Fireproof coating for radiation control area as well as preparation method and application of fireproof coating

Abstract

The invention relates to the technical field of coatings and provides a fireproof coating for a radiation control area as well as a preparation method and application of the fireproof coating. The fireproof coating for the radiation control area comprises the following components in parts by weight: 40-50 parts of epoxy resin, 12-18 parts of a curing agent, 5-10 parts of filler, 8-16 parts of a flame retardant, 0.1-1 part of a dispersing agent, 0.1-1 part of a defoaming agent, 1-5 parts of carboxyl-terminated hyperbranched polyester and 1-5 parts of polyetherimide. According to the technical scheme, the problems of relatively low bonding strength and relatively poor radiation resistance of fireproof coatings in related technologies are solved.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, and in particular to a fire retardant coating for radiation control areas and a preparation method and application thereof. Background Art

[0002] Although the existing fire retardant coatings have excellent fire retardant properties, they have the problem of insufficient bonding strength, which makes it very easy for the fire retardant coatings to peel off and crack during use. Once a fire occurs, the coating cannot be firmly attached to the substrate, and it cannot effectively form a heat-insulating and oxygen-isolating protective layer. The flame and heat will quickly penetrate the coating, which is not conducive to the protection of the substrate; at the same time, due to the special environmental factors in the radiation control area, higher requirements are placed on the radiation resistance of the fire retardant coating. When high-intensity ionizing radiation, such as α, β, γ rays and neutron radiation, continuously acts on the fire retardant coating, these radiations will destroy the organic molecular structure in the coating, causing it to undergo chemical reactions such as cross-linking and degradation, resulting in a significant decrease in the performance of the coating, and the inability to effectively bind the various components in the coating tightly together, resulting in defects such as blistering and shedding of the coating, increasing maintenance costs, shortening the service life of the coating, and reducing the overall safety and reliability of the fire retardant coating when used in radiation control areas.

[0003] Therefore, the problems of insufficient bonding strength and poor radiation resistance of fire retardant coatings need to be solved urgently, and it is necessary to further develop a fire retardant coating with high bonding strength and radiation resistance. Summary of the invention

[0004] The present invention provides a fire retardant coating for radiation control areas and a preparation method and application thereof, which solve the problems of low bonding strength and poor radiation resistance of the fire retardant coating in the related art.

[0005] The technical solution of the present invention is as follows: The present invention provides a fire retardant coating for a radiation control area, comprising the following components in parts by weight: 40-50 parts of epoxy resin, 12-18 parts of curing agent, 5-10 parts of filler, 8-16 parts of flame retardant, 0.1-1 part of dispersant, 0.1-1 part of defoamer, 1-5 parts of terminal carboxyl hyperbranched polyester, and 1-5 parts of polyetherimide.

[0006] As a further technical solution, the number of carboxyl groups in the carboxyl-terminated hyperbranched polyester is 12 to 48 mol.

[0007] As a further technical solution, the mass ratio of the carboxyl-terminated hyperbranched polyester to the polyetherimide is <1.

[0008] In the present invention, a terminal carboxyl hyperbranched polyester having a carboxyl number of 12 to 48 mol is synergistically prepared with polyetherimide, and the mass ratio of the terminal carboxyl hyperbranched polyester to the polyetherimide is less than 1, thereby further improving the bonding strength of the fire retardant coating and also improving the wear resistance of the fire retardant coating.

[0009] As a further technical solution, the mass ratio of the carboxyl-terminated hyperbranched polyester to the polyetherimide is 2:3-4.

[0010] In the present invention, carboxyl-terminated hyperbranched polyester and polyetherimide are added in a mass ratio of 2:3-4 to the epoxy resin-based fire-retardant coating, thereby further improving the bonding strength of the fire-retardant coating.

[0011] As a further technical solution, the filler includes one or more of white carbon black, wollastonite powder, and titanium dioxide; The flame retardant comprises ammonium polyphosphate, melamine and pentaerythritol; The mass ratio of the ammonium polyphosphate, melamine and pentaerythritol is 2-4:1:1; The carboxyl-terminated hyperbranched polyester includes an aromatic carboxyl-terminated hyperbranched polyester.

[0012] As a further technical solution, the curing agent includes an amine curing agent; The dispersant includes one or more of dispersant BYK-163, dispersant BYK-110, and dispersant BYK-194N; The defoamer includes one or both of defoamer ACP-0001 and defoamer BYK-A530.

[0013] As a further technical solution, the filler is also modified; the modification method comprises the following steps: melting 2-carboxyphenyliminodiacetic acid, adding the filler, mixing, cooling, and obtaining a modified filler.

[0014] As a further technical solution, the mass ratio of the 2-carboxyphenyliminodiacetic acid to the filler is 1:5-10.

[0015] In the present invention, after 2-carboxyphenyliminodiacetic acid is melted, the filler in the fire retardant coating is coated and modified, thereby further improving the bonding strength and wear resistance of the fire retardant coating.

[0016] The present invention also proposes a method for preparing a fire retardant coating for a radiation controlled area, comprising the following steps: S1, dissolving the polyetherimide in an organic solvent to obtain a polyetherimide solution; S2, mixing the remaining components of the fire retardant coating to obtain a mixture; S3, mixing the polyetherimide solution with the mixed material to obtain a fire retardant coating.

[0017] The present invention also proposes the use of the fire retardant coating for radiation control areas or the fire retardant coating prepared by the preparation method in radiation control areas.

[0018] The working principle and beneficial effects of the present invention are: In the present invention, epoxy resin is used as the main component of the fire retardant coating of the radiation control zone, and terminal carboxyl hyperbranched polyester and polyetherimide are added for synergy, thereby significantly improving the bonding strength and radiation resistance of the fire retardant coating. DETAILED DESCRIPTION

[0019] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0020] In the following examples and comparative examples, the grade of polyetherimide is 2200R; The brand of epoxy resin is NPEL-128; The particle size of titanium dioxide is 50 nm; The particle size of white carbon black is 80nm; Different types of carboxyl-terminated hyperbranched polyesters were purchased from Wuhan Hyperbranched Resin Technology Co., Ltd.

[0021] Example 1 A fireproof coating for radiation control areas, comprising the following components in parts by weight: 40 parts of epoxy resin, 12 parts of alicyclic amine curing agent TAC-900, 5 parts of titanium dioxide, 8 parts of flame retardant, 0.1 parts of dispersant BYK-163, 0.1 parts of defoamer ACP-0001, 1 part of carboxyl-terminated hyperbranched polyester, and 1 part of polyetherimide; The carboxyl-terminated hyperbranched polyester is an aromatic carboxyl-terminated hyperbranched polyester with a carboxyl number of 12 mol and a model number of HyPerC302; The flame retardant comprises ammonium polyphosphate, melamine and pentaerythritol in a mass ratio of 3:1:1; A method for preparing a fire retardant coating for a radiation controlled area comprises the following steps: S1, dissolving polyetherimide in an organic solvent to obtain a polyetherimide solution; S2, mixing the remaining components of the fire retardant coating to obtain a mixture; S3, mixing the polyetherimide solution with the mixed material to obtain a fire retardant coating.

[0022] Example 2 A fireproof coating for radiation control areas, comprising the following components in parts by weight: 50 parts of epoxy resin, 18 parts of alicyclic amine curing agent TAC-900, 5 parts of titanium dioxide, 5 parts of white carbon black, 16 parts of flame retardant, 1 part of dispersant BYK-194N, 0.5 parts of defoamer ACP-0001, 0.5 parts of defoamer BYK-A530, 5 parts of carboxyl-terminated hyperbranched polyester, and 5 parts of polyetherimide; The carboxyl-terminated hyperbranched polyester is an aromatic carboxyl-terminated hyperbranched polyester with a carboxyl number of 48 mol and a model number of HyPerC304; The flame retardant comprises ammonium polyphosphate, melamine and pentaerythritol in a mass ratio of 4:1:1; A method for preparing a fire retardant coating for a radiation controlled area comprises the following steps: S1, dissolving polyetherimide in an organic solvent to obtain a polyetherimide solution; S2, mixing the remaining components of the fire retardant coating to obtain a mixture; S3, mixing the polyetherimide solution with the mixed material to obtain a fire retardant coating.

[0023] Example 3 A fireproof coating for radiation control areas, comprising the following components in parts by weight: 45 parts of epoxy resin, 14 parts of alicyclic amine curing agent TAC-900, 8 parts of titanium dioxide, 12 parts of flame retardant, 0.2 parts of dispersant BYK-163, 0.3 parts of dispersant BYK-110, 0.5 parts of defoamer ACP-0001, 3 parts of carboxyl-terminated hyperbranched polyester, and 3 parts of polyetherimide; The carboxyl-terminated hyperbranched polyester is an aromatic carboxyl-terminated hyperbranched polyester with a carboxyl number of 24 mol and a model number of HyPerC303; The flame retardant comprises ammonium polyphosphate, melamine and pentaerythritol in a mass ratio of 2:1:1; A method for preparing a fire retardant coating for a radiation controlled area comprises the following steps: S1, dissolving polyetherimide in an organic solvent to obtain a polyetherimide solution; S2, mixing the remaining components of the fire retardant coating to obtain a mixture; S3, mixing the polyetherimide solution with the mixed material to obtain a fire retardant coating.

[0024] Example 4 The only difference between this embodiment and embodiment 3 is that the components of the fire retardant coating for radiation control areas include 4 parts of carboxyl-terminated hyperbranched polyester and 2 parts of polyetherimide.

[0025] Example 5 The only difference between this embodiment and embodiment 3 is that the components of the fire retardant coating for radiation control areas include 2.7 parts of terminal carboxyl hyperbranched polyester and 3.3 parts of polyetherimide.

[0026] Example 6 The only difference between this embodiment and embodiment 3 is that the fire retardant coating for radiation control areas contains 1.5 parts of carboxyl-terminated hyperbranched polyester and 4.5 parts of polyetherimide.

[0027] Example 7 The only difference between this embodiment and embodiment 3 is that the components of the fire retardant coating for radiation control areas include 2.4 parts of terminal carboxyl hyperbranched polyester and 3.6 parts of polyetherimide.

[0028] Example 8 The only difference between this embodiment and embodiment 3 is that the components of the fire retardant coating for radiation control areas include 2 parts of carboxyl-terminated hyperbranched polyester and 4 parts of polyetherimide.

[0029] Example 9 The only difference between this embodiment and embodiment 8 is that titanium dioxide is replaced by an equal amount of modified titanium dioxide. The preparation method of modified titanium dioxide comprises the following steps: 2-carboxyphenyliminodiacetic acid and titanium dioxide are mixed to obtain modified titanium dioxide; the mass ratio of 2-carboxyphenyliminodiacetic acid to titanium dioxide is 1:5.

[0030] Example 10 The only difference between this embodiment and embodiment 9 is that the preparation method of modified titanium dioxide includes the following steps: melting 2-carboxyphenyliminodiacetic acid, adding titanium dioxide to mix, cooling, and obtaining modified titanium dioxide; the mass ratio of 2-carboxyphenyliminodiacetic acid to titanium dioxide is 1:5.

[0031] Embodiment 11 The only difference between this embodiment and embodiment 8 is that titanium dioxide is replaced by an equal amount of modified titanium dioxide. The preparation method of modified titanium dioxide comprises the following steps: after melting 2-carboxyphenyliminodiacetic acid, adding titanium dioxide to mix, cooling, and obtaining modified titanium dioxide; the mass ratio of 2-carboxyphenyliminodiacetic acid to titanium dioxide is 1:10.

[0032] Comparative Example 1 The difference between this comparative example and Example 3 is that in the components of the fire retardant coating for radiation control areas, 6 parts of carboxyl-terminated hyperbranched polyester are added, and no polyetherimide is added; A method for preparing a fire retardant coating for a radiation controlled area comprises the following steps: The components of the fire retardant coating are mixed to obtain the fire retardant coating.

[0033] Comparative Example 2 The difference between this comparative example and Example 3 is that the components of the fire retardant coating for radiation control areas contain 6 parts of polyetherimide and no carboxyl-terminated hyperbranched polyester.

[0034] The following performance tests were performed on the fire retardant coatings prepared in Examples 1 to 11 and Comparative Examples 1 to 2: Bond strength: Tested in accordance with standard GB 14907-2018 "Fire retardant coating for steel structures"; Abrasion resistance: The mass loss test was carried out according to the standard GB / T 1768-2006 "Determination of abrasion resistance of paints and varnishes - Rotating rubber grinding wheel method". Each sample was tested three times in parallel and the mass loss results were averaged. Test conditions: rubber grinding wheel model CS-10, load 1000g, speed 1000r; Radiation resistance: The test was carried out in accordance with the standard NB / T 20133.3-2012 "Specifications for protective coatings for pressurized water reactor nuclear power plant facilities and equipment Part 3: Test methods for the effects of gamma ray irradiation on coating systems". The test plate material was steel test plate, and the test was carried out using test procedure a with an irradiation dose rate of 2.80Gy / s.

[0035] The results are shown in Table 1 below.

[0036] Table 1 Performance test results

[0037] Compared with Comparative Examples 1-2, the fire retardant coatings prepared in Examples 1-11 have higher bonding strength, and the coatings are intact after irradiation without cracking, blistering, or falling off, indicating that the epoxy resin is used as the main component of the fire retardant coating in the radiation control zone, and the end carboxyl hyperbranched polyester and polyetherimide are added for synergy, which significantly improves the bonding strength and radiation resistance of the fire retardant coating.

[0038] Compared with Examples 3 to 4, the fire retardant coatings prepared in Examples 5 to 8 have higher bonding strength and lower mass loss, indicating that the mass ratio of the terminal carboxyl hyperbranched polyester to the polyetherimide is less than 1, which further improves the bonding strength and wear resistance of the fire retardant coating.

[0039] Compared with Examples 5-6, the fire retardant coatings prepared in Examples 7-8 have higher bonding strength, indicating that adding carboxyl-terminated hyperbranched polyester and polyetherimide in a mass ratio of 2:3-4 to the epoxy resin-based fire retardant coating further improves the bonding strength of the fire retardant coating.

[0040] Compared with Examples 8 to 9, the fire retardant coatings prepared in Examples 10 to 11 have higher bonding strength and lower mass loss, indicating that the bonding strength and wear resistance of the fire retardant coating are further improved by coating and modifying the filler in the fire retardant coating after melting 2-carboxyphenyliminodiacetic acid.

[0041] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A fire retardant coating for use in radiation controlled areas, characterized in that: The invention comprises the following components in parts by weight: 40-50 parts of epoxy resin, 12-18 parts of curing agent, 5-10 parts of filler, 8-16 parts of flame retardant, 0.1-1 parts of dispersant, 0.1-1 parts of defoaming agent, 1-5 parts of terminal carboxyl hyperbranched polyester and 1-5 parts of polyetherimide.

2. A fire retardant coating for radiation control areas according to claim 1, characterized in that: The number of carboxyl groups in the carboxyl-terminated hyperbranched polyester is 12 to 48 mol.

3. A fire retardant coating for radiation control areas according to claim 2, characterized in that: The mass ratio of the carboxyl-terminated hyperbranched polyester to the polyetherimide is less than 1.

4. A fire retardant coating for radiation control areas according to claim 3, characterized in that: The mass ratio of the carboxyl-terminated hyperbranched polyester to the polyetherimide is 2:3-4.

5. The fire retardant coating for radiation control areas according to claim 1, characterized in that: The filler includes one or more of white carbon black, wollastonite powder, and titanium dioxide; The components of the flame retardant include ammonium polyphosphate, melamine and pentaerythritol.

6. A fire retardant coating for radiation control areas according to claim 1, characterized in that: The curing agent includes an amine curing agent; The dispersant includes one or more of dispersant BYK-163, dispersant BYK-110, and dispersant BYK-194N; The defoamer includes one or both of defoamer ACP-0001 and defoamer BYK-A530.

7. A fire retardant coating for radiation control areas according to claim 5, characterized in that: The filler has also been modified; the modification method comprises the following steps: melting 2-carboxyphenyliminodiacetic acid, adding the filler, mixing, cooling, and obtaining a modified filler.

8. A fire retardant coating for radiation control areas according to claim 7, characterized in that: The mass ratio of the 2-carboxyphenyliminodiacetic acid to the filler is 1:5-10.

9. A method for preparing a fire retardant coating for a radiation controlled area according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1, dissolving the polyetherimide in an organic solvent to obtain a polyetherimide solution; S2, mixing the remaining components of the fire retardant coating to obtain a mixture; S3, mixing the polyetherimide solution with the mixed material to obtain a fire retardant coating.

10. Use of a fire retardant coating for radiation controlled areas according to any one of claims 1 to 8 or a fire retardant coating prepared by the preparation method according to claim 9 in radiation controlled areas.

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