A self-repairing radiation resistant coating paint, a radiation resistant coating and a preparation method thereof

Abstract

The application provides a self-repairing radiation resistant coating paint, a radiation resistant coating and a preparation method thereof, the self-repairing radiation resistant coating paint comprises component A and component B with a mass ratio of 1:(0.5-1.5), the component A comprises 8-40 parts of amino polysiloxane, 8-40 parts of a filler and 0-5 parts of a wetting dispersant, and the component B is a modified epoxy resin. The amino polysiloxane is modified by an ammonium salt side chain, and the modified epoxy resin is a calixarene modification. The application adopts silicone resin and epoxy resin with excellent radiation resistance as film-forming substances, synthesizes polysiloxane with a side chain ammonium salt and calixarene modified epoxy resin, improves the compatibility of the two resins by using the host-guest interaction between calixarene and the ammonium salt, and realizes self-repairing of the radiation resistant coating. The host-guest interaction does not require additional heat or pH conditions, and the effect is not affected by a humid environment.

Description

Technical Field

[0001] The present invention relates to the technical field of coating protection, and in particular to a self-repairing anti-radiation coating, an anti-radiation coating and a preparation method thereof. Background Art

[0002] Nuclear power is an environmentally friendly and highly efficient new energy source. However, with the increasing number of nuclear power plant construction projects, concerns about nuclear power safety are growing. The high energy of radiation can easily destroy chemical bonds, accelerating material aging and shortening the normal service life of equipment. Therefore, coatings with radiation resistance are required for use in nuclear power plants. As a crucial protective layer for nuclear power plant equipment, radiation-resistant coatings can extend the service life of equipment and enhance nuclear power safety. Silicone resins are polysiloxane systems with a Si-O-Si backbone, with organic groups attached to the silicon atoms. The high bond energy of the silicon-oxygen bonds in the silicone resin backbone imparts excellent heat resistance, radiation resistance, and weathering resistance. The presence of benzene rings in the epoxy resin backbone also contributes to its radiation resistance, making it a common resin used in radiation-resistant coatings. However, radiation-resistant coatings are inevitably susceptible to mechanical damage during use, shortening their service life and increasing the cost of material repair and replacement.

[0003] Self-healing coatings are functional coatings that have the ability to self-repair after damage, or under certain external conditions. Self-healing coatings can be divided into two main categories: externally assisted self-healing and intrinsic self-healing. Intrinsic self-healing utilizes reversible chemical bonds to achieve multiple repairs, overcoming the shortcomings of externally assisted self-healing. However, most reversible chemical reactions require energy input (heat, light) or pH changes, limiting the material's application. Of the few truly self-healing polymer materials, most are based on water-sensitive hydrogen bonds.

[0004] CN201811478430.9 discloses an anti-radiation building coating and a preparation method thereof. The anti-radiation building coating comprises component A and component B in a mass ratio of 1:1.5 and an additive accounting for 1%-2% of the total mass of component A and component B. Component A comprises, by mass, 30 parts of epoxy resin, 5-10 parts of silicone resin, 0.1 part of catalyst, and 10-15 parts of dispersant. Component B comprises, by mass, 10-15 parts of aldehyde-ketone resin, 2-5 parts of radiation inhibitor, 0.5-1.5 parts of graphene, and 3-5 parts of pigments and fillers. The coating can significantly improve the radiation resistance of the coating itself, and at the same time improve the crack resistance of the coating after it is applied to the surface of the building. It is not easy to crack or fall off. The coating itself has the function of self-healing and repairing. Even if cracking occurs, it will heal quickly to prevent further cracking, thereby always ensuring the overall radiation resistance of the coating. The repair method adopted is external self-repair, plus the self-healing repair ball self-repair method. This method of self-repair is a one-time self-repair, which is irreversible and unsustainable.

[0005] CN201710330204.5 discloses a calixarene-type photocurable polyurethane resin and a self-repairing coating prepared therefrom. The calixarene-type photocurable polyurethane resin is prepared by the following steps: (1) preparing an isocyanate-terminated prepolymer; (2) preparing an isocyanate-semi-terminated prepolymer; and (3) introducing a calixarene monomer into the isocyanate-semi-terminated prepolymer prepared in step (2) to prepare the calixarene-type photocurable polyurethane. The present invention grafts photocurable coumarins, double bonds, and other groups onto calixarene to prepare a calixarene-type photocurable self-repairing polyurethane resin. While ensuring good self-repairing performance, it also greatly improves the hardness of the self-repairing coating. Summary of the Invention

[0006] The existing technology addresses the high cost of repairing and replacing radiation-resistant coatings, and the fact that conventional self-healing coatings often require external conditions to respond or are sensitive to water, which affects their self-healing effects. The present invention provides a self-healing radiation-resistant coating, a radiation-resistant coating, and a preparation method thereof. The coating comprises an aminopolysiloxane with an ammonium salt-modified side chain and a calixarene-modified epoxy resin. The coating utilizes a calixarene supramolecular system with a benzene ring structure. The high bond energy of the benzene ring structure ensures its stability under radiation. Furthermore, the host-guest interaction between the calixarene and the ammonium salt enables self-healing without the need for external conditions.

[0007] A self-repairing anti-radiation coating, comprising component A and component B in a mass ratio of 1:(0.5-1.5), wherein component A comprises 8-40 parts of aminopolysiloxane, 8-40 parts of filler, and 0-5 parts of wetting dispersant, and component B is a modified epoxy resin;

[0008] The aminopolysiloxane is obtained by reacting a silane coupling agent with aminosilane under catalyst conditions;

[0009] The amount of the above-mentioned silane coupling agent is 10-30 parts, the amount of aminosilane is 2-10 parts, and the amount of the catalyst is 0.1-1 part;

[0010] The modified epoxy resin is obtained by reacting calixarene with epoxy resin;

[0011] The amount of the calixarene is 2-15 parts, and the amount of the epoxy resin is 5-30 parts. The epoxy resin is a multifunctional epoxy resin.

[0012] The usage ratio of the calixarene to the amino group in the aminopolysiloxane is (1-1.2):1.

[0013] The silane coupling agent is any one of octamethylcyclotetrasiloxane (D4), methyltrimethoxysilane (MTMS), methyltriethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, and dimethyldiethoxysilane, or a mixture of any two or more in any proportion.

[0014] The above-mentioned aminosilane is any one of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-propyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, N-β(aminoethyl)-γ-aminopropylmethyldiethoxysilane, and aminoethylaminopropyltrimethoxysilane, or a mixture of two or more in any proportion;

[0015] The catalyst is any one of potassium hydroxide, sodium hydroxide, aqueous ammonia, sodium ethoxide, and sodium methoxide.

[0016] The filler is any one of rutile titanium dioxide, quartz powder, talc powder, and calcium carbonate, or a mixture of two or more of the above in any proportion.

[0017] The above-mentioned calixarene is any one of calix[4]arene, 4-sulfonylcalix[4]arene, and 4-tert-butylcalix[4]arene, or a mixture of two or more of them in any proportion; and the above-mentioned epoxy resin is a multifunctional epoxy resin.

[0018] The modified epoxy resin also includes a diluent, which is any one of isopropyl alcohol, n-butanol, propylene glycol methyl ether, and xylene, or a mixture of two or more in any proportion; the amount of the diluent is 5-20 parts. Without the diluent, the viscosity of the paint is too high, which is not conducive to construction, and the film is not easy to level.

[0019] The reaction temperature of the aminopolysiloxane preparation process is 120-150°C and the reaction time is 5-10h; the reaction temperature of the modified epoxy resin preparation process is 100-150°C and the reaction time is 4-6h. The modified epoxy resin preparation process can be catalyzed by organic base or not.

[0020] The synthesis steps for component A are as follows: 10-30 parts of one or more silane coupling agents, 2-10 parts of aminosilane, and 0.1-1 part of catalyst are sequentially added to a four-necked flask purged with nitrogen. After mixing thoroughly, the mixture is heated in a constant temperature oil bath to the desired reaction temperature (120-150°C) with stirring for 5-10 hours. The mixture is then neutralized with acid to obtain an aminopolysiloxane with ammonium salt-modified side chains. Subsequently, 8-40 parts of filler and 0-5 parts of a wetting and dispersing agent are added and mixed thoroughly.

[0021] The specific steps for synthesizing component B are as follows: adding 2-15 parts of a phenolic hydroxyl group-containing compound calixarene to 5-30 parts of an epoxy resin, stirring and reacting for more than 4-5 hours to obtain a modified epoxy resin; or first adding 2-15 parts of a phenolic hydroxyl group-containing compound calixarene to 5-30 parts of an epoxy resin, and then adding 5-20 parts of a diluent, stirring and reacting for more than 4-5 hours to obtain a modified epoxy resin.

[0022] The anti-radiation coating is obtained using the above-mentioned self-repairing anti-radiation coating. The preparation method of the coating includes the following steps: after preparing component A and component B, they are fully mixed and stirred for 25-35 minutes to obtain the self-repairing anti-radiation coating; the above-mentioned self-repairing anti-radiation coating is applied to the surface of the protective material and cured at room temperature for 7-8 days to obtain the above-mentioned anti-radiation coating.

[0023] Compared with the prior art, this application has the following advantages:

[0024] (1) The present application uses silicone resin and epoxy resin with excellent radiation resistance as film-forming materials, synthesizes polysiloxane with side chain ammonium salt and epoxy resin modified with calixarene, and utilizes the host-guest interaction between calixarene and ammonium salt to improve the compatibility of the two resins, while realizing the self-repair of the radiation-resistant coating; this host-guest interaction does not require external heating or pH conditions, and a humid environment will not affect its effect.

[0025] (2) The filler used is rutile titanium dioxide with radiation resistance, which enhances radiation resistance, increases coating hardness and hiding power, and the dispersant enhances the dispersion ability of the filler.

[0026] (3) The coating self-healing effect is achieved through the host-guest interaction between aminopolysiloxane and modified epoxy. At the same time, polysiloxane itself has a high bond energy and is radiation-resistant with the radiation-resistant filler rutile titanium dioxide, achieving a combined radiation-resistant effect. The synergistic cooperation of the various components greatly improves the self-healing performance while ensuring good radiation resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The figures are the effects of the samples of each embodiment and comparative example after irradiation;

[0028] Figure 2 The figures are the effects of scratches on the samples of each embodiment and comparative example after 24 hours. DETAILED DESCRIPTION

[0029] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0030] In the following examples and comparative examples, the reaction conditions not specifically described were all operated at room temperature. In each example and comparative example, the coating was dried and cured for 24 hours after application to obtain the coating.

[0031] Example 1

[0032] Component A was synthesized as follows: 20 parts octamethylcyclotetrasiloxane D4, 5 parts methyltriethoxysilane, 10 parts γ-aminopropyltrimethoxysilane, and 0.1 parts KOH were added sequentially to a four-necked flask purged with nitrogen. After mixing thoroughly, the mixture was heated to 140°C in a constant-temperature oil bath with stirring for 8 hours. The reaction was then neutralized with acetic acid to terminate the reaction. Subsequently, 15 parts rutile titanium dioxide, 5 parts talc, and 2 parts wetting and dispersing agent were added.

[0033] The synthesis process of component B is as follows: 7 parts of 4-tert-butylcalix[4]arene are added to 15 parts of epoxy resin and 7 parts of propylene glycol methyl ether, and stirred at 110°C for 6 hours to obtain a modified epoxy resin.

[0034] Mix component A and component B at a ratio of 2:1, stir thoroughly for 30 minutes and then apply.

[0035] Example 2

[0036] Component A was synthesized as follows: 15 parts of D4, 5 parts of methyltrimethoxysilane (MTMS), 5 parts of γ-aminopropyltrimethoxysilane, and 0.1 parts of KOH were added sequentially to a four-necked flask purged with nitrogen. After mixing thoroughly, the mixture was heated to 130°C in a constant-temperature oil bath with stirring for 6 hours. The reaction was then neutralized with acetic acid to terminate the reaction. Subsequently, 16 parts of rutile titanium dioxide, 4 parts of talc, and 2 parts of a wetting and dispersing agent were added.

[0037] The synthesis process of component B is as follows: 3 parts of calix[4]arene are added to 10 parts of epoxy resin and 5 parts of propylene glycol methyl ether, and stirred at 150°C for more than 4 hours to obtain modified epoxy resin.

[0038] Mix component A and component B at a ratio of 1:1.2, stir thoroughly for 30 minutes and then apply.

[0039] Example 3

[0040] Component A was synthesized as follows: 15 parts D4, 3 parts MTMS, 5 parts γ-aminopropylmethyldimethoxysilane, and 0.2 parts KOH were added sequentially to a four-necked flask purged with nitrogen. After mixing thoroughly, the mixture was heated to 140°C in a constant-temperature oil bath with stirring for 5 hours. The reaction was then neutralized with acetic acid to terminate the reaction. Subsequently, 10 parts calcium carbonate, 10 parts rutile titanium dioxide, and 2 parts wetting and dispersing agent were added.

[0041] The synthesis process of component B is as follows: 7 parts of calix[4]arene are added to 20 parts of epoxy resin and 5 parts of propylene glycol methyl ether, and stirred at 100°C for 6 hours to obtain modified epoxy resin.

[0042] Mix component A and component B at a ratio of 1:1, stir thoroughly for 30 minutes and then apply.

[0043] Example 4

[0044] Component A was synthesized as follows: 15 parts D4, 3 parts MTMS, 5 parts γ-aminopropylmethyldimethoxysilane, and 0.2 parts KOH were added sequentially to a four-necked flask purged with nitrogen. After mixing thoroughly, the mixture was heated to 140°C in a constant-temperature oil bath with stirring for 5 hours. The reaction was then neutralized with acetic acid to terminate the reaction. Subsequently, 10 parts calcium carbonate, 10 parts rutile titanium dioxide, and 2 parts wetting and dispersing agent were added.

[0045] The synthesis process of component B is as follows: 5 parts of calix[5]arene are added to 30 parts of epoxy resin, 10 parts of propylene glycol methyl ether, and 10 parts of xylene, and stirred at 140°C for 4 hours to obtain a modified epoxy resin.

[0046] Mix component A and component B at a ratio of 1:1.5, stir thoroughly for 30 minutes and apply.

[0047] Example 5

[0048] Component A was synthesized as follows: 15 parts D4, 3 parts MTMS, 5 parts γ-aminopropylmethyldimethoxysilane, and 0.2 parts KOH were added sequentially to a four-necked flask purged with nitrogen. After mixing thoroughly, the mixture was heated to 140°C in a constant-temperature oil bath with stirring for 5 hours. The reaction was then neutralized with acetic acid to terminate the reaction. Subsequently, 10 parts calcium carbonate, 10 parts rutile titanium dioxide, and 2 parts wetting and dispersing agent were added.

[0049] The synthesis process of component B is as follows: 2 parts of calix[5]arene are added to 10 parts of epoxy resin and 5 parts of xylene, and stirred at 140°C for 4 hours to obtain modified epoxy resin.

[0050] Mix component A and component B at a ratio of 1:1.5, stir thoroughly for 30 minutes and then apply.

[0051] Example 6

[0052] Component A was synthesized as follows: 15 parts D4, 3 parts MTMS, 5 parts γ-aminopropylmethyldimethoxysilane, and 0.2 parts KOH were added sequentially to a four-necked flask purged with nitrogen. After mixing thoroughly, the mixture was heated to 140°C in a constant-temperature oil bath with stirring for 5 hours. The reaction was then neutralized with acetic acid to terminate the reaction. Subsequently, 10 parts rutile titanium dioxide and 2 parts wetting and dispersing agent were added.

[0053] The synthesis process of component B is as follows: 15 parts of calix[5]arene are added to 30 parts of epoxy resin and 20 parts of xylene, and stirred at 140°C for 4 hours to obtain modified epoxy resin.

[0054] Mix component A and component B at a ratio of 1:0.5, stir thoroughly for 30 minutes and then apply.

[0055] Comparative Example 1

[0056] The difference between Comparative Example 1 and Example 1 is that the epoxy resin in component B is not modified with calixarene.

[0057] Component A was synthesized as follows: 20 parts of D4, 5 parts of methyltriethoxysilane, 10 parts of γ-aminopropyltrimethoxysilane, and 0.1 parts of KOH were added sequentially to a four-necked flask purged with nitrogen. After mixing thoroughly, the mixture was heated to 140°C in a constant-temperature oil bath with stirring for 8 hours. The reaction was then neutralized with acetic acid to terminate the reaction. Subsequently, 15 parts of rutile titanium dioxide, 5 parts of talc, and 2 parts of a wetting and dispersing agent were added.

[0058] The synthesis process of component B is as follows: 7 parts of 4-tert-butylcalix[4]arene are added to 15 parts of epoxy resin and 7 parts of propylene glycol methyl ether, and stirred at 140°C for 7 hours to obtain a modified epoxy resin.

[0059] Mix component A and component B at a ratio of 2:1, stir thoroughly for 30 minutes and then apply.

[0060] Comparative Example 2

[0061] The difference between Comparative Example 2 and Example 1 is that the polysiloxane in component A does not contain a side chain ammonium salt (a siloxane without a side chain ammonium salt cannot cure epoxy resin, and only the siloxane itself can be cured).

[0062] The polysiloxane synthesis process is as follows: 20 parts of D4, 5 parts of methyltriethoxysilane, and 0.1 parts of KOH were added sequentially to a four-necked flask purged with nitrogen. After mixing thoroughly, the mixture was heated to 140°C in a constant-temperature oil bath with stirring for 8 hours. The reaction was then neutralized with acetic acid to terminate the reaction. Subsequently, 15 parts of rutile titanium dioxide, 5 parts of talc, and 2 parts of a wetting and dispersing agent were added. The mixture was dried and solidified.

[0063] Test Example 1: Performance Test:

[0064] The panels were made according to standard requirements. The concrete blocks were sized at 20 cm × 10 cm × 4 cm. After degreasing and dust removal, the concrete blocks were sealed with epoxy putty and the surfaces were repaired. 24 hours later, the coatings prepared in the examples and comparative examples (dry film thickness of 90-120 μm) were sprayed on. The panels were cured at room temperature for 14 days. The appearance of the coatings was observed and recorded. A 1-2 mm wide scratch was made on the coatings with a knife. The panels were left at room temperature for 24 hours and the appearance of the coatings was recorded. The water resistance of the coatings was tested according to GB / T 1733-1993. Other liquids were tested by spraying. Salt spray resistance was tested according to GB / T 10125-2012. Moisture and heat resistance was tested according to GB / T 1740-2007. Impact resistance was tested according to GB / T 1732-2020. Radiation resistance was tested according to NB / T 20133.3-2012.

[0065] The test results are shown in Table 1 below:

[0066] Table 1:

[0067]

[0068]

[0069] According to the test results in the above table, each embodiment of the present application has good radiation resistance and scratch self-repair function. Figure 1 and Figure 2 As shown. None of the examples and comparative samples showed significant cracking after irradiation. This is due to the high bond energy of polysiloxane, which exhibits good radiation resistance with epoxy resin. Furthermore, the addition of epoxy resin provides some toughness to the polysiloxane, making the film less prone to cracking. In coatings with amino and calixarene modified structures (Examples 1-6), scratches were self-healed after 24 hours through the host-guest interaction between the two, with no visible scratches.

[0070] However, in Comparative Examples 1 and 2 without amino group and calixarene modified structures, there is no host-guest interaction, the scratch is irreversible, and still exists after 24 hours.

[0071] The embodiments of the present application not only achieve self-repair of the coating by utilizing the supramolecular effect of calixarene and amino groups, but also have no significant impact on the water resistance, acid and alkali resistance, salt spray resistance and other properties of the silicone-epoxy composite coating, avoiding the water sensitivity and acid and alkali sensitivity of self-repairing methods such as hydrogen bonding and metal ion chelation, and is more conducive to the durability of the coating.

[0072] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A self-repairing anti-radiation coating, characterized by: The self-repairing anti-radiation coating comprises component A and component B in a mass ratio of 1:(0.5-1.5), wherein component A comprises 8-40 parts of aminopolysiloxane, 8-40 parts of filler, and 0-5 parts of wetting dispersant, and component B is a modified epoxy resin; The aminopolysiloxane is a polysiloxane with an ammonium salt modified side chain obtained by reacting a silane coupling agent with aminosilane under catalyst conditions and then neutralizing with an acid; The amount of the silane coupling agent is 10-30 parts, the amount of aminosilane is 2-10 parts, and the amount of the catalyst is 0.1-1 part; The modified epoxy resin is obtained by reacting calixarene with epoxy resin; The calixarene structure contains phenolic hydroxyl groups; The amount of the calixarene is 2-15 parts, and the amount of the epoxy resin is 5-30 parts.

2. The self-repairing anti-radiation coating according to claim 1, characterized in that: The silane coupling agent is any one of octamethylcyclotetrasiloxane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, and dimethyldiethoxysilane, or a mixture of two or more in any proportion.

3. The self-repairing anti-radiation coating according to claim 1, characterized in that: The aminosilane is any one of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldiethoxysilane, and aminoethylaminopropyltrimethoxysilane, or a mixture of two or more in any proportion.

4. The self-repairing anti-radiation coating according to claim 1, characterized in that: The catalyst is any one of potassium hydroxide, sodium hydroxide, aqueous ammonia, sodium ethoxide and sodium methoxide.

5. The self-repairing anti-radiation coating according to claim 1, characterized in that: The filler is any one of rutile titanium dioxide, quartz powder, talc powder, and calcium carbonate, or a mixture of two or more of the above in any proportion.

6. The self-repairing anti-radiation coating according to claim 1, characterized in that: The calixarene is any one of calix[4]arene, 4-sulfonylcalix[4]arene, and 4-tert-butylcalix[4]arene, or a mixture of two or more of them in any proportion; and the epoxy resin is a multifunctional epoxy resin.

7. The self-repairing anti-radiation coating according to claim 1, characterized in that: The modified epoxy resin further comprises a diluent, which is any one of isopropyl alcohol, n-butanol, propylene glycol methyl ether, and xylene, or a mixture of two or more in any proportion; the amount of the diluent is 5-20 parts.

8. The self-repairing anti-radiation coating according to claim 1, characterized in that: The reaction temperature of the aminopolysiloxane preparation process is 120-150° C., and the reaction time is 5-10 hours; the reaction temperature of the modified epoxy resin preparation process is 100-150° C., and the reaction time is 4-6 hours.

9. A radiation-resistant coating, characterized in that: The self-repairing anti-radiation coating is prepared using the self-repairing anti-radiation coating according to any one of claims 1 to 8.

10. The method for preparing a radiation-resistant coating according to claim 9, characterized in that: The following steps are involved: After component A and component B are prepared, they are fully mixed and stirred for 25-35 minutes to obtain a self-repairing anti-radiation coating; The self-repairing anti-radiation coating is applied to the surface of the protective material and cured at room temperature for 7-8 days to obtain the anti-radiation coating.

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