CN107722239A - A kind of epoxide resin material and preparation method thereof - Google Patents

Abstract

The invention provides a kind of epoxide resin material and preparation method thereof, epoxide resin material is made by the raw material including following parts by weight：100 parts of epoxy resin composition；10~20 parts of the CNT base iron-based imidazole ion liquid with the structure of formula II；10~20 parts of amine terminated polyether；Epoxy resin composition includes bisphenol A diglycidyl ether, has the endurable active toughener and the dicarboxylic acid diglycidyl ester of 4,5 oxepane 1,2 of structure shown in formula I.The epoxide resin material has good mechanical performance and anti-leaching performance.Irradiation dose 10⁶Afterwards, compression strength 20MPa, 10m high perpendicular drop to mattess and do not produce obvious fragmentation；Volume Changes are less than 1% after freezing-thawing test, and compression strength, which reduces, is less than 10%；Volumetric expansion is less than 2%；Related nuclide leaching rate is limited to Cs within 42nd day⁺＜ 5 × 10^‑4cm/d、Co²⁺＜ 1 × 10^‑4cm/d。

Description

A kind of epoxy resin material and preparation method thereof

technical field

The invention relates to the technical field of epoxy resin, in particular to an epoxy resin material and a preparation method thereof.

Background technique

The development and utilization of nuclear energy has brought huge economic and social benefits to human beings, but at the same time produced a large amount of radioactive waste, which has brought a greater threat to the living environment of human beings. Therefore, how to safely and effectively dispose of radioactive waste to maximize its isolation from the biosphere has become an increasingly urgent and important issue facing the nuclear industry and nuclear science, and is a key factor affecting the sustainable and healthy development of nuclear energy. For the disposal of radioactive waste, people think that the most reasonable measure is to solidify the radioactive waste first, and then carry out the final geological disposal of the obtained solidified radioactive waste. Effective solidification of radioactive waste can achieve three purposes: one is to transform liquid radioactive substances into solidified bodies that are convenient for safe transportation, storage and disposal operations; the other is to solidify radionuclides to prevent radionuclides from entering humans. biosphere; the third is to reduce the volume of waste. There are many radioactive waste immobilization methods that have been developed. For medium and low radioactive waste, there are mainly cement immobilization, asphalt immobilization and plastic immobilization; for high radioactive waste, there are mainly glass immobilization and artificial rock immobilization with great development potential. In terms of solidification treatment of radioactive waste, cement solidification technology was developed the earliest and has a history of more than 40 years. Cement solidification is a mature technology, which has been widely adopted by nuclear power plants, nuclear industry departments and nuclear research centers in many countries, and has large-scale engineering applications in Germany, France, the United States, Japan, and India. my country's Qinshan Nuclear Power Plant, Daya Bay Nuclear Power Plant, etc. have all adopted cement solidification process to deal with. At present, the waste solidified by cement is mainly concentrated waste liquid, spent ion exchange resin and filter residue of light water reactor nuclear power plant, and nuclear fuel. Compared with cement solidification, polymer solidification has the following advantages: ①The nuclide leaching rate is lower, slightly lower than asphalt solidification, and 2 to 4 orders of magnitude lower than cement solidification, which is of great significance for long-term safe isolation; ②Inclusive waste Higher volume, less quantity of cured product, reduced disposal costs. Among polymers, epoxy resin has better radiation resistance, so it can be used as a matrix resin for curing radioactive waste. However, there is currently no engineering example of epoxy resin curing radioactive waste in China.

At present, general-purpose epoxy resins have the following disadvantages when dealing with radioactive wet waste (waste resin, radioactive salt block): (1) The mechanical properties of room temperature curing epoxy are insufficient, (2) The anti-leaching performance of the material after irradiation is difficult to reach GB14569.2 - Relevant requirements in the 1993 "Low and Medium Level Radioactive Waste Solidified Body Performance Requirements Plastic Solidified Body" standard.

Contents of the invention

In view of this, the object of the present invention is to provide an epoxy resin material and a preparation method thereof, the epoxy resin material has good mechanical properties and leaching resistance after irradiation.

The invention provides an epoxy resin material, which is prepared from raw materials comprising the following components in parts by weight:

100 parts of epoxy resin mixture;

10-20 parts of carbon nanotube-based iron-based imidazole ionic liquid;

10-20 parts of amino-terminated polyether;

The epoxy resin mixture includes bisphenol A diglycidyl ether, an active toughening agent and 4,5-epoxyhexane-1,2-dicarboxylic acid diglycidyl ester; the active toughening agent has the structure of formula I :

n=1～10;

The carbon nanotube-based iron-based imidazole ionic liquid has the structure of formula II:

The R is selected from -CH ₃ , -C ₄ H ₉ , -C ₆ H ₁₃ or -C ₁₁ H ₂₃ .

Preferably, the mass ratio of bisphenol A diglycidyl ether, active toughening agent and 4,5-epoxyhexane-1,2-dicarboxylic acid diglycidyl ester is 100:25-40:10-15 .

Preferably, the amino-terminated polyether is selected from one or more of D-230, D-200, T-403 and T-5000 amino-terminated polyethers.

Preferably, the reactive toughening agent has an epoxy value of 0.12-0.14.

Preferably, the bisphenol A diglycidyl ether is selected from the model E-51 bisphenol A diglycidyl ether; the 4,5-epoxyhexane-1,2-dicarboxylic acid diglycidyl ester is selected from The model is TDE-85 4,5-epoxyhexane-1,2-dicarboxylic acid diglycidyl ester.

Preferably, the active toughening agent is made by the following method:

a) After dichloroethane, boron trifluoride ether solution and ethylene glycol are mixed, epichlorohydrin is added dropwise for reaction, and the obtained reaction solution is washed until neutral, and then dichloroethane is distilled off to obtain terminal Hydroxypolyepichlorohydrin;

b) reacting the toluene solution of hydroxyl-terminated polyepichlorohydrin with NaOH, neutralizing the obtained reaction liquid, washing with water, and distilling the toluene to obtain the active toughening agent.

Preferably, the reaction temperature in step a) is 38-42° C.; the reaction time is 55-65 minutes;

The reaction temperature in the step b) is 85-95° C.; the reaction time is 3.5-4.5 hours.

Preferably, the carbon nanotube-based iron-based imidazolium ionic liquid is prepared by the following method:

a) reacting 1-alkylimidazole and methyl chloride to obtain 1-alkyl-3-methylimidazolium chloride salt ionic liquid; the alkyl group in the 1-alkylimidazole is selected from methyl, butyl, hexyl or deca An alkyl group; 1-alkyl-3-methylimidazolium chloride salt ionic liquid is reacted with ferric chloride to obtain an iron-based imidazolium ionic liquid;

b) In the presence of dimethylformamide, dicyclohexylcarbodiimide and 4-dimethylaminopyridine, react carboxyl carbon nanotubes with iron-based imidazole ionic liquid to obtain carbon nanotube-based iron-based imidazole ionic liquid .

Preferably, the reaction temperature of the carboxyl carbon nanotubes and the iron-based imidazolium ionic liquid is 55-65°C; the reaction time of the carboxyl carbon nanotubes and the iron-based imidazolium ionic liquid is 22-26 hours.

The present invention provides a kind of preparation method of epoxy resin material described in above-mentioned technical scheme, comprises the following steps:

100 parts of epoxy resin mixture, 10-20 parts of carbon nanotube-based iron-based imidazole ionic liquid and 10-20 parts of amino-terminated polyether are mixed and cured to obtain an epoxy resin material.

The invention provides an epoxy resin material, which is prepared from raw materials comprising the following components in parts by weight: 100 parts of epoxy resin mixture; 10-20 parts of carbon nanotube-based iron-based imidazole ionic liquid; 10-20 parts of amino-terminated polyether 20 parts; the epoxy resin mixture includes bisphenol A diglycidyl ether, active toughening agent and 4,5-epoxy hexane-1,2-diglycidyl carboxylate; the active toughening agent has Formula I structure; the carbon nanotube-based iron-based imidazolium ionic liquid has a formula II structure. The epoxy resin material provided by the invention has good mechanical properties and anti-leaching properties after irradiation under the compatibility of the above components. The experimental results show that: after the irradiation dose is 10 ⁶ , the compressive strength is 20MPa (the degree of reduction is less than 10%), and the vertical drop from a height of 10m to the concrete floor does not produce obvious fragmentation; after the freeze-thaw test, the volume change is less than 1%, and there is no Cracks are visible to the naked eye, and the decrease in compressive strength is less than 10%; the volume expansion is less than 2%; the sample is leached in deionized water at 25°C, and the leaching rate of relevant nuclides on the 42nd day is limited to Cs ⁺ <5×10 ^-4 cm/d, Co ²⁺ <1×10 ^-4 cm/d.

detailed description

The invention provides an epoxy resin material, which is prepared from raw materials comprising the following components in parts by weight:

100 parts of epoxy resin mixture;

10-20 parts of carbon nanotube-based iron-based imidazole ionic liquid;

10-20 parts of amino-terminated polyether;

The epoxy resin mixture includes bisphenol A diglycidyl ether, an active toughening agent and 4,5-epoxyhexane-1,2-dicarboxylic acid diglycidyl ester; the active toughening agent has the structure of formula I :

n=1～10;

The carbon nanotube-based iron-based imidazole ionic liquid has the structure of formula II:

The R is selected from -CH ₃ , -C ₄ H ₉ , -C ₆ H ₁₃ or -C ₁₁ H ₂₃ .

The epoxy resin material provided by the invention has good mechanical properties and anti-leaching properties after irradiation under the compatibility of the above components.

In parts by weight, the raw materials for the preparation of the epoxy resin material provided by the present invention include 100 parts of epoxy resin mixture; the epoxy resin mixture includes bisphenol A diglycidyl ether, active toughening agent and 4,5-ring Diglycidyl oxyhexane-1,2-dicarboxylate; the bisphenol A diglycidyl ether, active toughening agent and 4,5-epoxyhexane-1,2-diglycidyl dicarboxylate The mass ratio is preferably 100:25-40:10-15; in a specific embodiment of the present invention, the epoxy resin mixture includes bisphenol A diglycidyl ether, active toughening agent and 4,5-epoxyhexyl The mass ratio of diglycidyl alkane-1,2-dicarboxylate is 100:30:10; 100:40:10; or 100:25:10. The bisphenol A diglycidyl ether is preferably selected from the model E-51 bisphenol A diglycidyl ether; the 4,5-epoxyhexane-1,2-dicarboxylic acid diglycidyl ester is preferably selected from the model It is TDE-854,5-epoxyhexane-1,2-dicarboxylic acid diglycidyl ester.

In the present invention, there is no special limitation on the sources of the bisphenol A diglycidyl ether and 4,5-epoxyhexane-1,2-dicarboxylic acid diglycidyl ester, and commercially available products are preferably used.

In the present invention, the epoxy value of the active toughening agent is preferably 0.12-0.14. The active toughening agent is preferably prepared by the following method:

a) After dichloroethane, boron trifluoride ether solution and ethylene glycol are mixed, epichlorohydrin is added dropwise for reaction, and the obtained reaction solution is washed until neutral, and then dichloroethane is distilled off to obtain terminal Hydroxypolyepichlorohydrin;

b) reacting the toluene solution of hydroxyl-terminated polyepichlorohydrin with NaOH, neutralizing the obtained reaction liquid, washing with water, and distilling the toluene to obtain the active toughening agent.

In the present invention, after mixing dichloroethane, boron trifluoride ether solution and ethylene glycol, epichlorohydrin is added dropwise for reaction, and the obtained reaction solution is washed to neutrality, and then dichloroethane is distilled off to obtain terminal Hydroxypolyepichlorohydrin. When the epichlorohydrin is added dropwise, the system temperature is 18-23°C; after the epichlorohydrin is added dropwise, the temperature of the system is raised to 38-42°C for reaction. In the present invention, the reaction temperature in step a) is preferably 38-42°C, more preferably 40°C; the reaction time is preferably 55-65min, more preferably 60min. In the present invention, the obtained reaction solution is preferably cooled to room temperature, and then washed to neutrality with saturated sodium bicarbonate solution and deionized water.

After the hydroxyl-terminated polyepichlorohydrin is obtained, the present invention reacts the toluene solution of the hydroxyl-terminated polyepichlorohydrin with NaOH, neutralizes the obtained reaction solution, washes it with water, and distills the toluene to obtain the active toughening agent. In the present invention, hydroxyl-terminated polyepichlorohydrin is dissolved in toluene, and NaOH is added after the system is heated to 85-95°C for reaction, more preferably at 90°C; the reaction time is preferably 3.5-4.5 hours, more preferably 4 hours. In the present invention, it is preferred to add HCl solution to neutralize the remaining NaOH.

The raw materials for preparing the epoxy resin material provided by the invention include 10-20 parts of carbon nanotube-based iron-based imidazole ionic liquid. The carbon nanotube-based iron-based imidazole ionic liquid has the structure of formula II:

The R is selected from -CH ₃ , -C ₄ H ₉ , -C ₆ H ₁₃ or -C ₁₁ H ₂₃ .

In the present invention, the carbon nanotube-based iron-based imidazolium ionic liquid is preferably prepared by the following method:

a) reacting 1-alkylimidazole and methyl chloride to obtain 1-alkyl-3-methylimidazolium chloride salt ionic liquid; the alkyl group in the 1-alkylimidazole is selected from methyl, butyl, hexyl or deca An alkyl group; 1-alkyl-3-methylimidazolium chloride salt ionic liquid is reacted with ferric chloride to obtain an iron-based imidazolium ionic liquid;

b) In the presence of dimethylformamide, dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine (DMAP), react carboxyl carbon nanotubes with iron-based imidazole ionic liquid to obtain carbon nanotubes Iron-based imidazolium ionic liquid.

In the present invention, the synthetic route of described iron-based imidazolium ionic liquid is as shown in reaction scheme 1:

In the reaction scheme 1, the R is -CH ₃ , -C ₄ H ₉ , -C ₆ H ₁₃ or -C ₁₁ H ₂₃ .

In the present invention, there is no special limitation on the source of the carboxy carbon nanotubes, and carboxy carbon nanotubes well known to those skilled in the art can be used. In the present invention, the carboxyl carbon nanotubes are preferably prepared according to the following method:

Mixing carbon nanotubes with sulfuric acid-nitric acid mixed acid, ultrasonication, and reflux reaction, mixing the reaction product with water and suction filtering with a polytetrafluoroethylene membrane until the pH value of the filtrate is about 7, to obtain carboxyl carbon nanotubes.

In the present invention, the reaction temperature of the carboxyl carbon nanotube and iron-based imidazolium ionic liquid is preferably 55-65°C, more preferably 58-62°C, most preferably 60°C; The time of liquid reaction is preferably 22-26h, more preferably 23h-15h, most preferably 24h.

In the present invention, after the reaction product of carboxyl carbon nanotubes and iron-based imidazole ionic liquid is centrifuged to obtain the crude product, the crude product is washed with acetonitrile for several times and centrifuged to remove impurities such as excess raw materials, and finally placed in a vacuum oven for drying to obtain carbon Nanotube-based iron-based imidazolium ionic liquid.

In a specific embodiment of the present invention, the synthesis route of carbon nanotube-based iron-based imidazole ionic liquid is shown in reaction scheme 2:

The raw materials for preparing the epoxy resin material provided by the invention include 10-20 parts of amino-terminated polyether. In the present invention, the amino-terminated polyether is preferably selected from one or more of D-230, D-200, T-403 and T-5000 amino-terminated polyethers. The amino-terminated polyether of the above-mentioned model is produced by Hongbaoli Group Co., Ltd.

The present invention provides a kind of preparation method of epoxy resin material described in above-mentioned technical scheme, comprises the following steps:

100 parts of epoxy resin mixture, 10-20 parts of carbon nanotube-based iron-based imidazole ionic liquid and 10-20 parts of amino-terminated polyether are mixed and cured to obtain an epoxy resin material.

In the present invention, the epoxy resin mixture, the carbon nanotube-based iron-based imidazole ionic liquid and the amino-terminated polyether are preferably mixed uniformly to remove air bubbles. In the present invention, the curing temperature is preferably 20-25°C.

The invention provides an epoxy resin material, which is prepared from raw materials comprising the following components in parts by weight: 100 parts of epoxy resin mixture; 10-20 parts of carbon nanotube-based iron-based imidazole ionic liquid; 10-20 parts of amino-terminated polyether 20 parts; the epoxy resin mixture includes bisphenol A diglycidyl ether, active toughening agent and 4,5-epoxy hexane-1,2-diglycidyl carboxylate; the active toughening agent has Formula I structure; the carbon nanotube-based iron-based imidazolium ionic liquid has a formula II structure. The epoxy resin material provided by the invention has good mechanical properties and anti-leaching properties after irradiation under the compatibility of the above components. The experimental results show that: after the irradiation dose is 10 ⁶ , the compressive strength is 20MPa (the degree of reduction is less than 10%), and the vertical drop from a height of 10m to the concrete floor does not produce obvious fragmentation; after the freeze-thaw test, the volume change is less than 1%, and there is no Cracks are visible to the naked eye, and the decrease in compressive strength is less than 10%; the volume expansion is less than 2%; the sample is leached in deionized water at 25°C, and the leaching rate of relevant nuclides on the 42nd day is limited to Cs ⁺ <5×10 ^-4 cm/d, Co ²⁺ <1×10 ^-4 cm/d.

In order to further illustrate the present invention, an epoxy resin material provided by the present invention and its preparation method are described in detail below in conjunction with examples, but they should not be construed as limiting the protection scope of the present invention.

Example 1

Add a certain amount of dichloroethane, boron trifluoride·ether solution and ethylene glycol into the reaction kettle, stir evenly, start to add epichlorohydrin dropwise, and control the whole reaction temperature at 18-23°C. After the epichlorohydrin was added dropwise, the temperature of the reaction solution was raised to 40° C., and the reaction was carried out for one hour. After the reaction solution is cooled to room temperature, it is washed repeatedly with saturated sodium bicarbonate solution and deionized water until it becomes neutral, and dichloroethane is distilled off to obtain hydroxyl-terminated polyepichlorohydrin (PECH). Dissolve the self-made PECH in an appropriate amount of toluene, heat up to 90°C and add a certain amount of analytically pure NaOH. After reacting for four hours, add HCl aqueous solution to neutralize the remaining NaOH, and wash repeatedly with deionized water until the solution is neutral. properties, after distilling the toluene, it becomes epoxy A, and the epoxy value is 0.12;

Add freshly distilled methyl chloride dropwise to 1-methylimidazole, and react under the condition of heating and stirring at 60° C. to obtain 3-methylimidazolium chloride salt ionic liquid. After the hydrolysis, the obtained 3-methylimidazolium chloride salt ionic liquid is reacted with ferric chloride to obtain the iron-based imidazolium ionic liquid. Then carboxylated MWNT and iron-based imidazolium ionic liquid were added into DMF, DCC and DMAP, and ultrasonicated for 10min at 60°C. C under heating and stirring for 24h. After the reaction is completed, the crude product is obtained by centrifugation, and the product is washed with acetonitrile for several times, and impurities such as excess raw materials are removed by centrifugation. Finally vacuum oven 60. C is dried to obtain carbon nanotube-based 3-methyliron-based imidazolium ionic liquid B.

Mix 100 parts of epoxy resin mixture (E-51: Epoxy A: TDE-85=100:30:10) with 10 parts of carbon nanotube-based iron-based imidazole ionic liquid, 20 parts of polyetheramine epoxy curing agent D- Mix at 230°C, stir evenly, remove air bubbles, and prepare an adhesive, place it at 20-25°C and cure for 24 hours to obtain an epoxy resin material and conduct a performance test.

Test standard: GB14569.2-1993 "Low and medium level radioactive waste solidified body performance requirements plastic solidified body"

Test results: After an irradiation dose of 10 ⁶ Gy:

Compressive strength: 20MPa (the degree of reduction is less than 10%), and the vertical drop from a height of 10m to the concrete floor does not produce obvious fragmentation;

Freeze-thaw resistance: After the freeze-thaw test, the volume change is less than 1%, no visible cracks, and the compressive strength is reduced by less than 10%;

Volume expansion is less than 2%;

Simulated water resistance and immersion resistance: the sample is leached in deionized water at 25°C, and the leaching rate of relevant nuclides on the 42nd day is limited to Cs ⁺ <5×10 ^-4 cm/d, Co ²⁺ <1×10 ^-4 cm/d d.

Example 2

Add a certain amount of dichloroethane, boron trifluoride·ether solution and ethylene glycol into the reaction kettle, stir evenly, start to add epichlorohydrin dropwise, and control the whole reaction temperature at 18-23°C. After the epichlorohydrin was added dropwise, the temperature of the reaction solution was raised to 40° C., and the reaction was carried out for two hours. After the reaction solution is cooled to room temperature, it is washed repeatedly with saturated sodium bicarbonate solution and deionized water until it becomes neutral, and dichloroethane is distilled off to obtain hydroxyl-terminated polyepichlorohydrin (PECH). Dissolve the self-made PECH in an appropriate amount of toluene, heat up to 90°C and add a certain amount of analytically pure NaOH. After reacting for four hours, add HCl aqueous solution to neutralize the remaining NaOH, and wash repeatedly with deionized water until the solution is neutral. properties, after distilling the toluene, it becomes epoxy A, and the epoxy value is 0.14;

Add freshly distilled methyl chloride dropwise to 1-methylimidazole, and react under the condition of heating and stirring at 60° C. to obtain 3-butylimidazolium chloride salt ionic liquid. After hydrolysis, the obtained 3-butylimidazolium chloride salt ionic liquid is reacted with ferric chloride to obtain the iron-based imidazolium ionic liquid. Then carboxylated MWNT and iron-based imidazolium ionic liquid were added into DMF, DCC and DMAP, and ultrasonicated for 10min at 60°C. C under heating and stirring for 24h. After the reaction is completed, the crude product is obtained by centrifugation, and the product is washed with acetonitrile for several times, and impurities such as excess raw materials are removed by centrifugation. Finally vacuum oven 60. C is dried to obtain carbon nanotube-based 3-butyliron-based imidazolium ionic liquid B.

Mix 100 parts of epoxy resin mixture (E-51:A:TDE-85=100:40:10) with 15 parts of carbon nanotube-based iron-based imidazole ionic liquid and 20 parts of polyetheramine epoxy curing agent T-403 , stir evenly, remove air bubbles, and prepare an adhesive, place it at 20-25°C and cure for 24 hours to obtain an epoxy resin material and conduct a performance test.

Test standard: GB14569.2-1993 "Low and medium level radioactive waste solidified body performance requirements plastic solidified body"

Test results: After an irradiation dose of 106Gy:

Compressive strength: 20MPa (the degree of reduction is less than 10%), and the vertical drop from a height of 10m to the concrete floor does not produce obvious fragmentation;

Freeze-thaw resistance: After the freeze-thaw test, the volume change is less than 1%, no visible cracks, and the compressive strength is reduced by less than 10%;

Volume expansion is less than 2%;

Simulated water resistance and immersion resistance: the sample is leached in deionized water at 25°C, and the leaching rate of relevant nuclides on the 42nd day is limited to Cs ⁺ <5×10 ^-4 cm/d, Co ²⁺ <1×10 ^-4 cm/d d.

Example 3

Add a certain amount of dichloroethane, boron trifluoride·ether solution and ethylene glycol into the reaction kettle, stir evenly, start to add epichlorohydrin dropwise, and control the whole reaction temperature at 18-23°C. After the epichlorohydrin was added dropwise, the temperature of the reaction solution was raised to 40° C., and the reaction was carried out for two hours. After the reaction solution is cooled to room temperature, it is washed repeatedly with saturated sodium bicarbonate solution and deionized water until it becomes neutral, and dichloroethane is distilled off to obtain hydroxyl-terminated polyepichlorohydrin (PECH). Dissolve the self-made PECH in an appropriate amount of toluene, heat up to 90°C and add a certain amount of analytically pure NaOH. After reacting for four hours, add HCl aqueous solution to neutralize the remaining NaOH, and wash repeatedly with deionized water until the solution is neutral. properties, after distilling the toluene, it becomes epoxy A, and the epoxy value is 0.14;

Add freshly distilled methyl chloride dropwise to 1-methylimidazole, and react under the condition of heating and stirring at 60° C. to obtain 3-hexylimidazolium chloride salt ionic liquid. After hydrolysis, the obtained 3-hexylimidazolium chloride salt ionic liquid is reacted with ferric chloride to obtain the iron-based imidazolium ionic liquid. Then carboxylated MWNT and iron-based imidazolium ionic liquid were added into DMF, DCC and DMAP, and ultrasonicated for 10min at 60°C. C under heating and stirring for 24h. After the reaction is completed, the crude product is obtained by centrifugation, and the product is washed with acetonitrile for several times, and impurities such as excess raw materials are removed by centrifugation. Finally vacuum oven 60. C is dried to obtain carbon nanotube-based 3-hexyliron-based imidazolium ionic liquid B.

Mix 100 parts of epoxy resin mixture (E-51:A:TDE-85=100:25:10) with 15 parts of carbon nanotube-based iron-based imidazole ionic liquid and 10 parts of polyetheramine epoxy curing agent T-5000 , stir evenly, remove air bubbles, and prepare an adhesive, place it at 20-25°C and cure for 24 hours to obtain an epoxy resin material and conduct a performance test.

Test standard: GB14569.2-1993 "Low and medium level radioactive waste solidified body performance requirements plastic solidified body"

Test results: After an irradiation dose of 10 ⁶ Gy:

Compressive strength: 20MPa (the degree of reduction is less than 10%), and the vertical drop from a height of 10m to the concrete floor does not produce obvious fragmentation;

Freeze-thaw resistance: After the freeze-thaw test, the volume change is less than 1%, no visible cracks, and the compressive strength is reduced by less than 10%%;

Volume expansion is less than 2%;

Simulated water resistance and immersion resistance: the sample is leached in deionized water at 25°C, and the leaching rate of relevant nuclides on the 42nd day is limited to Cs ⁺ <5×10 ^-4 cm/d, Co ²⁺ <1×10 ^-4 cm/d d

Example 4

Epoxy A and carbon nanotube-based iron-based imidazole ionic liquids were prepared by using Example 1.

Mix 100 parts of epoxy resin mixture (E-51: Epoxy A: TDE-85=100:40:10) with 15 parts of carbon nanotube-based iron-based imidazole ionic liquid, 15 parts of polyetheramine epoxy curing agent T- Mix at 5000°C, stir evenly, remove air bubbles, and prepare an adhesive. After curing at 20-25°C for 24 hours, an epoxy resin material is obtained and performance tests are performed.

Test standard: GB14569.2-1993 "Low and medium level radioactive waste solidified body performance requirements plastic solidified body"

Test results: After an irradiation dose of 10 ⁶ Gy:

Compressive strength: 20MPa (the degree of reduction is less than 10%), and the vertical drop from a height of 10m to the concrete floor does not produce obvious fragmentation;

Freeze-thaw resistance: After the freeze-thaw test, the volume change is less than 1%, no visible cracks, and the compressive strength is reduced by less than 10%;

Volume expansion is less than 2%;

Simulated water resistance and immersion resistance: the sample is leached in deionized water at 25°C, and the leaching rate of relevant nuclides on the 42nd day is limited to Cs ⁺ <5×10 ^-4 cm/d, Co ²⁺ <1×10 ^-4 cm/d d.

As can be seen from the above examples, the present invention provides an epoxy resin material, which is prepared from raw materials comprising the following components by weight: 100 parts of epoxy resin mixture; 10-20 parts of carbon nanotube-based iron-based imidazole ionic liquid; 10-20 parts of amino-terminated polyether; the epoxy resin mixture includes bisphenol A diglycidyl ether, active toughening agent and 4,5-epoxyhexane-1,2-dicarboxylic acid diglycidyl ester; The active toughening agent has a structure of formula I; the carbon nanotube-based iron-based imidazole ionic liquid has a structure of formula II. The epoxy resin material provided by the invention has good mechanical properties and anti-leaching properties after irradiation under the compatibility of the above components. The experimental results show that: after the irradiation dose is 10 ⁶ , the compressive strength is 20MPa (the degree of reduction is less than 10%), and the vertical drop from a height of 10m to the concrete floor does not produce obvious fragmentation; after the freeze-thaw test, the volume change is less than 1%, and there is no Cracks are visible to the naked eye, and the decrease in compressive strength is less than 10%; the volume expansion is less than 2%; the sample is leached in deionized water at 25°C, and the leaching rate of relevant nuclides on the 42nd day is limited to Cs ⁺ <5×10 ^-4 cm/d, Co ²⁺ <1×10 ^-4 cm/d.

The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (10)

1. a kind of epoxide resin material, it is made by the raw material including following parts by weight of component：

100 parts of epoxy resin composition；

10~20 parts of CNT base iron-based imidazole ion liquid；

10~20 parts of amine terminated polyether；

The epoxy resin composition includes bisphenol A diglycidyl ether, endurable active toughener and 4,5- oxepane -1,2- diformazans Sour 2-glycidyl ester；The endurable active toughener has structure shown in formula I：

N=1~10；

The CNT base iron-based imidazole ion liquid has the structure of formula II：

The R is selected from-CH₃,-C₄H₉,-C₆H₁₃Or-C₁₁H₂₃。

2. epoxide resin material according to claim 1, it is characterised in that the bisphenol A diglycidyl ether, activity increase The mass ratio of tough dose and 4,5- oxepane -1,2- dicarboxylic acid diglycidyl esters is 100:25~40:10~15.

3. epoxide resin material according to claim 1, it is characterised in that the amine terminated polyether is selected from model D- 230th, the one or more in D-200, T-403 and T-5000 amine terminated polyether.

4. epoxide resin material according to claim 1, it is characterised in that the endurable active toughener obtains epoxide number as 0.12 ~0.14.

5. epoxide resin material according to claim 1, it is characterised in that the bisphenol A diglycidyl ether is selected from type Number it is E-51 bisphenol A diglycidyl ethers；4,5- oxepanes -1,2- the dicarboxylic acid diglycidyl esters are selected from model TDE-85 4,5- oxepane -1,2- dicarboxylic acid diglycidyl esters.

6. epoxide resin material according to claim 1, it is characterised in that the endurable active toughener is by following methods system ：

A) after mixing dichloroethanes, boron trifluoride ether solution and ethylene glycol, epoxychloropropane is added dropwise, reaction, obtains Reaction solution is rinsed to neutrality, then steams dichloroethanes, obtains Based On Hydroxy-terminated Polyepichlorohydrin；

B) toluene solution of Based On Hydroxy-terminated Polyepichlorohydrin and NaOH are reacted, obtained reaction solution is neutralized, washing, then by first Benzene steams, and obtains endurable active toughener.

7. epoxide resin material according to claim 6, it is characterised in that in the step a) temperature of reaction for 38~ 42℃；The time of reaction is 55~65min；

The temperature of reaction is 85~95 DEG C in the step b)；The time of reaction is 3.5~4.5h.

8. epoxide resin material according to claim 1, it is characterised in that the CNT base iron-based imidazol ion liquid Body is made by following methods：

A) 1- alkyl imidazoles and chloromethanes are reacted, obtains 1- alkyl -3- methylimidazole villaumite ionic liquids；The 1- alkyl miaow Alkyl is selected from methyl, butyl, hexyl or undecyl in azoles；By 1- alkyl -3- methylimidazole villaumites ionic liquid and tri-chlorination Iron reacts, and obtains iron-based imidazole ion liquid；

B) in the presence of dimethylformamide, dicyclohexylcarbodiimide and DMAP, by carboxyl CNT Reacted with iron-based imidazole ion liquid, obtain CNT base iron-based imidazole ion liquid.

9. epoxide resin material according to claim 8, it is characterised in that the carboxyl CNT and iron-based imidazoles from The temperature of sub- liquid reactions is 55~65 DEG C；The time of carboxyl CNT and the reaction of iron-based imidazole ion liquid is 22~26h.

10. the preparation method of epoxide resin material, comprises the following steps described in a kind of claim 1~9 any one：

By 100 parts of epoxy resin composition, 10~20 parts of CNT base iron-based imidazole ion liquid and amine terminated polyether 10~ 20 parts of mixing, solidification, obtain epoxide resin material.