Imidazole functionalized sepiolite modified epoxy resin composite material and preparation method thereof
By functionalizing the sepiolite with imidazole and mixing it with epoxy resin to form an anhydride-imidazole curing synergistic system, the problem of insufficient mechanical properties and thermal stability of traditional epoxy resin materials is solved, and the comprehensive performance of the material is significantly improved.
Patent Information
- Application Number
- CN202411788902.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-06
- Publication Date
- 2025-02-28
- Estimated Expiration
- Not applicable · inactive patent
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of new materials, in particular to an imidazole-functionalized sepiolite-modified epoxy resin composite material and a preparation method thereof. Background Art
[0002] Sepiolite is a natural inorganic nanomaterial with the advantages of high specific surface area and good thermal stability. It is an ideal nanofiller and is widely used in polymer materials such as polystyrene and rubber. It has a great effect on improving the mechanical properties and thermal stability of the materials. In recent years, sepiolite has been modified. The organic sepiolite modified with hexadecyltrimethylammonium bromide, surfactants, etc. can be better used in polymer materials.
[0003] Epoxy resin has good mechanical strength, electrical insulation properties, etc. It has abundant products, mainly epoxy resin coatings, adhesives, etc., which are widely used in machinery manufacturing, electrical industry, civil engineering and other fields. Using sepiolite as a nanofiller to enhance and modify epoxy resin can improve the comprehensive performance of the material. However, the compatibility of unmodified sepiolite with epoxy resin is poor, and the solution agglomerates and aggregates, which affects the reinforcing effect of sepiolite on epoxy resin materials. Therefore, it is necessary to organically modify the sepiolite. Summary of the invention
[0004] 1. Technical issues to be resolved In view of the deficiencies in the prior art, the present invention provides an imidazole-functionalized sepiolite-modified epoxy resin composite material and a preparation method thereof, which solves the problems of low mechanical properties and poor thermal stability of traditional epoxy resins.
[0005] (II) Technical solution To achieve the above object, the present invention provides the following technical solution: an imidazole-functionalized sepiolite-modified epoxy resin composite material, wherein the preparation method of the imidazole-functionalized sepiolite-modified epoxy resin composite material comprises the following steps: (1) The sepiolite is activated in a dilute hydrochloric acid solution, and then 100 parts by weight of the acid-activated sepiolite is added to a reaction container, deionized water, ethanol, and 20-60 parts of 3-aminopropyltrimethoxysilane are added, ultrasonically dispersed and heated to 60-90°C, reacted for 3-8 hours, centrifuged after the reaction, and washed with deionized water to obtain amino-functionalized sepiolite.
[0006] (2) Adding ethanol solvent and amino-functionalized sepiolite into a reaction vessel, ultrasonically dispersing and adding glutaric anhydride, heating to 30-50 °C, reacting for 2-6 h, centrifuging after the reaction, washing with ethanol and dichloromethane, and obtaining carboxyl-functionalized sepiolite.
[0007] (3) Adding N,N-dimethylformamide solvent, amino-functionalized sepiolite and histamine into a reaction container, ultrasonically dispersing, adding a condensing agent and a catalyst, and reacting, centrifuging after the reaction, washing with dichloromethane and acetone, and obtaining imidazole-functionalized sepiolite.
[0008] (4) Add acetone solvent and imidazole-functionalized sepiolite into a reaction container, add epoxy resin, silicone defoamer and leveling agent after ultrasonic dispersion, and emulsify at high speed. Use methyl hexahydrophthalic anhydride as a curing agent to obtain an imidazole-functionalized sepiolite-modified epoxy resin composite material.
[0009] Preferably, in step (2), the amino-functionalized sepiolite is 100 parts and the glutaric anhydride is 250-800 parts by weight.
[0010] Preferably, in step (3), the condensing agent is O-benzotriazole-tetramethyluronium hexafluorophosphate and the catalyst is triethylamine.
[0011] Preferably, in step (3), the amino-functionalized sepiolite is 100 parts, histamine is 80-250 parts, the condensing agent is 70-220 parts, and the catalyst is 55-180 parts, by weight.
[0012] Preferably, the reaction in step (3) is carried out at 25-45° C. for 12-36 h.
[0013] Preferably, in step (4), the amount of imidazole-functionalized sepiolite is 0.5-3 parts, and the amount of epoxy resin is 100 parts, by weight.
[0014] 3. Beneficial technical effects Compared with the prior art, the present invention has the following beneficial technical effects: The imidazole-functionalized sepiolite modified epoxy resin composite material is modified by 3-aminopropyltrimethoxysilane to introduce amino groups on the surface of acid-activated sepiolite, then the amino groups react with glutaric anhydride, the glutaric anhydride is ring-opened to generate carboxyl groups, and carboxyl-functionalized sepiolite is obtained; further, in a purification system of O-benzotriazole-tetramethyluronium hexafluorophosphate and triethylamine, the abundant carboxyl groups on the surface of the carboxyl-functionalized sepiolite are subjected to amidation reaction with the amino groups of the histamine side chain, thereby obtaining the imidazole-functionalized sepiolite; the obtained imidazole functional groups are introduced on the surface of the sepiolite, and the organic functionalization modification of the sepiolite is realized.
[0015] Imidazole-functionalized sepiolite is used as a nanofiller and is blended and modified with epoxy resin. In the methylhexahydrophthalic anhydride curing system, the imidazole functional groups modified on the surface of the sepiolite can act as a curing accelerator to form an anhydride-imidazole curing synergistic system, so that the epoxy resin is cross-linked and cured on the surface of the sepiolite. The imidazole-functionalized sepiolite serves as a chemical cross-linking site, which limits the movement of the epoxy resin molecular chain, is beneficial to improving the thermal stability of the epoxy resin, and has a significant effect on increasing the thermal decomposition temperature. After imidazole-functionalized modification, the sepiolite is more evenly dispersed in the epoxy resin matrix, which can better play the reinforcing role of the nanofiller and significantly enhance the mechanical properties of the epoxy resin, such as the compressive strength. DETAILED DESCRIPTION
[0016] To achieve the above object, the present invention provides the following embodiments and examples: an imidazole-functionalized sepiolite-modified epoxy resin composite material, the preparation method of which is as follows: (1) The sepiolite is activated in a dilute hydrochloric acid solution, and then 100 parts by weight of the acid-activated sepiolite is added to a reaction container, deionized water, ethanol, and 20-60 parts of 3-aminopropyltrimethoxysilane are added, ultrasonically dispersed and heated to 60-90°C, reacted for 3-8 hours, centrifuged after the reaction, and washed with deionized water to obtain amino-functionalized sepiolite.
[0017] (2) Adding an ethanol solvent and 100 parts by weight of amino-functionalized sepiolite into a reaction container, ultrasonically dispersing and adding 250-800 parts of glutaric anhydride, heating to 30-50°C, reacting for 2-6 hours, centrifuging after the reaction, washing with ethanol and dichloromethane, and obtaining carboxyl-functionalized sepiolite.
[0018] (3) Add N,N-dimethylformamide solvent, 100 parts by weight of amino-functionalized sepiolite and 80-250 parts by weight of histamine into a reaction container, disperse by ultrasonic and add 70-220 parts of condensation agent O-benzotriazole-tetramethyluronium hexafluorophosphate and 55-180 parts of catalyst triethylamine, react at 25-45 °C for 12-36 h, centrifuge after the reaction, wash with dichloromethane and acetone to obtain imidazole-functionalized sepiolite.
[0019] (4) Add acetone solvent and 0.5-3 parts by weight of imidazole-functionalized sepiolite into a reaction container, add 100 parts of epoxy resin, silicone defoamer and leveling agent after ultrasonic dispersion, and emulsify at high speed, use methyl hexahydrophthalic anhydride as a curing agent, and obtain an imidazole-functionalized sepiolite-modified epoxy resin composite material.
[0020] Example 1
[0021] (1) The sepiolite was activated in a 2% dilute hydrochloric acid solution. Then, 1 g of the acid-activated sepiolite was added to a reaction container. 3 mL of deionized water, 30 mL of ethanol, and 0.2 g of 3-aminopropyltrimethoxysilane were added. The mixture was ultrasonically dispersed and heated to 60 °C. The reaction was continued for 3 h. After the reaction, the mixture was centrifuged and washed with deionized water to obtain amino-functionalized sepiolite.
[0022] (2) Add 200 mL of ethanol solvent and 2 g of amino-functionalized sepiolite into a reaction container, disperse by ultrasonication, add 5 g of glutaric anhydride, heat to 30 °C, react for 2 h, centrifuge after the reaction, wash with ethanol and dichloromethane to obtain carboxyl-functionalized sepiolite.
[0023] (3) Add 80 mL of N,N-dimethylformamide solvent, 2 g of amino-functionalized sepiolite and 1.6 g of histamine into the reaction container, disperse by ultrasonication, add 1.4 g of condensation agent O-benzotriazole-tetramethyluronium hexafluorophosphate and 1.1 g of catalyst triethylamine, and react at 25 °C for 12 h. After the reaction, centrifuge and wash with dichloromethane and acetone to obtain imidazole-functionalized sepiolite.
[0024] (4) Acetone solvent and 0.05 g of imidazole-functionalized sepiolite were added to a reaction container. After ultrasonic dispersion, 10 g of epoxy resin, 0.04 g of silicone defoamer and 0.03 g of leveling agent were added and emulsified at high speed. Methylhexahydrophthalic anhydride was used as a curing agent to obtain an imidazole-functionalized sepiolite-modified epoxy resin composite material.
[0025] Example 2
[0026] (1) The sepiolite was activated in a 3% dilute hydrochloric acid solution. Then, 1 g of the acid-activated sepiolite was added to a reaction container. 4 mL of deionized water, 40 mL of ethanol, and 0.3 g of 3-aminopropyltrimethoxysilane were added. The mixture was ultrasonically dispersed and heated to 60 °C. The reaction was continued for 4 h. After the reaction, the mixture was centrifuged and washed with deionized water to obtain amino-functionalized sepiolite.
[0027] (2) Add 200 mL of ethanol solvent and 2 g of amino-functionalized sepiolite into a reaction container, disperse by ultrasonication, add 7 g of glutaric anhydride, heat to 30 °C, react for 3 h, centrifuge after the reaction, wash with ethanol and dichloromethane to obtain carboxyl-functionalized sepiolite.
[0028] (3) Add 150 mL of N,N-dimethylformamide solvent, 2 g of amino-functionalized sepiolite and 2.2 g of histamine into the reaction container, disperse by ultrasonication, add 2 g of condensation agent O-benzotriazole-tetramethyluronium hexafluorophosphate and 1.5 g of catalyst triethylamine, and react at 25 °C for 24 h. After the reaction, centrifuge and wash with dichloromethane and acetone to obtain imidazole-functionalized sepiolite.
[0029] (4) Acetone solvent and 0.1 g of imidazole-functionalized sepiolite were added to a reaction container. After ultrasonic dispersion, 10 g of epoxy resin, 0.05 g of silicone defoamer and 0.04 g of leveling agent were added and emulsified at high speed. Methylhexahydrophthalic anhydride was used as a curing agent to obtain an imidazole-functionalized sepiolite-modified epoxy resin composite material.
[0030] Example 3
[0031] (1) The sepiolite was activated in a 4% dilute hydrochloric acid solution. Then, 1 g of the acid-activated sepiolite was added to a reaction container. 6 mL of deionized water, 50 mL of ethanol, and 0.4 g of 3-aminopropyltrimethoxysilane were added. The mixture was ultrasonically dispersed and heated to 80 °C. The reaction was continued for 4 h. After the reaction, the mixture was centrifuged and washed with deionized water to obtain amino-functionalized sepiolite.
[0032] (2) Add 500 mL of ethanol solvent and 2 g of amino-functionalized sepiolite into a reaction container, disperse by ultrasonication, add 10 g of glutaric anhydride, heat to 40 °C, react for 4 h, centrifuge after the reaction, wash with ethanol and dichloromethane to obtain carboxyl-functionalized sepiolite.
[0033] (3) Add 300 mL of N,N-dimethylformamide solvent, 2 g of amino-functionalized sepiolite and 3 g of histamine into the reaction container, disperse by ultrasonication, add 2.5 g of condensation agent O-benzotriazole-tetramethyluronium hexafluorophosphate and 2.2 g of catalyst triethylamine, and react at 35 °C for 24 h. After the reaction, centrifuge and wash with dichloromethane and acetone to obtain imidazole-functionalized sepiolite.
[0034] (4) Acetone solvent and 0.18 g of imidazole-functionalized sepiolite were added to a reaction container. After ultrasonic dispersion, 10 g of epoxy resin, 0.08 g of silicone defoamer and 0.06 g of leveling agent were added and emulsified at high speed. Methylhexahydrophthalic anhydride was used as a curing agent to obtain an imidazole-functionalized sepiolite-modified epoxy resin composite material.
[0035] Example 4
[0036] (1) The sepiolite was activated in a 6% dilute hydrochloric acid solution. Then, 1 g of the acid-activated sepiolite was added to a reaction vessel. 8 mL of deionized water, 70 mL of ethanol, and 0.5 g of 3-aminopropyltrimethoxysilane were added. The mixture was ultrasonically dispersed and heated to 80 °C. The reaction was continued for 5 h. After the reaction, the mixture was centrifuged and washed with deionized water to obtain amino-functionalized sepiolite.
[0037] (2) Add 650 mL of ethanol solvent and 2 g of amino-functionalized sepiolite into a reaction container, disperse by ultrasonication, add 12 g of glutaric anhydride, heat to 50 °C, react for 2 h, centrifuge after the reaction, wash with ethanol and dichloromethane to obtain carboxyl-functionalized sepiolite.
[0038] (3) Add 400 mL of N,N-dimethylformamide solvent, 2 g of amino-functionalized sepiolite and 4.2 g of histamine into the reaction container, disperse by ultrasonic, add 3.8 g of condensation agent O-benzotriazole-tetramethyluronium hexafluorophosphate and 3 g of catalyst triethylamine, and react at 35 °C for 24 h. After the reaction, centrifuge and wash with dichloromethane and acetone to obtain imidazole-functionalized sepiolite.
[0039] (4) Acetone solvent and 0.25 g of imidazole-functionalized sepiolite were added to a reaction container. After ultrasonic dispersion, 10 g of epoxy resin, 0.1 g of silicone defoamer and 0.08 g of leveling agent were added and emulsified at high speed. Methylhexahydrophthalic anhydride was used as a curing agent to obtain an imidazole-functionalized sepiolite-modified epoxy resin composite material.
[0040] Example 5
[0041] (1) The sepiolite was activated in a 6% dilute hydrochloric acid solution. Then, 1 g of the acid-activated sepiolite was added to a reaction container. 10 mL of deionized water, 80 mL of ethanol, and 0.6 g of 3-aminopropyltrimethoxysilane were added. The mixture was ultrasonically dispersed and heated to 90 °C. The reaction was continued for 8 h. After the reaction, the mixture was centrifuged and washed with deionized water to obtain amino-functionalized sepiolite.
[0042] (2) Add 800 mL of ethanol solvent and 2 g of amino-functionalized sepiolite into a reaction container, disperse by ultrasonication, add 16 g of glutaric anhydride, heat to 50 °C, react for 6 h, centrifuge after the reaction, wash with ethanol and dichloromethane to obtain carboxyl-functionalized sepiolite.
[0043] (3) Add 500 mL of N,N-dimethylformamide solvent, 2 g of amino-functionalized sepiolite and 5 g of histamine into the reaction container, disperse by ultrasonication, add 4.4 g of condensation agent O-benzotriazole-tetramethyluronium hexafluorophosphate and 3.6 g of catalyst triethylamine, and react at 45 °C for 36 h. After the reaction, centrifuge and wash with dichloromethane and acetone to obtain imidazole-functionalized sepiolite.
[0044] (4) Acetone solvent and 0.3 g of imidazole-functionalized sepiolite were added to a reaction container. After ultrasonic dispersion, 10 g of epoxy resin, 0.12 g of silicone defoamer and 0.1 g of leveling agent were added and emulsified at high speed. Methylhexahydrophthalic anhydride was used as a curing agent to obtain an imidazole-functionalized sepiolite-modified epoxy resin composite material.
[0045] Comparative Example 1 (1) The sepiolite was activated in a 5% dilute hydrochloric acid solution. Then, 1 g of the acid-activated sepiolite was added to a reaction container. 8 mL of deionized water, 60 mL of ethanol, and 0.7 g of 3-aminopropyltrimethoxysilane were added. The mixture was ultrasonically dispersed and heated to 60 °C. The reaction was continued for 5 h. After the reaction, the mixture was centrifuged and washed with deionized water to obtain amino-functionalized sepiolite.
[0046] (2) Add 500 mL of ethanol solvent and 2 g of amino-functionalized sepiolite into a reaction container, disperse by ultrasonication, add 10 g of glutaric anhydride, heat to 30 °C, react for 4 h, centrifuge after the reaction, wash with ethanol and dichloromethane to obtain carboxyl-functionalized sepiolite.
[0047] (3) Acetone solvent and 0.15 g of carboxyl functionalized sepiolite were added to a reaction container. After ultrasonic dispersion, 10 g of epoxy resin, 0.08 g of silicone defoamer and 0.05 g of leveling agent were added and emulsified at high speed. Methylhexahydrophthalic anhydride was used as a curing agent to obtain a sepiolite-modified epoxy resin composite material.
[0048] The imidazole-functionalized sepiolite-modified epoxy resin composite material obtained in the example and the sepiolite-modified epoxy resin composite material obtained in the comparative example were poured into a mold, cured at 70-100°C for 3-5 h, and then cured at 130-150°C for 5-8 h to prepare an epoxy resin film with a specification of 4 cm×0.5 cm×0.5 cm. The bending strength was tested using an HZ universal testing machine using GB / T 9341-2008 as the test standard.
[0049]
[0050] The epoxy resin film was made into a 3 cm × 1 cm thin film sample and placed in an ATS-type TGA thermogravimetric analyzer with a heating rate of 20 ℃ / min and a test temperature of 20-800 ℃ to test the heat resistance.
[0051]
Claims
1. An imidazole-functionalized sepiolite-modified epoxy resin composite material, characterized in that: The preparation method of the imidazole-functionalized sepiolite-modified epoxy resin composite material comprises the following steps: (1) Activate sepiolite in a dilute hydrochloric acid solution, then add 100 parts by weight of the acid-activated sepiolite into a reaction container, add deionized water, ethanol, and 20-60 parts of 3-aminopropyltrimethoxysilane, ultrasonically disperse and heat to 60-90°C, react for 3-8 hours, centrifuge after the reaction, and wash with deionized water to obtain amino-functionalized sepiolite; (2) adding ethanol solvent and amino-functionalized sepiolite into a reaction container, dispersing by ultrasonication and adding glutaric anhydride, heating to 30-50 °C, reacting for 2-6 h, centrifuging after the reaction, washing with ethanol and dichloromethane to obtain carboxyl-functionalized sepiolite; (3) adding N,N-dimethylformamide solvent, amino-functionalized sepiolite and histamine into a reaction container, performing ultrasonic dispersion, adding a condensation agent and a catalyst, and reacting, performing centrifugal separation after the reaction, and washing with dichloromethane and acetone to obtain imidazole-functionalized sepiolite; (4) Add acetone solvent and imidazole-functionalized sepiolite into a reaction container, add epoxy resin, silicone defoamer and leveling agent after ultrasonic dispersion, and emulsify at high speed. Use methyl hexahydrophthalic anhydride as a curing agent to obtain an imidazole-functionalized sepiolite-modified epoxy resin composite material.
2. The imidazole-functionalized sepiolite-modified epoxy resin composite material according to claim 1, characterized in that: In the step (2), the amino-functionalized sepiolite is 100 parts and the glutaric anhydride is 250-800 parts by weight.
3. The imidazole-functionalized sepiolite-modified epoxy resin composite material according to claim 1, characterized in that: In the step (3), the condensation agent is O-benzotriazole-tetramethyluronium hexafluorophosphate, and the catalyst is triethylamine.
4. The imidazole-functionalized sepiolite-modified epoxy resin composite material according to claim 1, characterized in that: In the step (3), based on weight parts, the amino-functionalized sepiolite is 100 parts, the histamine is 80-250 parts, the condensation agent is 70-220 parts, and the catalyst is 55-180 parts.
5. The imidazole-functionalized sepiolite-modified epoxy resin composite material according to claim 1, characterized in that: The reaction in step (3) is carried out at 25-45°C for 12-36 hours.
6. The imidazole-functionalized sepiolite-modified epoxy resin composite material according to claim 1, characterized in that: In the step (4), the imidazole-functionalized sepiolite is 0.5-3 parts by weight, and the epoxy resin is 100 parts by weight.