WO2017166913A1

WO2017166913A1 - Radiation-resistant fluorine-silicon containing epoxy-resin coating and preparation method thereof

Info

Publication number: WO2017166913A1
Application number: PCT/CN2017/072219
Authority: WO
Inventors: 戴李宗; 毛杰; 袁丛辉; 王诗榕; 武彤; 吴俣哲; 许一婷; 罗伟昂; 王书传; 陈国荣
Original assignee: 厦门大学; 信和新材料股份有限公司
Priority date: 2016-04-01
Filing date: 2017-01-23
Publication date: 2017-10-05
Also published as: CN105778717A

Abstract

Provided are a radiation-resistant fluorine-silicon containing an epoxy-resin coating and a preparation method thereof, the coating consisting of, in parts by mass: 80-150 parts of a bisphenol AF type fluorine-containing epoxy resin, 10-30 parts of a reactive diluent, 5-20 parts of a metallic oxide nano powder, 30-50 parts of a compounded curing agent, and 0.2-0.8 parts of a defoaming agent. The compounded curing agent of the present invention, comprising organic amine and octa(aminopropyl) polyhedral oligomeric silsesquioxane, participates in the curing of bisphenol AF type fluorine-containing epoxy resin and results in a coating material with good radiation resistance.

Description

Fluorine-containing silicon epoxy resin radiation-resistant coating and preparation method thereof

Technical field

The invention belongs to a functional coating in the field of coatings, in particular to a fluorine-containing silicon epoxy resin radiation-resistant coating and a preparation method thereof.

technical background

As fossil energy fuel reserves continue to decrease and environmental pollution is increasing, more and more countries are turning their attention to clean energy nuclear power. Since 2005, China has added nuclear power plant construction projects every year. The National Development and Reform Commission's "National Nuclear Power Development Special Plan (2005-2020)" pointed out that by 2020, the country will build more than 20 sets of 1 million kilowatt nuclear power plants. The development of nuclear power and "nuclear power going out" have all risen to national strategies. At a time when China's nuclear power industry is booming, research and development of radiation-resistant special coatings for nuclear power plant units and related equipment is receiving increasing attention. Many equipments and facilities of nuclear power plants need to be coated and protected. Special coatings for coating protection are required to have high radiation resistance and decontamination, corrosion resistance and other special chemical properties, and can absorb radiation to protect the surrounding of the source. environment of.

Studies have shown that radioactive irradiation accelerates the aging degradation of the main film-forming substance in the coating—polymerization, or causes the polymer to react with high-energy radiation to generate free radicals and oxygen atoms in the air, causing the polymer to cause polymerization. The cross-linking reaction becomes brittle and crack, which affects the performance of the coating. Therefore, the properties of the main film-forming materials of the radiation-resistant coating have a significant effect on the radiation resistance of the coating. At present, the radiation resistant base materials for nuclear industry coatings are epoxy resin, modified phenolic acid, chlorinated rubber, alkyd, vinyl resin, etc. The amine-cured epoxy resin is particularly suitable for coatings resistant to gamma radiation.

Fluorinated epoxy is a type of epoxy resin with a fluorine atom on the main chain or side groups of the polymer. The bond energy of the FC bond formed by the fluorine atom and the carbon atom is large (485 kJ/mol), and the electron cloud of the fluorine atom is CC. The shielding of the bond protects the CC bond from radiation and chemicals, making the fluoropolymer excellent in corrosion resistance and durability. However, it is difficult to obtain the best performance of the special coating products by using only the fluorine-containing epoxy. The selection and use of the curing agent and the addition of the auxiliary materials play a vital role in the final performance of the product. It is well known that Si-O bond can have high radiation resistance, and Changshu is equal (a silicone-epoxy radiation-resistant coating and its preparation method, Chinese Patent, Publication No.: CN 104263194A) discloses an epoxy resin. Radiation-resistant coating compounded with silicone resin. Although the coating material is resistant to radiation, the use of silicone resin in a large amount of the main film-forming material will definitely reduce the mechanical properties and corrosion resistance of the coating material. In view of the fact that the π bond on the benzene ring enables the radiant energy received by individual electrons to be uniformly dispersed to all the electrons on the π bond, reducing the local C-C bond The chain breakage that occurs during excitation enhances the radiation resistance of the material, and the Si-O bond of the high bond energy and the electron cloud of the fluorine atom in the FC bond shield the CC bond, thereby protecting the CC bond, thereby effectively improving the material. Radiation resistance. . Therefore, the present invention is directed to the deficiencies of the prior art, and based on the use of a fluorine-containing bisphenol AF epoxy, an organic amine and an octaphenylamino polysilsesquioxane (OAPPOSS) compound curing agent are used to participate in the bisphenol AF type. The curing of the fluorine-containing epoxy resin gives a coating material excellent in radiation resistance without sacrificing mechanical properties.

Summary of the invention

The invention aims to provide a fluorine-containing silicon epoxy resin radiation-resistant paint and a preparation method thereof.

The formulation of the fluorine-containing silicon epoxy resin radiation-resistant coating is as follows:

80-150 parts of bisphenol AF type fluorine-containing epoxy resin, 10-30 parts of reactive diluent, 5-20 parts of metal oxide nano powder, 30-50 parts of curing agent, and 0.2-0.8 parts of antifoaming agent.

The preparation method of the bisphenol AF type fluorine-containing epoxy resin refers to the steps provided by the public patent CN201310352654.6:

(1) 30 to 40 parts of a fluorine-containing monomer and 20 to 30 parts of epichlorohydrin are placed in a reaction vessel, and the solution is stirred and heated at 65 °C.

(2) Using 5 to 10 parts of NaOH and 15 to 20 parts of water to form an alkali solution, and adding to the reaction vessel for 1 to 1.5 hours, the temperature control is still controlled at 65 °C.

(3) The lye was added dropwise, and the reaction was refluxed at 70 ° C for 1.5 hours, and the system was milky yellow.

(4) Add deionized water and toluene, stir evenly, and then stand for liquid separation, remove the water layer, repeat the operation several times to remove the water layer, separate the organic phase, and distill off the solvent toluene and unreacted epichlorohydrin under reduced pressure. , a pale yellow viscous resin.

The reactive diluent may be selected from the group consisting of 1,6-hexanediol diacrylate, β-hydroxyethyl methacrylate, tolyl glycidyl ether, castor oil polyglycidyl ether, and ethylene glycol diglycidyl ether. Kind.

The metal oxide nanopowder is one or more of ZnO, Al ₂ O ₃ , TiO ₂ , and Fe ₂ O ₃ of 50 to 300 nm.

The curing agent is an organic compound such as ethylenediamine, diethylenetriamine, m-phenylenediamine or 4,4-diaminodiphenylmethane used in combination with an epoxy resin. The silsesquioxane (OAPPOSS) wherein the ratio of the amine curing agent to the OAPPOSS is from 10:1 to 5. The preparation method of OAPPOSS is described in the literature M. Laine, et al. Octa (aminophenyl) silsesquioxane as a Nanoconstruction Site. J. Am. Steps in Chem. Soc. 2001, 123, 12416-12417.

(1) 5 to 10 parts of octaphenyl polysilsesquioxane (OPS) were dispersed in 30 to 60 parts by volume of a nitric acid solution in an ice water bath, and uniformly stirred for 30 minutes.

(2) The OPS nitric acid solution was further reacted at room temperature for 15 to 30 hours, filtered with suction and washed with water for 3 to 5 times to obtain a yellow precipitate.

(3) 5 to 10 parts of the yellow precipitate obtained in (2) and 0.5 to 2 parts of palladium carbon catalyst are placed in a round bottom flask, and 10 to 20 parts by volume of tetrahydrofuran (THF) and 10 to 20 parts by volume are added under argon atmosphere. Triethylamine (TEA), the reaction solution was heated to 60 ° C, 4 to 10 parts by volume of formic acid was added, and the reaction was continued for 5 to 10 hours.

(4) After completion of the reaction, it was filtered with suction and washed with ethyl acetate and water for 3 to 5 portions to give a pale yellow solid.

The antifoaming agent is preferably dimethicone.

The preparation method of the fluorine-containing silicon epoxy resin radiation-resistant coating is as follows: First, the metal oxide nano powder and the antifoaming agent are sequentially dissolved in the reactive diluent, and stirred for 0.5 to 1 hour to obtain a uniform emulsion, which is under ultrasonic vibration. The epoxy resin was added portionwise to the emulsion in portions, and stirred for 0.5 to 2 hours to uniformly obtain the A component. Next, the amine curing agent and OAPPOSS were added to xylene to be uniformly dispersed to obtain a B component. The fluorine-containing silicon epoxy resin radiation-resistant coating can be obtained by mixing the components A and B.

The fluorine-containing silicon epoxy resin radiation-resistant paint of the invention has the following characteristics:

(1) Fluorine-containing epoxy is used as the main film-forming material of the coating. Compared with ordinary epoxy and phenolic modified epoxy, the paint film not only has higher radiation resistance, but also F-C bond in fluorine-containing epoxy resin. The bond energy is large, and the electron cloud of the fluorine atom shields the C-C bond to protect the C-C bond from radiation and chemicals, and gives the coating better antifouling and anti-corrosion properties, so that the coating material has Excellent weather resistance.

(2) The organic amine and octaphenylamino polysilsesquioxane (OAPPOSS) are used to compound the curing agent. The addition of OAPPOSS improves the thermal stability of the epoxy resin. Compared with the conventional POSS, octaphenylamino polysilsesquioxane contains a plurality of functional groups which can participate in epoxy curing, and can be well dispersed in the epoxy group, and OAPPOSS has eight benzene ring structures and π on the benzene ring. The bond can uniformly disperse the radiant energy received by the individual electrons to all the electrons on the π bond, reduce the chain breakage of the local CC bond due to excitation, and improve the radiation resistance of the material.

detailed description

The invention is further illustrated by the following examples.

Example 1

5g of metal oxide nanopowder and 0.2g of antifoaming agent were sequentially dissolved in 10g of reactive diluent, and stirred for 0.5 hours to obtain a uniform emulsion. 80g of epoxy resin was added to the emulsion in batches under ultrasonic vibration, and stirred for 0.5 hour to uniformity. The component A is obtained. 20 g of an amine curing agent and 5 g of OAPPOSS were added to 10 mL of xylene to be uniformly dispersed to obtain a B component. The components A and B are mixed to obtain a fluorine-containing silicone epoxy radiation-resistant paint.

The preparation of the fluorine-containing resin involved is as follows with reference to the disclosed patent CN201310352654.6:

(1) 30 g of 2,2-bis(hydroxyphenyl)-, 1,1,3.3,3-hexafluoropropane and 28 g of epichlorohydrin were added to a three-necked flask equipped with a stir bar and a temperature control device, and the solution was stirred. , heating 65 ° C.

(2) Take 6g of NaOH and 17g of deionized water to form an alkali solution, and add it to the reaction vessel within 1.5 hours. The temperature control is still controlled at 65 °C.

(4) Add 27 mL of deionized water and 54 mL of toluene, stir evenly, and then stand for liquid separation, remove the water layer, repeat the operation several times to remove the aqueous layer, separate the organic phase, and distill off the solvent toluene and unreacted epoxy under reduced pressure. Chloropropane gives a pale yellow viscous fluororesin.

The preparation method of the OAPPOSS involved is described in the literature by M. Laine, et al. Octa (aminophenyl) silsesquioxane as a Nanoconstruction Site. J. Am. Chem. Soc. 2001, 123, 12416-12417. The steps are as follows:

(1) 5 g of octaphenyl polysilsesquioxane (OPS) was dispersed in a 30 mL nitric acid solution in an ice water bath, and uniformly stirred for 30 minutes.

(2) The OPS nitric acid solution was further reacted at room temperature for 15 hours, filtered with suction and washed with water three times to obtain a yellow precipitate.

(3) 5 g of the yellow precipitate obtained in (2) and 0.5 g of palladium carbon catalyst were placed in a round bottom flask, 10 mL of tetrahydrofuran (THF) and 10 mL of triethylamine (TEA) were added under argon atmosphere, and the reaction liquid was heated to 60 ° C. Add 4 mL of formic acid and continue the reaction for 5 h.

(4) After the completion of the reaction, the mixture was filtered, washed with ethyl acetate and water three times to give a pale yellow solid.

Example 2

15g of metal oxide nanopowder and 0.5g of antifoaming agent were sequentially dissolved in 15g of reactive diluent, and stirred for 1 hour to obtain a uniform emulsion. 120g of epoxy resin was added to the emulsion in batches under ultrasonic vibration, and stirred for 1.5 hours until uniform. The component A is obtained. 30 g of the amine curing agent and 10 g of OAPPOSS were added to 10 mL of xylene to be uniformly dispersed to obtain a B component. The components A and B are mixed to obtain a fluorine-containing silicone epoxy radiation-resistant paint.

(1) 8 g of octaphenyl polysilsesquioxane (OPS) was dispersed in a 30-60 mL nitric acid solution in an ice water bath, and uniformly stirred for 30 minutes.

(2) The OPS nitric acid solution was further reacted at room temperature for 20 hours, filtered with suction and washed with water for 5 times to obtain a yellow precipitate.

(3) 8 g of the yellow precipitate obtained in (2) and 1 g of palladium carbon catalyst were placed in a round bottom flask, and 15 mL of tetrahydrofuran (THF) and 15 mL of triethylamine (TEA) were added under argon atmosphere, and the reaction liquid was heated to 60 ° C. 8 mL of formic acid was added and the reaction was continued for 10 h.

(4) After completion of the reaction, the mixture was filtered, washed with ethyl acetate and water, and then evaporated,

Example 3

20g of metal oxide nanopowder and 0.8g of antifoaming agent were sequentially dissolved in 30g of reactive diluent, and stirred for 1 hour to obtain a uniform emulsion. 150g of epoxy resin was added to the emulsion in batches under ultrasonic vibration, and stirred for 2 hours until uniform. The component A is obtained. 40 g of an amine curing agent and 20 g of OAPPOSS were added to 20 mL of xylene to be uniformly dispersed to obtain a B component. The components A and B are mixed to obtain a fluorine-containing silicone epoxy radiation-resistant paint.

(1) 40 g of 2,2-bis(hydroxyphenyl)-, 1,1,3.3,3-hexafluoropropane and 30 g of epichlorohydrin were added to a three-necked flask equipped with a stir bar and a temperature control device, and the solution was stirred. , heating 65 ° C.

(2) Take 10g of NaOH and 20g of deionized water to form an alkali solution, and add it to the reaction vessel within 1.5 hours. Temperature control is still controlled at 65 °C.

(1) 10 g of octaphenyl polysilsesquioxane (OPS) was dispersed in a 40 mL nitric acid solution in an ice water bath, and uniformly stirred for 30 minutes.

(2) The OPS nitric acid solution was further reacted at room temperature for 30 hours, filtered with suction and washed with water for 5 times to obtain a yellow precipitate.

(3) 10 g of the yellow precipitate obtained in (2) and 2 g of palladium carbon catalyst were placed in a round bottom flask, and 15 mL of tetrahydrofuran (THF) and 15 mL of triethylamine (TEA) were added under argon atmosphere, and the reaction liquid was heated to 60 ° C. 10 mL of formic acid was added and the reaction was continued for 10 h.

Table 1 Performance test results of the radiation resistant coatings of Examples 1 to 3

Claims

A fluorine-containing silicon epoxy resin radiation-resistant coating characterized in that the composition by mass ratio is as follows: bisphenol AF type fluorine-containing epoxy resin 80-150 parts, reactive diluent 10-30 parts, metal oxide nano powder 5 to 20 parts, 30 to 50 parts of a curing agent, and 0.2 to 0.8 parts of an antifoaming agent.
A fluorine-containing silicon epoxy resin radiation-resistant paint according to claim 1, wherein the preparation method of the bisphenol AF type fluorine-containing epoxy resin is as follows:

The fluoromonomer and epichlorohydrin are added to the reaction vessel to raise the temperature, the lye is added to the reaction vessel, the reactant is refluxed, then deionized water and toluene are added, and the liquid layer is allowed to stand to remove the water layer, and the organic layer is separated. The solvent was distilled off under reduced pressure to remove toluene and unreacted epichlorohydrin to obtain a bisphenol AF type fluorine-containing epoxy resin, and the obtained bisphenol AF type fluorine-containing epoxy resin was a pale yellow viscous resin.
A fluorine-containing silicone epoxy radiation-resistant paint according to claim 2, wherein the mass ratio of said fluorine-containing monomer, epichlorohydrin, NaOH and water is (6-8): (4-6) : (1 ~ 2): (3 ~ 4); the temperature of the temperature rising reaction may be 65 ° C, the temperature rise reaction time may be 1 ~ 1.5h; the reflux temperature may be 70 ° C, the reflux time may be 1.5h; the aqueous layer can be removed 2 to 3 times.
A fluorine-containing silicone epoxy radiation-resistant coating according to claim 1 or 2, wherein the reactive diluent is selected from the group consisting of 1,6-hexanediol diacrylate and β-hydroxyethyl methacrylate. One of toluene glycidyl ether, castor oil polyglycidyl ether, and ethylene glycol diglycidyl ether.
The fluorosilicone epoxy resin radiation-resistant coating according to claim 1, wherein the metal oxide nanopowder is at least one selected from the group consisting of ZnO, Al 2 O 3 , TiO 2 and Fe 2 O 3 ; The metal oxide nanopowder has a particle diameter of 50 to 300 nm.
A fluorine-containing silicone epoxy radiation-resistant coating according to claim 1, wherein the compound curing agent is an amine curing agent compounded with octaphenylamino polysilsesquioxane. The amine curing agent is selected from the group consisting of ethylenediamine, diethylenetriamine, m-phenylenediamine, 4,4-diaminodiphenylmethane, etc.; amine curing agent and octaphenylamino polysilsesquioxane The mass ratio of the alkane is 10: (1 to 5).
A fluorine-containing silicone epoxy radiation-resistant coating according to claim 6, wherein the octaphenylamino polysilsesquioxane is prepared as follows:

1) 5 to 10 parts of octaphenyl polysilsesquioxane is dispersed in 30 to 60 parts by volume of nitric acid solution in an ice water bath, and uniformly stirred for 30 minutes;

2) The OPS nitric acid solution is further reacted at room temperature for 15 to 30 hours, filtered and washed with water for 3 to 5 times to obtain yellow. Color precipitation

3) 5 to 10 parts of the yellow precipitate obtained in the step 2) and 0.5 to 2 parts of palladium carbon catalyst are placed in a reaction vessel, and 10 to 20 parts by volume of tetrahydrofuran and 10 to 20 parts by volume of triethylamine are added under argon atmosphere, and the reaction liquid Heating to 60 ° C, adding 4 to 10 parts by volume of formic acid, and continuing the reaction for 5 to 10 hours;

4) After completion of the reaction, the mixture was filtered with suction and washed with ethyl acetate and water for 3 to 5 portions to give a pale yellow solid.
A fluorine-containing silicone epoxy radiation resistant coating according to claim 1, wherein said antifoaming agent is dimethyl silicone oil.
A method for preparing a fluorine-containing silicon epoxy resin radiation-resistant coating according to claim 1, comprising the steps of:

1) The metal oxide nanopowder and the antifoaming agent are sequentially dissolved in the active diluent to obtain an emulsion, and an epoxy resin is added to the emulsion to obtain a component A;

2) The amine curing agent and octaphenylamino polysilsesquioxane are added to the xylene to be uniformly dispersed to obtain component B;

3) Mixing component A and component B to obtain a fluorine-containing silicon epoxy resin radiation-resistant coating.
The method for preparing a fluorine-containing silicon epoxy resin radiation-resistant coating according to claim 9, wherein in the step 1), the epoxy resin is added to the emulsion and added to the emulsion in batches under ultrasonic vibration. Epoxy resin.