. DETAILED DESCRIPTION

[0050] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0051] In this document, the terms "left, right, up, down, front, back" and the like are established based on the positional relationship shown in the drawings, and the corresponding positional relationship may also change accordingly according to the different drawings, therefore, they cannot be understood as absolute limitations on the protection scope.

[0052] The method for preparing the anti-permeation anti-corrosion filler from waste rubber comprises the following steps:

[0053] S1: The waste rubber is crushed and sieved to obtain rubber particles with a particle size of 30-220 μm, and the rubber film thickness is adapted, that is, the particle size should not be too large to affect the hydrophobicity of the rubber film, and the particle size should not be too small to cause cracks in the coating. Then the rubber particles are sequentially subjected to acid washing, alkali washing and water washing to remove surface residual oil stains, dust and other impurities, and then the surface residual moisture is removed.

[0054] In step S1, the acid washing uses hydrochloric acid with pH<2 to remove basic substances on the surface of the rubber particles. The alkali washing uses sodium hydroxide solution with pH>12 to remove oil stains and acidic impurities on the surface of the rubber particles. The water washing uses distilled water to wash away the residual acid and alkali on the surface of the particles until the pH is in the range of 6.5-7.5.

[0055] S2: The rubber particles treated in step S1 are added into tetrachloroethylene with a mass concentration of not less than 90%, stirred for 3-24 h. The larger the particle size of the rubber particles, the longer the stirring time, which is conducive to the full wetting of the surface of the rubber particles by tetrachloroethylene. Then, the rubber particles are transferred into a sealed container and heated to 130℃ for constant temperature reaction. After the appearance of flocculent product on the surface of the rubber particles, the rubber particles are transferred into a filter screen.

[0056] In step S2, the flocculent product is the filamentous rubber after chlorination by tetrachloroethylene. During the crushing process of the waste and old rubber, the filamentous rubber formed on the surface of the rubber by stretching is chlorinated by tetrachloroethylene, and the filamentous rubber becomes the flocculent product. The flocculent product has too weak tensile strength, and thus needs to be treated completely.

[0057] S3: The flocculent product is dried, and then a blast rotary furnace is used to remove the flocculent product on the surface of the rubber particles. The rotation speed is adjusted until the particles are uniformly tumbled in the rotary furnace, and then the rotation speed is kept until no obvious flocculent product is blown out of the rotary furnace within 10 min and the mass of the rubber particles no longer changes, indicating that the surface of the rubber particles has been fully chlorinated and the chlorinated product (i.e. the flocculent product) on the surface of the rubber particles has been completely removed.

[0058] In step S3, the flocculent product can be dried by using drying methods such as blast drying, vacuum drying and freeze drying.

[0059] S4: The rubber particles treated in step S3 are again added into tetrachloroethylene with a mass concentration of not less than 90%, and then stirred again. The stirring time is at least 1 h. The larger the particle size of the rubber particles, the longer the stirring time, which is conducive to the full wetting of the surface of the rubber particles by tetrachloroethylene. Then, the rubber particles are heated to 130℃ and continuously stirred. Chlorine gas is bubbled during the stirring process. The bubbling rate is 1-3 bubbles per second. The continuous bubbling operation is performed for 6-12 h. The larger the rubber particles, the faster the bubbling rate and the longer the bubbling time.

[0060] In step S4, tetrachloroethylene as a solvent can promote the contact between chlorine gas and rubber molecules, and improve the reaction efficiency. The high temperature of 130℃ and the chlorine gas bubbling environment can ensure that the reaction is fully carried out.

[0061] S5: The rubber particles treated in step S4 are drained until no tetrachloroethylene drops within 3 min, and a rubber-based anti-permeation corrosion filler is obtained.

[0062] The rubber-based anti-permeation anticorrosive filler obtained in step S5 must be stored in a sealed container, and a certain amount of the same solvent as the coating must be added for moisturizing storage during storage. When used, it can be directly added to the base material coating in proportion and stirred uniformly.

[0063] The rubber-based anti-permeation anticorrosive filler prepared by the method of the present application is used in combination with a base material coating. The present embodiment provides an anticorrosive coating including the anti-permeation anticorrosive filler prepared by the method of the present application and an epoxy-based coating. The diluent used in the epoxy-based coating is an ethyl acetate diluent. Therefore, the filler has been soaked in the ethyl acetate diluent in advance before use.

[0064] The method for preparing an anti-permeation anticorrosive filler based on waste rubber according to the present application involves adding the treated waste rubber twice into tetrachloroethylene with a mass concentration of not less than 90%. In the first time, the tetrachloroethylene sufficiently wets and chlorinates the rubber particles. In the second time, chlorine gas is bubbled. The hydrogen atoms in the rubber molecules react with the chlorine gas in the tetrachloroethylene solvent. The chlorine gas gradually replaces the hydrogen atoms in the rubber molecules. The anti-permeation anticorrosive filler prepared by the method has improved chlorine content, which enhances the corrosion resistance. The anticorrosive coating made of the filler can effectively solve the problem of water molecule diffusion and effectively inhibit the permeation and migration of corrosion medium chloride ions, which can greatly improve the anti-permeation performance.

[0065] Example 1

[0066] The method for preparing an anti-permeation anticorrosive filler based on waste rubber includes the following steps:

[0067] S1: The waste rubber is crushed using a crusher, and then the crushed rubber particles are sieved using a screen. The rubber particles with a particle size greater than 50 μm are first sieved out, and the rubber particles with a particle size less than or equal to 50 μm are sieved again to remove the rubber particles with a particle size less than 30 μm, obtaining rubber particles with a particle size of 30-50 μm. Then, the obtained rubber particles are sequentially subjected to acid washing, alkali washing and water washing, and then the residual water on the surface of the rubber particles is removed.

[0068] S2: The rubber particles treated in step S1 are added to tetrachloroethylene with a mass concentration of not less than 90% and stirred for 3 h. Then, the rubber particles are transferred to a sealed container and heated to 130℃ for constant temperature reaction for 12 h. The surface of the rubber particles appears flocculated product. Then, the rubber particles are transferred to a filter screen.

[0069] S3: The flocculated product is dried by blowing air. Then, the rubber particles are placed in a blowing rotary furnace and rotated for 2 h to remove the flocculated product on the surface of the rubber particles.

[0070] S4: The rubber particles treated in step S3 are added to tetrachloroethylene with a mass concentration of not less than 90%, and stirred again for 1 h, and then heated to 130°C while continuously stirring, and bubbling operation is performed using chlorine gas during the stirring process, the bubbling operation rate is 1 bubble per second, and the continuous bubbling operation is performed for 6 h.

[0071] S5: The rubber particles treated in step S4 are drained until no tetrachloroethylene drips within 3 min, and a rubber-based anti-permeation anticorrosive filler is obtained.

[0072] The anti-permeation anticorrosive filler prepared in Example 1 is as shown in Figure 1 .

[0073] Referring to Figure 2 and Figure 4 , the anti-permeation anticorrosive filler prepared in Example 1 is soaked in ethyl acetate diluent for 12 h and then drained of the solvent, and the anti-permeation anticorrosive filler is mixed with an epoxy-based coating at a mass ratio (excluding volatile solvents) of 1:1 to prepare an anticorrosive coating. Referring to Figure 3 and Figure 7 , the anti-permeation anticorrosive filler prepared in Example 1 is soaked in ethyl acetate diluent for 12 h and then drained of the solvent, and the anti-permeation anticorrosive filler is mixed with an epoxy-based coating at a mass ratio (excluding volatile solvents) of 1:3 to prepare an anticorrosive coating.

[0074] Example 2

[0075] A method for preparing an anti-permeation anticorrosive filler from waste rubber includes the following steps:

[0076] S1: The waste rubber is crushed using a crusher, and then the crushed rubber particles are sieved using a screen, and the rubber particles with a particle size greater than 120 μm are sieved out first, and the rubber particles with a particle size less than or equal to 120 μm are sieved again, and the rubber particles with a particle size less than 100 μm are sieved out, and rubber particles with a particle size of 100-120 μm are obtained. Subsequently, the obtained rubber particles are sequentially subjected to acid washing, alkali washing and water washing treatment, and then the residual water on the surface of the rubber particles is removed.

[0077] S2: The rubber particles treated in step S1 are added to tetrachloroethylene with a mass concentration of not less than 90% and stirred for 12 h, and then transferred to a sealed container and heated to 130°C and reacted at a constant temperature for 18 h, and a flocculent product appears on the surface of the rubber particles, and then the rubber particles are transferred to a filter screen.

[0078] S3: The flocculent product is air-dried, and then the rubber particles are placed in a blast rotary furnace and rotated for 2 h to remove the flocculent product on the surface of the rubber particles.

[0079] S4: The rubber particles treated in step S3 are added to tetrachloroethylene with a mass concentration of not less than 90%, stirred again for 2 h, then heated to 130°C and continuously stirred, and bubbling operation is performed with chlorine gas during stirring, the bubbling rate is 2 bubbles per second, and the continuous bubbling operation is 9 h.

[0080] S5: The rubber particles treated in step S4 are drained until no tetrachloroethylene drips within 3 min, and a rubber-based anti-permeation corrosion filler is obtained.

[0081] Reference Figure 10 The anti-permeation corrosion filler prepared in Example 2 is soaked in ethyl acetate diluent for 12 h and the solvent is drained, and the anti-permeation corrosion filler is mixed with the epoxy-based coating at a mass ratio (excluding volatile solvents) of 1:1 to prepare a corrosion-resistant coating. Figure 13 The anti-permeation corrosion filler prepared in Example 2 is soaked in ethyl acetate diluent for 12 h and the solvent is drained, and the anti-permeation corrosion filler is mixed with the epoxy-based coating at a mass ratio (excluding volatile solvents) of 1:3 to prepare a corrosion-resistant coating.

[0082] Example 3

[0083] A method for preparing an anti-permeation corrosion filler from waste rubber, comprising the following steps:

[0084] S1: The waste rubber is crushed using a crusher, and then the crushed rubber particles are sieved using a screen, and the rubber particles with a particle size greater than 220 μm are sieved out first, and the rubber particles with a particle size less than or equal to 220 μm are sieved again, and the rubber particles with a particle size less than 200 μm are sieved out, and rubber particles with a particle size of 200-220 μm are obtained. Subsequently, the obtained rubber particles are sequentially subjected to acid washing, alkali washing and water washing treatment, and then the residual water on the surface of the rubber particles is removed.

[0085] S2: The rubber particles treated in step S1 are added to tetrachloroethylene with a mass concentration of not less than 90% and stirred for 20 h, then transferred to a sealed container and heated to 130°C and reacted at constant temperature for 22 h, and a flocculent product appears on the surface of the rubber particles, and then the rubber particles are transferred to a filter screen.

[0086] S3: The flocculent product is air-dried, and then the rubber particles are placed in a blast rotary furnace and rotated for 2 h to remove the flocculent product on the surface of the rubber particles.

[0087] S4: The rubber particles treated in step S3 are added to tetrachloroethylene with a mass concentration of not less than 90%, stirred again for 2 h, then heated to 130°C and continuously stirred, and bubbling operation is performed with chlorine gas during stirring, the bubbling rate is 2 bubbles per second, and the continuous bubbling operation is 9 h.

[0088] S5: draining the rubber particles treated in step S4 until no tetrachloroethylene drips within 3 minutes to obtain a rubber-based anti-permeation anticorrosive filler.

[0089] Reference Figure 16 The anti-permeation anticorrosive filler prepared in Example 3 was mixed with an epoxy-based coating at a mass ratio (excluding volatile solvents) of 1:1 to prepare an anticorrosive coating after the anti-permeation anticorrosive filler was soaked in ethyl acetate diluent for 12 hours and the solvent was drained. Figure 19 The anti-permeation anticorrosive filler prepared in Example 3 was mixed with an epoxy-based coating at a mass ratio (excluding volatile solvents) of 1:3 to prepare an anticorrosive coating after the anti-permeation anticorrosive filler was soaked in ethyl acetate diluent for 12 hours and the solvent was drained.

[0090] Example 4

[0091] A method for preparing an anti-permeation anticorrosive filler from waste rubber includes the following steps:

[0092] S1: The waste rubber is crushed using a crusher, and then the crushed rubber particles are sieved using a screen. Rubber particles with a particle size greater than 220 μm are first sieved out, and rubber particles with a particle size less than or equal to 220 μm are sieved again to remove rubber particles with a particle size less than 200 μm. The obtained rubber particles are then sequentially subjected to acid washing, alkali washing, and water washing, and then the residual water on the surface of the rubber particles is removed.

[0093] S2: The rubber particles treated in step S1 are added to tetrachloroethylene with a mass concentration of not less than 90% and stirred for 24 hours. Then, the rubber particles are transferred to a sealed container and heated to 130°C for 24 hours. A flocculated product appears on the surface of the rubber particles, and then the rubber particles are transferred to a filter screen.

[0094] S3: The flocculated product is air-dried, and then the rubber particles are placed in a blast rotary furnace for 2 hours to remove the flocculated product on the surface of the rubber particles.

[0095] S4: The rubber particles treated in step S3 are added to tetrachloroethylene with a mass concentration of not less than 90%, and stirred for 3 hours. Then, the rubber particles are heated to 130°C while being continuously stirred, and chlorine gas is bubbled at a rate of 3 bubbles per second during the stirring process. The bubbling operation is continuously performed for 12 hours.

[0096] S5: The rubber particles treated in step S4 are drained until no tetrachloroethylene drips within 3 minutes to obtain a rubber-based anti-permeation anticorrosive filler.

[0097] Reference Figure 22The anti-permeation anticorrosive filler prepared in Example 4 was mixed with the epoxy-based paint to prepare an anticorrosive paint at a mass ratio (excluding volatile solvents) of 1:1. The anticorrosive paint was prepared by immersing the anti-permeation anticorrosive filler in the ethyl acetate diluent for 12 h and draining the solvent. Figure 25 The anti-permeation anticorrosive filler prepared in Example 4 was mixed with the epoxy-based paint to prepare an anticorrosive paint at a mass ratio (excluding volatile solvents) of 1:3. The anticorrosive paint was prepared by immersing the anti-permeation anticorrosive filler in the ethyl acetate diluent for 12 h and draining the solvent.

[0098] In order to detect the effect of the anti-permeation anticorrosive filler prepared in Examples 1-4, the anti-permeation anticorrosive filler prepared in Examples 1-4 was mixed with the epoxy-based paint to prepare an anticorrosive paint at a mass ratio (excluding volatile solvents) of 1:1 and 1:3, and then the prepared anticorrosive paint was subjected to contact angle test and tensile strength test, and the test results are shown in Table 1. The contact angle test used a contact angle measuring instrument, and the tensile strength test used a universal testing machine.

[0099] The contact angle test process was as follows: first, the test instrument was calibrated with a ceramic calibration rod, and then the surface tension value of the distilled water sample used for testing was tested at a test temperature of 25°C, and the standard value was 71.97 mN / m. The test result was that the average of the left and right surface tension values of the distilled water sample was 71.69 mN / m, and the distilled water sample met the requirements. The test sample was cut into a size of 1x3 cm, and was fixed with a clamp. The test sample was placed on the sample table. The sample table was moved to an appropriate height, so that the surface of the test sample was close to the tip of the needle. A droplet was formed on the needle, and the needle was stably suspended. The sample table was slowly moved upwards until the surface of the test sample just contacted the bottom of the droplet, and the droplet was detached from the needle. After the droplet was detached from the needle, the image was quickly captured, saved and the test data was exported.

[0100] The contact angle test diagram of the anticorrosive paint formed by mixing the anti-permeation anticorrosive filler of Example 1 with the epoxy-based paint at a mass ratio of 1:1 is shown in FIG. 1. Figure 5 The contact angle test diagram of the anticorrosive paint formed by mixing the anti-permeation anticorrosive filler with the epoxy-based paint at a mass ratio of 1:3 is shown in FIG. 2. Figure 8 The contact angle test diagram of the anticorrosive paint formed by mixing the anti-permeation anticorrosive filler of Example 2 with the epoxy-based paint at a mass ratio of 1:1 is shown in FIG. 3. Figure 11 The contact angle test diagram of the anticorrosive paint formed by mixing the anti-permeation anticorrosive filler with the epoxy-based paint at a mass ratio of 1:3 is shown in FIG. 4. Figure 14 The contact angle test diagram of the anticorrosive paint formed by mixing the anti-permeation anticorrosive filler of Example 3 with the epoxy-based paint at a mass ratio of 1:1 is shown in FIG. 5. Figure 17 The contact angle test diagram of the anticorrosive paint formed by mixing the anti-permeation anticorrosive filler with the epoxy-based paint at a mass ratio of 1:3 is shown in FIG. 6. Figure 20The contact angle test chart of the anti-corrosion coating formed by mixing the anti-permeation anti-corrosion filler of Example 4 and the epoxy-based coating at a mass ratio of 1:1 is referred to Figure 23 The contact angle test chart of the anti-corrosion coating formed by mixing the anti-permeation anti-corrosion filler and the epoxy-based coating at a mass ratio of 1:3 is referred to Figure 26 .

[0101] The anti-permeation performance of the anti-corrosion coating and the contact angle are closely related. Generally, the greater the contact angle, the worse the wettability of the coating to water, the less likely the water penetrates into the micro-cracks of the coating, and the better the anti-permeation performance of the coating. Especially in the marine environment with high salt and high humidity, the coating must have strong anti-permeation performance. As can be seen from the contact angle data in Table 1, the anti-corrosion coating prepared from the anti-permeation anti-corrosion filler of the present application has excellent anti-permeation performance.

[0102] The tensile strength test process is as follows: first, ensure that the surface of the test sample is flat, free of bubbles, cracks, delamination and other defects. The test sample is cut into a size of 2x5 cm. The test sample is tested according to GB / T 528-2009 (dumbbell-shaped sample), the thickness of the adhesive film sample is 1.7 mm, the width of the narrow parallel section is 10 mm, and the initial gauge length is 27 mm. The test sample is clamped in the upper clamp, and then the lower clamp is moved to the appropriate clamping position to clamp the lower end of the test sample. Start the universal testing machine, slowly and uniformly load, observe the force measuring pointer and draw the curve, record the data and export the test data.

[0103] The tensile strength chart of the anti-corrosion coating formed by mixing the anti-permeation anti-corrosion filler of Example 1 and the epoxy-based coating at a mass ratio of 1:1 is referred to Figure 6 The tensile strength chart of the anti-corrosion coating formed by mixing the anti-permeation anti-corrosion filler and the epoxy-based coating at a mass ratio of 1:3 is referred to Figure 9 The tensile strength chart of the anti-corrosion coating formed by mixing the anti-permeation anti-corrosion filler of Example 2 and the epoxy-based coating at a mass ratio of 1:1 is referred to Figure 12 The tensile strength chart of the anti-corrosion coating formed by mixing the anti-permeation anti-corrosion filler and the epoxy-based coating at a mass ratio of 1:3 is referred to Figure 15 The tensile strength chart of the anti-corrosion coating formed by mixing the anti-permeation anti-corrosion filler of Example 3 and the epoxy-based coating at a mass ratio of 1:1 is referred to Figure 18 The tensile strength chart of the anti-corrosion coating formed by mixing the anti-permeation anti-corrosion filler and the epoxy-based coating at a mass ratio of 1:3 is referred to Figure 21 The tensile strength chart of the anti-corrosion coating formed by mixing the anti-permeation anti-corrosion filler of Example 4 and the epoxy-based coating at a mass ratio of 1:1 is referred to Figure 24 The tensile strength chart of the anti-corrosion coating formed by mixing the anti-permeation anti-corrosion filler and the epoxy-based coating at a mass ratio of 1:3 is referred to Figure 27 .

[0104] In the high-salt and high-humidity environment, when the temperature changes, the expansion coefficients of the substrate and the coating are different, and the tensile strength test mainly tests two aspects of the performance of the coating: first, good tensile strength and elongation at break are conducive to inhibiting the formation of microcracks on the surface of the coating; second, the coating with high tensile strength is not easy to fall off in a large range. From the tensile strength data in Table 1, it can be known that the anticorrosive coating prepared from the anti-infiltration anticorrosive filler of the present application is not easy to form microcracks on the surface and is not easy to fall off in a large range.

[0105]

[0106] The above embodiments only illustrate the basic principles and characteristics of the present application, but are not limited by the above embodiments, and it should be understood that various changes and modifications can be made to the present application without departing from the spirit and scope of the present application, and these changes and modifications all fall within the scope of the present application. The scope of protection of the present application is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a permeation resistant anticorrosive filler using waste rubber, characterized by, The method comprises the following steps: S1: crushing and sieving waste rubber to obtain rubber particles, and then sequentially performing acid washing, alkali washing and water washing on the rubber particles, and removing surface residual moisture; S2: adding the rubber particles treated in step S1 into tetrachloroethylene, stirring, then transferring into a sealed container, heating to 130℃ and constant temperature reaction, and transferring into a filter screen after flocculent product appears on the surface of the rubber particles; S3: drying the flocculent product, and then removing the flocculent product on the surface of the rubber particles by using a blast rotary furnace; S4: adding the rubber particles treated in step S3 into tetrachloroethylene again, stirring again, then heating to 130℃ and continuously stirring, and performing bubbling operation in the stirring process; S5: draining the rubber particles treated in step S4 to obtain rubber-based anti-permeation and anti-corrosion fillers.

2. The method for preparing anti-permeation and anti-corrosion filler using waste and old rubber according to claim 1, characterized in that, In step S1, the particle size of the rubber particles is 30-220 μm.

3. The method of claim 1, wherein the waste rubber is used to prepare the impermeable anticorrosive filler. In step S1, hydrochloric acid with pH<2 is used to perform acid washing on the rubber particles.

4. The method of claim 1, wherein the waste rubber is used to prepare the impermeable anticorrosive filler. In step S1, sodium hydroxide solution with pH>12 is used to perform alkali washing on the rubber particles.

5. The method of claim 1, wherein the waste rubber is used to produce the anti-permeation and anti-corrosion filler. In step S2 or step S4, the mass concentration of tetrachloroethylene is not less than 90%.

6. The method of claim 1, wherein the waste rubber is used to prepare the impermeable anticorrosive filler. In step S2, the stirring time is 3-24 h.

7. The method of claim 1, wherein the waste rubber is used to produce the anti-permeation and anti-corrosion filler. In step S3, the drying method is blast drying, vacuum drying or freeze drying.

8. The method of claim 1, wherein the waste rubber is used to produce the anti-permeation and anti-corrosion filler. In step S4, the stirring time is at least 1 h.

9. The method of claim 1, wherein the waste rubber is used to produce the anti-permeation and anti-corrosion filler. In step S4, chlorine is used to perform bubbling operation in the stirring process, the bubbling operation rate is 1-3 bubbles per second, and the continuous bubbling operation time is 6-12 h.

10. A corrosion protection coating, characterized in that The anti-permeation and anti-corrosion fillers prepared by using the method according to any one of claims 1-9 and an epoxy-based coating, wherein the diluent used by the epoxy-based coating is ethyl acetate diluent.

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