阅读说明：本技术 环氧树脂涂料及其制备方法和应用 (Epoxy resin coating and preparation method and application thereof ) 是由 王书传 张武军 彭家全 梁上海 于 2021-07-02 设计创作，主要内容包括：本发明属于核电防护涂料领域,具体涉及环氧树脂涂料及其制备方法和应用。本发明提供的环氧树脂涂料,包括基料和胺类固化剂,所述基料包括特定重量份的有机硅低聚物改性的自乳化环氧树脂、无机水化材料、矿物纤维、耐辐射填料、润湿分散剂。本发明提供的环氧树脂涂料,具有优异的耐辐照能力、化学介质耐受性和防腐蚀性；同时涂料固体份高,单道施工膜厚高达200μm不开裂,可无需腻子直接应用于混凝土表面。(The invention belongs to the field of nuclear power protective coatings, and particularly relates to an epoxy resin coating as well as a preparation method and application thereof. The epoxy resin coating provided by the invention comprises a base material and an amine curing agent, wherein the base material comprises organosilicon oligomer modified self-emulsifying epoxy resin, an inorganic hydration material, mineral fibers, a radiation-resistant filler and a wetting dispersant in specific parts by weight. The epoxy resin coating provided by the invention has excellent irradiation resistance, chemical medium tolerance and corrosion resistance; meanwhile, the coating has high solid content, the thickness of a single construction film is up to 200 mu m, and the coating does not crack and can be directly applied to the surface of concrete without putty.)

1. The epoxy resin coating is characterized by comprising a base material and an amine curing agent, wherein the base material comprises the following components in parts by weight:

2. the epoxy resin coating according to claim 1, wherein the silicone oligomer-modified self-emulsifying epoxy resin is prepared by a method comprising the steps of: and mixing and heating the organic silicon oligomer and the self-emulsifying epoxy resin for modification to obtain the organic silicon oligomer modified self-emulsifying epoxy resin.

3. The epoxy resin coating according to claim 1 or 2, wherein the number average molecular weight of the silicone oligomer is 500-2000, preferably the number average molecular weight of the silicone oligomer is 500-1000;

the self-emulsifying epoxy resin is self-emulsifying bisphenol A epoxy resin or self-emulsifying novolac epoxy resin; preferably, the self-emulsifying bisphenol A epoxy resin is self-emulsifying bisphenol A epoxy resin with the epoxy equivalent of 170-200, and the self-emulsifying novolac epoxy resin is self-emulsifying linear novolac epoxy resin with the functionality of 2.2-3.6 and the epoxy equivalent of 170-200.

4. The epoxy resin coating according to any one of claims 1 to 3, wherein the mass ratio of the silicone oligomer to the self-emulsifying epoxy resin is (10-40):100, preferably the mass ratio of the silicone oligomer to the self-emulsifying epoxy resin is (15-25): 100.

5. The epoxy resin coating according to any one of claims 1 to 4, wherein the modification temperature is 40 to 50 ℃ and the modification time is 0.5 to 3 hours.

6. The epoxy resin coating according to any one of claims 1 to 5, wherein the silicone oligomer is prepared by a method comprising the steps of:

mixing gamma-glycidoxypropyltrimethoxysilane, alkoxysilane and water, and hydrolyzing to obtain the organic silicon oligomer;

the alkoxy silane is at least one selected from methyl alkoxy silane and phenyl alkoxy silane.

7. The epoxy resin coating according to claim 6,

the methylalkoxysilane is dimethyldiethoxysilane, and the phenylalkoxysilane is diphenyldiethoxysilane;

the hydrolysis temperature is 55-65 ℃, and the hydrolysis time is 4-5 h;

the mass ratio of the gamma-glycidoxypropyltrimethoxysilane to the alkoxy silane to the water is 100 (15-20) to (8-15).

8. The epoxy resin coating according to any one of claims 1 to 7, wherein the inorganic hydrating material is selected from one or both of cement, gypsum; preferably, the cement is Portland cement, and the gypsum is anhydrous gypsum;

the mineral fiber is selected from carbon fiber powder;

the radiation-resistant filler is titanium dioxide or quartz powder;

the wetting dispersant is a non-ionic wetting dispersant, preferably, the wetting dispersant is selected from Tego series wetting dispersants, and more preferably, the wetting dispersant is Tego 760W.

9. The epoxy resin coating according to any one of claims 1 to 8, wherein the amine-based curing agent comprises, in parts by weight:

40-60 parts of aqueous amine adduct;

40-60 parts of water.

10. The epoxy resin coating according to claim 9,

the aqueous amine adduct is a dispersion type aqueous amine adduct, preferably, the dispersion type aqueous amine adduct is selected from aqueous polyamide adducts;

the mass ratio of the base material to the amine curing agent is 100 (80-100).

11. A method for preparing the epoxy resin paint according to any one of claims 1 to 10, comprising the steps of: mixing the base material and the amine curing agent to obtain the product.

12. Use of the epoxy resin paint according to any one of claims 1 to 10 or the epoxy resin paint prepared by the preparation method according to claim 11 for nuclear power plant protection.

Technical Field

The invention belongs to the field of nuclear power protective coatings, and particularly relates to an epoxy resin coating as well as a preparation method and application thereof.

Background

Nuclear power is used as low-carbon energy, is an important component of new energy, and is an important basis for the sustainable development of future energy in China. According to the joint prediction of economic cooperation and development organization and the international energy agency, the global nuclear power generation amount is doubled on the existing basis by 2050, and the power generation proportion reaches 17% of the total power generation amount in the world. However, the proportion of nuclear power in the total power generation amount in China is low, and the nuclear power only accounts for about 3% and is far lower than the average level of 11% of the whole world. However, in the existing power generation structure, the single coal power accounts for 74 percent of the power generation structure. If the power demand doubles again, the coal consumption will exceed 16 million tons every year, so large electricity coal consumption, sulfur dioxide and smoke emission respectively increase more than 500 million tons and 5326 million tons every year, and long-distance coal transportation will aggravate the environment and transportation pressure. In addition, hydropower is limited by objective conditions, and the development difficulty is quite large. The development of renewable energy sources such as solar energy, biological energy and the like meets the bottleneck of core technology, and the use cost is extremely high. Therefore, in the next 30 years, the new energy sources do not have the condition of becoming the main energy sources of China. Therefore, clean, efficient and powerful nuclear power is preferred while ensuring safety.

The containment concrete is the most main structural part of a reactor of a nuclear island system, the concrete surface protective coating has great significance on the safety of the containment, and the coating tolerance and the construction efficiency are favorable for improving the construction efficiency and the quality of the containment.

The prior containment concrete surface protective coating material has the following problems:

1) the existing epoxy coating has poor adhesive force to a concrete base material under high accumulated irradiation dose, and the decontamination rate of nuclear pollutants is low;

2) the existing epoxy coating has low single construction film thickness, needs putty scraping in construction matching, has large polishing treatment amount, low construction efficiency and poor tolerance, and easily causes the foaming, falling and peeling of the coating after construction in a high-humidity environment of a containment vessel.

Therefore, the development of the epoxy resin coating which has high adhesive force to a concrete base material under high accumulated irradiation dose, high decontamination rate of nuclear pollutants, high tolerance, thick single construction film and difficult foaming, falling and peeling after construction under a high-humidity environment has important significance.

Disclosure of Invention

Therefore, the invention aims to solve the technical problems of the existing epoxy resin coating for protecting the nuclear power station, and further provides the epoxy resin coating and a preparation method and application thereof.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

the invention provides an epoxy resin coating, which comprises a base material and an amine curing agent, wherein the base material comprises the following components in parts by weight:

preferably, the preparation method of the silicone oligomer modified self-emulsifying epoxy resin comprises the following steps: and mixing and heating the organic silicon oligomer and the self-emulsifying epoxy resin for modification to obtain the organic silicon oligomer modified self-emulsifying epoxy resin.

Preferably, the number average molecular weight of the organosilicon oligomer is 500-2000, and preferably, the number average molecular weight of the organosilicon oligomer is 500-1000;

the self-emulsifying epoxy resin is self-emulsifying bisphenol A epoxy resin or self-emulsifying novolac epoxy resin; preferably, the self-emulsifying bisphenol A epoxy resin is self-emulsifying bisphenol A epoxy resin with the epoxy equivalent of 170-200, and the self-emulsifying novolac epoxy resin is self-emulsifying linear novolac epoxy resin with the functionality of 2.2-3.6 and the epoxy equivalent of 170-200.

Preferably, the mass ratio of the organic silicon oligomer to the self-emulsifying epoxy resin is (10-40):100, and preferably, the mass ratio of the organic silicon oligomer to the self-emulsifying epoxy resin is (15-25): 100.

Preferably, the modification temperature is 40-50 ℃, and the modification time is 0.5-3 h.

Preferably, the preparation method of the organic silicon oligomer comprises the following steps:

mixing gamma-glycidoxypropyltrimethoxysilane, alkoxysilane and water, and hydrolyzing to obtain the organic silicon oligomer;

the alkoxy silane is at least one selected from methyl alkoxy silane and phenyl alkoxy silane.

Preferably, the first and second liquid crystal materials are,

the methylalkoxysilane is dimethyldiethoxysilane, and the phenylalkoxysilane is diphenyldiethoxysilane;

the hydrolysis temperature is 55-65 ℃, and the hydrolysis time is 4-5 h;

the mass ratio of the gamma-glycidoxypropyltrimethoxysilane to the alkoxy silane to the water is 100 (15-20) to (8-15).

Preferably, the inorganic hydration material is selected from one or two of cement and gypsum; preferably, the cement is Portland cement, and the gypsum is anhydrous gypsum;

the mineral fiber is selected from carbon fiber powder, the carbon fiber powder can be commercially available carbon fiber powder, the carbon fiber can also be prepared by grinding the carbon fiber, and optionally, the length of the carbon fiber powder can be 50-80 μm.

The radiation-resistant filler is titanium dioxide or quartz powder.

The wetting dispersant is a non-ionic wetting dispersant, preferably, the wetting dispersant is selected from Tego series wetting dispersants, and more preferably, the wetting dispersant is Tego 760W.

Preferably, the amine curing agent comprises the following components in parts by weight:

40-60 parts of aqueous amine adduct;

40-60 parts of water.

Preferably, the first and second liquid crystal materials are,

the object of the present invention can be achieved without limiting the specific kind of the aqueous amine adduct, and the aqueous amine adduct is preferably a dispersion type aqueous amine adduct, preferably selected from aqueous polyamide adducts, and more preferably selected from aqueous amine adducts of Allnex corporation.

The mass ratio of the base material to the amine curing agent is 100 (80-100).

The invention also provides a preparation method of the epoxy resin coating, which comprises the following steps: mixing the base material and the amine curing agent to obtain the product.

The invention also provides the application of the epoxy resin coating or the epoxy resin coating prepared by the preparation method in nuclear power station protection.

The technical scheme of the invention has the following advantages:

1) the epoxy resin coating provided by the invention adopts the self-emulsifying epoxy resin modified by the organic silicon oligomer, the compatibility of the inorganic hydration material and the epoxy resin is effectively improved by Si-O-Si coupling of organic silicon and the inorganic hydration material in the modified epoxy resin, and meanwhile, the epoxy functional group and the amine curing agent are crosslinked and cured, so that an interpenetrating network formed by the mineral fiber, the radiation-resistant filler and the epoxy resin-amine is physically wound and chemically bonded, the crosslinking density is increased, and the irradiation resistance, the chemical medium tolerance and the corrosion resistance are improved; meanwhile, the coating is added with an inorganic hydration material with hydration, and the inorganic hydration material and water on the surface of concrete generate hydration in a high-humidity environment, so that the coating has excellent tolerance in coating construction; meanwhile, the coating has high solid content, the thickness of a single construction film is up to 200 mu m, and the coating does not crack and can be directly applied to the surface of concrete without putty. The coating provided by the invention can resist gamma ray cumulative irradiation dose up to 10⁷Gy, the decontamination rate of nuclear pollutants under the high accumulated irradiation dose is more than 90%, the adhesive force to the concrete substrate is more than 2.6MPa, the DBA and severe working condition test requirements are met, and the coating does not foam or fall off after being constructed in an environment with the humidity of more than 85%.

2) The epoxy resin coating provided by the invention further comprises the following steps of: and mixing and modifying the organic silicon oligomer and the self-emulsifying epoxy resin to obtain the organic silicon oligomer modified self-emulsifying epoxy resin. Preferably, the number average molecular weight of the organosilicon oligomer is 500-2000, and preferably, the number average molecular weight of the organosilicon oligomer is 500-1000; the self-emulsifying epoxy resin is self-emulsifying bisphenol A epoxy resin or self-emulsifying novolac epoxy resin; preferably, the self-emulsifying bisphenol A epoxy resin is self-emulsifying bisphenol A epoxy resin with the epoxy equivalent of 170-200, and the self-emulsifying novolac epoxy resin is self-emulsifying linear novolac epoxy resin with the functionality of 2.2-3.6 and the epoxy equivalent of 170-200. The organosilicon oligomer and the self-emulsifying epoxy resin are mixed and modified to prepare the self-emulsifying epoxy resin modified by the organosilicon oligomer, and the self-emulsifying epoxy resin is matched with other components, so that the irradiation tolerance capability of a gamma-ray agent can be further improved, and the decontamination rate of nuclear pollutants and the adhesive force of a coating under high accumulated irradiation dose can be further improved.

3) The epoxy resin coating provided by the invention further comprises the following steps of: mixing gamma-glycidoxypropyltrimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane and water for hydrolysis to obtain the organic silicon oligomer. According to the invention, the organosilicon oligomer prepared by the preparation method is mixed and modified with self-emulsifying epoxy resin, the modified silane and the inorganic hydrated material are coupled through Si-O-Si to effectively improve the compatibility of the inorganic hydrated material and the epoxy resin, meanwhile, the epoxy functional group and the amine curing agent are crosslinked and cured, and an interpenetrating network formed by the mineral fiber, the radiation-resistant filler and the epoxy resin-amine is physically wound and chemically bonded, so that the crosslinking density is increased, and the irradiation resistance, the chemical medium resistance, the corrosion resistance and the adhesion capability are improved.

Detailed Description

The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.

The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.

Example 1

The embodiment provides an epoxy resin coating, which comprises a base material and an amine curing agent, wherein the base material comprises the following raw materials:

the preparation method of the organic silicon oligomer modified self-emulsifying epoxy resin comprises the following steps:

1) mixing gamma-glycidoxypropyltrimethoxysilane (KH560), dimethyldiethoxysilane and water for hydrolysis, wherein the hydrolysis temperature is 60 ℃, the hydrolysis time is 4h, and the ratio of gamma-glycidoxypropyltrimethoxysilane: dimethyl diethoxysilane: the mass ratio of water is 100:20:10, so as to obtain the organic silicon oligomer (the number average molecular weight of the organic silicon oligomer is 500-1000);

2) mixing and heating the organic silicon oligomer and self-emulsifying epoxy resin (the self-emulsifying epoxy resin is self-emulsifying bisphenol A epoxy resin with the epoxy equivalent of 188-200, purchased from Allnex, model 147W) for modification at the modification temperature of 45 ℃ for 1h, wherein the mass ratio of the organic silicon oligomer to the self-emulsifying epoxy resin is 25:100, and obtaining the self-emulsifying epoxy resin modified by the organic silicon oligomer.

The amine curing agent comprises the following raw materials:

40g of aqueous amine adduct;

40g of water.

The inorganic hydration material is Portland cement, the mineral fiber is carbon fiber powder, the radiation-resistant filler is titanium dioxide, the wetting dispersant is Tego760W of Germany Digao, and the aqueous amine adduct is EH623W of Allnex company.

The preparation method of the epoxy resin coating comprises the following steps:

the base material and the amine curing agent are respectively and fully mixed, and the base material and the amine curing agent are mixed before use.

Example 2

The embodiment provides an epoxy resin coating, which comprises a base material and an amine curing agent, wherein the base material comprises the following raw materials:

the preparation method of the organic silicon oligomer modified self-emulsifying epoxy resin comprises the following steps:

1) mixing gamma-glycidoxypropyltrimethoxysilane (KH560), diphenyldiethoxysilane and water for hydrolysis, wherein the hydrolysis temperature is 65 ℃, the hydrolysis time is 4h, and the ratio of gamma-glycidoxypropyltrimethoxysilane: diphenyldiethoxysilane: the mass ratio of water is 100:20:10, so as to obtain the organic silicon oligomer (the number average molecular weight of the organic silicon oligomer is 600-1000);

2) mixing and heating the organic silicon oligomer and self-emulsifying epoxy resin (the self-emulsifying epoxy resin is self-emulsifying linear novolac epoxy resin with functionality of 2.3 and epoxy equivalent of 172-182, which is purchased from Huntsman corporation, model number PY340-2) for modification, wherein the modification temperature is 40 ℃, the modification time is 3h, and the mass ratio of the organic silicon oligomer to the self-emulsifying epoxy resin is 25:100, so as to obtain the self-emulsifying epoxy resin modified by the organic silicon oligomer.

The amine curing agent comprises the following raw materials:

60g of aqueous amine adduct;

50g of water.

The inorganic hydration material is anhydrous gypsum, the mineral fiber is carbon fiber powder, the radiation-resistant filler is quartz powder, the wetting dispersant is Tego760W of Germany Digao, and the aqueous amine adduct is EH623W of Allnex.

The preparation method of the epoxy resin coating comprises the following steps:

the base material and the amine curing agent are respectively and fully mixed, and the base material and the amine curing agent are mixed before use.

Example 3

The embodiment provides an epoxy resin coating, which comprises a base material and an amine curing agent, wherein the base material comprises the following raw materials:

the preparation method of the organic silicon oligomer modified self-emulsifying epoxy resin comprises the following steps:

1) mixing gamma-glycidoxypropyltrimethoxysilane (KH560), dimethyldiethoxysilane and water for hydrolysis, wherein the hydrolysis temperature is 55 ℃, the hydrolysis time is 5h, and the ratio of gamma-glycidoxypropyltrimethoxysilane: dimethyl diethoxysilane: the mass ratio of water is 100:15:15, so as to obtain the organic silicon oligomer (the number average molecular weight of the organic silicon oligomer is 600-800);

2) mixing and heating the organic silicon oligomer and self-emulsifying epoxy resin (the self-emulsifying epoxy resin is self-emulsifying bisphenol A epoxy resin with the epoxy equivalent of 188-200, purchased from Allnex, model 147W) for modification at the modification temperature of 40 ℃ for 1h, wherein the mass ratio of the organic silicon oligomer to the self-emulsifying epoxy resin is 15:100, and obtaining the organic silicon oligomer modified self-emulsifying epoxy resin. .

The amine curing agent comprises the following raw materials:

50g of aqueous amine adduct;

50g of water.

The inorganic hydration material is Portland cement, the mineral fiber is carbon fiber powder, the radiation-resistant filler is quartz powder, the wetting dispersant is Tego760W of Germany Digao, and the aqueous amine adduct is EH623W of Allnex.

The preparation method of the epoxy resin coating comprises the following steps:

the base material and the amine curing agent are respectively and fully mixed, and the base material and the amine curing agent are mixed before use.

Comparative example 1

The comparative example provides an epoxy resin coating, which comprises a base material and an amine curing agent, wherein the base material comprises the following raw materials:

the preparation method of the organic silicon oligomer comprises the following steps:

mixing gamma-glycidoxypropyltrimethoxysilane (KH560), dimethyldiethoxysilane and water for hydrolysis, wherein the hydrolysis temperature is 60 ℃, the hydrolysis time is 4h, and the ratio of gamma-glycidoxypropyltrimethoxysilane: dimethyl diethoxysilane: the mass ratio of water was 100:20:10, giving the silicone oligomer (number average molecular weight of silicone oligomer 500-1000).

The amine curing agent comprises the following raw materials:

40g of aqueous amine adduct;

40g of water.

The self-emulsifying epoxy resin is self-emulsifying bisphenol A epoxy resin with the epoxy equivalent of 188-200, which is purchased from Allnex company and is model 147W, the inorganic hydration material is Portland cement, the mineral fiber is carbon fiber powder, the radiation-resistant filler is titanium dioxide, the wetting dispersant is Tego760W of Germany Digao, and the aqueous amine adduct is EH623W of the Allnex company.

The preparation method of the epoxy resin coating comprises the following steps:

the base material and the amine curing agent are respectively and fully mixed, and the base material and the amine curing agent are mixed before use.

Test examples

The epoxy resin coatings prepared in examples 1 to 3 and comparative example 1 of the present invention were subjected to performance tests, wherein the base material selected concrete, the cumulative irradiation dose of the coating was first tested according to NB/T20133.3 test standard, and then the adhesion and nuclear pollutant decontamination rates were respectively tested on the basis of the cumulative irradiation dose, the adhesion test was performed according to GB/T5210 test standard, the nuclear pollutant decontamination rate was performed according to NB/T20133.4 test standard, and the test results are shown in table 1 below:

TABLE 1 epoxy coating Performance results

	Cumulative dose of radiation (Gy)	Adhesion (MPa)	Nuclear contaminant decontamination (%)
				Example 1	107	2.6	95
Example 2	107	3.2	90
				Example 3	107	3.0	92
Comparative example 1	107	1.7	85

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.