Flame-retardant high-temperature-resistant epoxy resin sealant as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of sealants, and particularly relates to a flame-retardant high-temperature-resistant epoxy resin sealant as well as a preparation method and application thereof. The sealant comprises a component A and a component B. The component A is prepared from, by weight, 100 parts of epoxy resin, 5-15 parts of diluent, 1-3 parts of dispersing agent, 1-3 parts of flatting agent, 3-5 parts of silane coupling agent, 4-8 parts of Ce-H6L metal organic framework and 5-9 parts of vermiculite nanosheet loaded magnesium hydroxystannate. And the component B comprises the following components in parts by weight: 100 parts of a curing agent, 1-3 parts of a curing accelerator and 6-10 parts of a silane coupling agent. By adding the Ce-H6L metal organic framework and the vermiculite nanosheet loaded magnesium hydroxystannate, the flame-retardant and high-temperature-resistant performance of the sealant is remarkably improved, and by adding the silane coupling agent, dispersion of the components is promoted, so that improvement of the mechanical property of the sealant is promoted.

Description

Technical Field

[0001] The present invention belongs to the technical field of sealants, and more specifically, relates to a flame retardant and high temperature resistant epoxy resin sealant and a preparation method and application thereof. Background Art

[0002] Epoxy resin (EP) is one of the three thermosetting resins with the largest usage and the widest application range. It has excellent mechanical properties, chemical corrosion resistance, adhesion and electrical insulation, and is widely used in coatings, adhesives and insulation packaging of electronic components. However, EP has poor flame retardancy. When it comes into contact with a fire source, it will release a large amount of heat and toxic smoke, and it will continue to burn after leaving the fire, which is very likely to cause a secondary fire, greatly limiting its application range. Therefore, it is of great research significance to modify its flame retardancy.

[0003] MOFs are rich in transition metal species, flame retardant elements and potential carbon sources, and their structures and properties are easily adjustable. Therefore, MOFs have great potential in the field of flame retardancy. The organic part of MOFs enhances the compatibility of fillers with polymer chains and reduces the burden of additional organic modifications. In addition, their organic structure also helps to carry flame retardant groups such as phosphorus, nitrogen and aromatic derivatives through appropriate modifications. MOFs are rich in metal elements, and their derived metal oxides also have excellent catalytic oxidation and catalytic carbonization activities. Therefore, it can be seen that MOFs have excellent potential value in the field of flame retardancy.

[0004] Inorganic metal salt flame retardants have potential flame retardant properties. The more common ones are hydroxystannate flame retardants, which have a unified chemical structure of MSn(OH) 6 , where M is a positive divalent metal (such as Ca, Mg, Fe, Zn, Sr, Cu, etc.). Hydroxystannate, as a flame retardant, will decompose to generate metal oxides when heated, covering the surface of the substrate to form a physical protective barrier, while promoting the carbon chain to form a dense and continuous carbon layer, blocking the release of heat and the entry of combustible gases.

[0005] Based on the above content, the present invention provides a new flame retardant and high temperature resistant epoxy resin sealant, which has excellent flame retardant and high temperature resistant properties and mechanical properties, and has a good application prospect in the field of building materials. Summary of the invention

[0006] The technical problem to be solved by the present invention is to overcome the defects and shortcomings of the prior art and provide a flame retardant and high temperature resistant epoxy resin sealant and its preparation method and application. The sealant comprises components A and B. Component A, by weight, comprises the following components: 100 parts of epoxy resin, 5 to 15 parts of diluent, 1 to 3 parts of dispersant; 1 to 3 parts of leveling agent; 3 to 5 parts of silane coupling agent; Ce-H 6L metal organic framework; 4-8 parts; vermiculite nanosheets loaded with magnesium hydroxystannate 5-9 parts; component B, by weight, includes the following components: 100 parts of curing agent, 1-3 parts of curing accelerator, and 6-10 parts of silane coupling agent. 6 L metal organic framework and vermiculite nanosheets loaded with magnesium hydroxystannate significantly improved the flame retardant and high temperature resistance of the sealant. The addition of silane coupling agent promoted the dispersion of the above components, thereby promoting the improvement of the mechanical properties of the sealant.

[0007] The purpose of the invention is to provide a flame retardant and high temperature resistant epoxy resin sealant.

[0008] Another object of the present invention is to provide a method for preparing a flame retardant and high temperature resistant epoxy resin sealant.

[0009] Another object of the present invention is to provide an application of a flame retardant and high temperature resistant epoxy resin sealant.

[0010] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0011] A flame retardant and high temperature resistant epoxy resin sealant, the sealant comprises components A and B,

[0012] Component A, by weight, includes the following components: 100 parts of epoxy resin, 5-15 parts of diluent, 1-3 parts of dispersant, 1-3 parts of leveling agent, 3-5 parts of silane coupling agent, Ce-H 6 L metal organic framework; 4 to 8 parts; vermiculite nanosheets loaded with magnesium hydroxystannate 5 to 9 parts;

[0013] Component B includes the following components by weight: 100 parts of a curing agent, 1-3 parts of a curing accelerator, and 6-10 parts of a silane coupling agent.

[0014] In the present invention, the preferred embodiment is that the Ce-H 6 The preparation method of the L metal organic framework comprises the following steps:

[0015] Hexa(4-'carboxyphenoxy')cyclotriphosphazene and cerium salt were added to a mixed solvent of DMF and water, ultrasonically dispersed for 10 to 30 minutes, and then transferred to a hydrothermal reactor, cooled to room temperature, filtered, washed, and dried to constant weight to obtain Ce-H 6 L.

[0016] Preferably, the volume ratio of DMF to water is 1:1; the molar ratio of hexa(4-'carboxyphenoxy')cyclotriphosphazene to cerium salt is 1:6-12; the cerium salt is one of cerium nitrate, cerium chloride and cerium acetate; the hydrothermal reaction conditions are hydrothermal reaction at 120-140°C for 25-35h, and the drying temperature is 80-100°C.

[0017] In the present invention, a more preferred solution is that in component A, the silane coupling agent is one of KH-550, KH-560, and KH-570; the epoxy resin is epoxy resin E51; the diluent is 3,4-epoxycyclohexyl methacrylate; the dispersant is BYK-9076; and the leveling agent is BYK-306.

[0018] In a further preferred embodiment of the present invention, the preparation method of the vermiculite nanosheets loaded with magnesium hydroxystannate is as follows:

[0019] (1) dispersing vermiculite in water, ultrasonically dispersing for 40 to 80 minutes to obtain a suspension, filtering, washing, and drying to a constant weight to obtain vermiculite nanosheets;

[0020] (2) adding magnesium salt to ethanol, ultrasonically dispersing for 20 to 40 minutes, then adding triethylamine, stirring for 20 to 30 minutes, then adding the vermiculite nanosheets obtained in step (1), and continuing to stir for 40 to 80 minutes; then adding sodium selenate, continuing to stir for 1 to 3 hours, aging overnight, centrifuging, washing, and vacuum drying at 60 to 80° C. for 10 to 20 hours to obtain vermiculite nanosheets loaded with magnesium hydroxystannate.

[0021] Preferably, in step (1), the ultrasonic power is 600-1000w, and the drying temperature is 60-80°C.

[0022] Further preferably, the magnesium salt is one of magnesium nitrate, magnesium chloride, and magnesium acetate; the ratio of the magnesium salt to triethylamine is 1 mmol: 100-140 mL; the ratio of the magnesium salt to vermiculite nanosheets is: 1 mmol: 0.2-0.4 g; and the molar ratio of the magnesium salt to sodium selenate is 1:1.

[0023] In the present invention, a further preferred embodiment is that in component B, the curing agent is at least one of triethylamine, triethylenetetramine, and maleic anhydride; the curing accelerator is at least one of pyridine, triethanolamine, and diethyltetramethylimidazole; and the silane coupling agent is one of KH-550, KH-560, and KH-570.

[0024] Based on the above-mentioned method for preparing a flame retardant and high temperature resistant epoxy resin sealant, the preparation method comprises the following steps:

[0025] Preparation of component A: epoxy resin, diluent, dispersant, leveling agent, silane coupling agent, Ce-H 6 The L metal organic framework and the vermiculite nanosheets loaded with magnesium hydroxystannate are mixed at 65-75° C. for 80-120 minutes; and cooled to room temperature to obtain component A.

[0026] Preparation of component B: Add the curing agent, curing accelerator and coupling agent into a kneader in sequence, fully knead at 65-75° C. for 80-120 min, and cool to room temperature to obtain component B.

[0027] Based on the application of the flame retardant and high temperature resistant epoxy resin sealant in the field of building materials.

[0028] The present invention has the following beneficial effects:

[0029] The present invention prepares Ce-H 6 L metal organic framework, which not only contains phosphorus and nitrogen elements, which can play a good flame retardant effect, but also contains Ce, and the metal oxide derived from it also has excellent catalytic oxidation and catalytic carbonization activity, which improves the flame retardant performance of the sealant; the present invention loads magnesium hydroxystannate on vermiculite nanosheets, makes good use of the interaction between vermiculite and magnesium hydroxystannate, promotes the improvement of the flame retardant and high temperature resistance of the sealant, and by adding a silane coupling agent, the dispersion of the above components can be well promoted, thereby improving the mechanical properties of the sealant. The sealant prepared by the present invention has excellent performance and good application prospects. DETAILED DESCRIPTION

[0030] The present invention is further described below with reference to specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0031] Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0032] Example 1

[0033] A flame retardant and high temperature resistant epoxy resin sealant, comprising components A and B.

[0034] Component A, by weight, includes the following components: 100 parts of epoxy resin E51, 10 parts of diluent, 2 parts of dispersant, 2 parts of leveling agent, 4 parts of silane coupling agent, Ce-H 6 6 parts of L metal organic framework, 7 parts of vermiculite nanosheet-loaded magnesium hydroxystannate; the diluent is 3,4-epoxycyclohexyl methacrylate; the dispersant is BYK-9076; the leveling agent is BYK-306; and the silane coupling agent is KH-560;

[0035] Component B, by weight, includes the following components: 100 parts of a curing agent, 2 parts of a curing accelerator, and 8 parts of a silane coupling agent; the curing agent is triethylenetetramine; the curing accelerator is triethanolamine; and the silane coupling agent is KH-560;

[0036] The Ce-H 6The preparation method of the L metal organic framework comprises the following steps:

[0037] 1 mol of hexa(4-'carboxyphenoxy')cyclotriphosphazene and 8 mol of cerium acetate were added to a mixed solvent of 300 mL of DMF and water, wherein the volume ratio of DMF to water was 1:1, and ultrasonically dispersed for 20 min, and then transferred to a hydrothermal reactor, hydrothermally reacted at 130 ° C for 30 h, cooled to room temperature, filtered, washed, and dried at 90 ° C to constant weight to obtain Ce-H 6 L.

[0038] The preparation method of the vermiculite nanosheet-loaded magnesium hydroxystannate is as follows:

[0039] (1) Dispersing 10 g of vermiculite in 100 mL of water, ultrasonically dispersing for 60 min, the ultrasonic power being 800 W, obtaining a suspension, filtering, washing, and drying at 80° C. to constant weight to obtain vermiculite nanosheets;

[0040] (2) Add 10 mmol of magnesium nitrate to 200 mL of ethanol, ultrasonically disperse for 30 min, then add 1200 mL of triethylamine, stir for 25 min, then add 3 g of the vermiculite nanosheets obtained in step (1), and continue stirring for 60 min; then add 10 mmol of sodium selenate, continue stirring for 2 h, age overnight, centrifuge, wash, and vacuum dry at 70 ° C for 16 h to obtain vermiculite nanosheets loaded with magnesium hydroxystannate.

[0041] A method for preparing a flame retardant and high temperature resistant epoxy resin sealant comprises the following steps:

[0042] Preparation of component A: epoxy resin, diluent, dispersant, leveling agent, silane coupling agent, Ce-H6L metal organic framework and vermiculite nanosheets loaded with magnesium hydroxystannate were mixed at 70° C. for 100 min; cooled to room temperature to obtain component A;

[0043] Preparation of component B: Add the curing agent, curing accelerator and coupling agent into a kneader in sequence, fully knead at 70° C. for 100 min, and cool to room temperature to obtain component B.

[0044] Example 2

[0045] A flame retardant and high temperature resistant epoxy resin sealant, comprising components A and B.

[0046] Component A, by weight, includes the following components: 100 parts of epoxy resin E51, 15 parts of diluent, 1 part of dispersant, 3 parts of leveling agent, 3 parts of silane coupling agent, Ce-H 68 parts of L metal organic framework, 5 parts of vermiculite nanosheet-loaded magnesium hydroxystannate; the diluent is 3,4-epoxycyclohexyl methacrylate; the dispersant is BYK-9076; the leveling agent is BYK-306; and the silane coupling agent is KH-570;

[0047] Component B, by weight, includes the following components: 100 parts of a curing agent, 1-3 parts of a curing accelerator, and 6-10 parts of a silane coupling agent; the curing agent is maleic anhydride; the curing accelerator is pyridine; and the silane coupling agent is KH-570;

[0048] The Ce-H 6 The preparation method of L metal organic framework is the same as that in Example 1.

[0049] The preparation method of the vermiculite nanosheet-loaded magnesium hydroxystannate is as follows:

[0050] (1) Dispersing 100 g of vermiculite in 200 mL of water, ultrasonically dispersing for 60 min, the ultrasonic power being 800 W, obtaining a suspension, filtering, washing, and drying at 80° C. to constant weight to obtain vermiculite nanosheets;

[0051] (2) Add 10 mmol of magnesium chloride to 200 mL of ethanol, ultrasonically disperse for 40 min, then add 1400 mL of triethylamine, stir for 20 min, then add 4 g of the vermiculite nanosheets obtained in step (1), and continue stirring for 80 min; then add 10 mmol of sodium selenate, continue stirring for 1 h, age overnight, centrifuge, wash, and vacuum dry at 80 ° C for 10 h to obtain vermiculite nanosheets loaded with magnesium hydroxystannate.

[0052] A method for preparing a flame retardant and high temperature resistant epoxy resin sealant comprises the following steps:

[0053] Preparation of component A: epoxy resin, diluent, dispersant, leveling agent, silane coupling agent, Ce-H6L metal organic framework and vermiculite nanosheets loaded with magnesium hydroxystannate were mixed at 75° C. for 80 min; cooled to room temperature to obtain component A;

[0054] Preparation of component B: Add the curing agent, curing accelerator and coupling agent into a kneader in sequence, fully knead at 75° C. for 80 minutes, and cool to room temperature to obtain component B.

[0055] Example 3

[0056] A flame retardant and high temperature resistant epoxy resin sealant, comprising components A and B.

[0057] Component A, by weight, includes the following components: 100 parts of epoxy resin E51, 5 parts of diluent, 3 parts of dispersant, 1 part of leveling agent, 5 parts of silane coupling agent, Ce-H 64 parts of L metal organic framework, 9 parts of vermiculite nanosheet-loaded magnesium hydroxystannate; the diluent is 3,4-epoxycyclohexyl methacrylate; the dispersant is BYK-9076; the leveling agent is BYK-306; and the silane coupling agent is KH-550;

[0058] Component B, by weight, includes the following components: 100 parts of a curing agent, 1 part of a curing accelerator, and 10 parts of a silane coupling agent; the curing agent is triethylamine; the curing accelerator is diethyltetramethylimidazole; and the silane coupling agent is KH-550;

[0059] The Ce-H 6 The preparation method of L metal organic framework is the same as that in Example 1.

[0060] The preparation method of the vermiculite nanosheet-loaded magnesium hydroxystannate is as follows:

[0061] (1) Dispersing 100 g of vermiculite in 200 mL of water, ultrasonically dispersing for 60 min, the ultrasonic power being 800 W, obtaining a suspension, filtering, washing, and drying at 80° C. to constant weight to obtain vermiculite nanosheets;

[0062] (2) Add 10 mmol of magnesium acetate to 200 mL of ethanol, ultrasonically disperse for 20 min, then add 1000 mL of triethylamine, stir for 30 min, then add 2 g of the vermiculite nanosheets obtained in step (1), and continue stirring for 40 min; then add 10 mmol of sodium selenate, continue stirring for 3 h, age overnight, centrifuge, wash, and vacuum dry at 60 ° C for 20 h to obtain vermiculite nanosheets loaded with magnesium hydroxystannate.

[0063] A method for preparing a flame retardant and high temperature resistant epoxy resin sealant comprises the following steps:

[0064] Preparation of component A: epoxy resin, diluent, dispersant, leveling agent, silane coupling agent, Ce-H6L metal organic framework and vermiculite nanosheets loaded with magnesium hydroxystannate were mixed at 65° C. for 120 min; cooled to room temperature to obtain component A;

[0065] Preparation of component B: Add the curing agent, curing accelerator and coupling agent into a kneader in sequence, fully knead at 65° C. for 120 min, and cool to room temperature to obtain component B.

[0066] Comparative Example 1

[0067] The difference between Comparative Example 1 and Example 1 is that an equal amount of vermiculite nanosheets is used to replace the vermiculite nanosheets loaded with magnesium hydroxystannate. The preparation method of the vermiculite nanosheets is to disperse 10g of vermiculite in 100mL of water, ultrasonically disperse for 60min, and the ultrasonic power is 800w to obtain a suspension, filter, wash, and dry at 80°C to constant weight to obtain vermiculite nanosheets. The same parts can be referred to in Example 1, which will not be repeated here.

[0068] Comparative Example 2

[0069] The difference between Comparative Example 2 and Example 1 is that an equal amount of magnesium hydroxystannate is used to replace the vermiculite nanosheets to load magnesium hydroxystannate. The preparation method of the magnesium hydroxystannate is to add 10mmol magnesium nitrate to 200mL ethanol, ultrasonically disperse for 30min, then add 1200mL triethylamine, stir for 85min, then add 10mmol sodium selenate, continue stirring for 2h, age overnight, centrifuge, wash, and vacuum dry at 70°C for 16h to obtain magnesium hydroxystannate. The same part can be found in Example 1, which will not be repeated here.

[0070] Comparative Example 3

[0071] The difference between Comparative Example 3 and Example 1 is that the same amount of Ce-H 6 L metal organic framework replaces vermiculite nanosheets to load magnesium hydroxystannate. The same parts can be found in Example 1, which will not be repeated here.

[0072] Comparative Example 4

[0073] The difference between Comparative Example 3 and Example 1 is that the same amount of Cu-H 6 L metal organic framework replaces Ce-H 6 L Metal-organic framework.

[0074] The performance of Examples 1-3 and Comparative Examples 1-4 was tested, and the specific results are shown in Table 1, wherein the prepared component A and component B were made into rubber sheets at a ratio of 3:1, and the tensile strength and limiting oxygen index were tested respectively. The specific test standards are: the tensile strength was tested in accordance with GB / T 1040.2:2006; the limiting oxygen index (LOI) was tested in accordance with ASTM D2863.

[0075] Table 1

[0076] Tensile strength / MPa Limiting oxygen index (LOI) / % Example 1 18.9 39.8 Example 2 18.1 38.9 Example 3 18.7 39.4 Comparative Example 1 17.5 35.7 Comparative Example 2 17.2 36.5 Comparative Example 3 16.6 34.8 Comparative Example 4 18.8 38.1

[0077] It can be seen from Table 1 that the flame retardant and high temperature resistant epoxy resin prepared by the present invention has excellent flame retardant and high temperature resistant properties, and also has excellent mechanical properties, wherein the limiting oxygen index (LOI) can reach up to 39.8% and the tensile strength can reach up to 18.9 MPa.

[0078] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A flame retardant and high temperature resistant epoxy resin sealant, characterized in that: The sealant comprises components A and B. Component A, by weight, includes the following components: 100 parts of epoxy resin, 5-15 parts of diluent, 1-3 parts of dispersant, 1-3 parts of leveling agent, 3-5 parts of silane coupling agent, 4-8 parts of Ce-H6L metal organic framework, and 5-9 parts of vermiculite nanosheet-loaded magnesium hydroxystannate; Component B includes the following components by weight: 100 parts of a curing agent, 1-3 parts of a curing accelerator, and 6-10 parts of a silane coupling agent.

2. A flame retardant and high temperature resistant epoxy resin sealant according to claim 1, characterized in that: The preparation method of the Ce-H6L metal organic framework comprises the following steps: Hexa(4-'carboxyphenoxy')cyclotriphosphazene and cerium salt were added to a mixed solvent of DMF and water, ultrasonically dispersed for 10 to 30 minutes, and then transferred to a hydrothermal reactor, cooled to room temperature, filtered, washed, and dried to constant weight to obtain Ce-H6L.

3. The flame retardant and high temperature resistant epoxy resin sealant according to claim 2, characterized in that: The volume ratio of DMF and water is 1:1; the molar ratio of hexa(4-'carboxyphenoxy')cyclotriphosphazene and cerium salt is 1:6-12; the cerium salt is one of cerium nitrate, cerium chloride and cerium acetate; the hydrothermal reaction conditions are hydrothermal reaction at 120-140°C for 25-35h, and the drying temperature is 80-100°C.

4. The flame retardant and high temperature resistant epoxy resin sealant according to claim 1, characterized in that: In component A, the silane coupling agent is one of KH-550, KH-560, and KH-570; the epoxy resin is epoxy resin E51; the diluent is 3,4-epoxycyclohexyl methacrylate; the dispersant is BYK-9076; and the leveling agent is BYK-306.

5. The flame retardant and high temperature resistant epoxy resin sealant according to claim 1, characterized in that: The preparation method of the vermiculite nanosheet-loaded magnesium hydroxystannate is as follows: (1) dispersing vermiculite in water, ultrasonically dispersing for 40 to 80 minutes to obtain a suspension, filtering, washing, and drying to a constant weight to obtain vermiculite nanosheets; (2) adding magnesium salt to ethanol, ultrasonically dispersing for 20 to 40 minutes, then adding triethylamine, stirring for 20 to 30 minutes, then adding the vermiculite nanosheets obtained in step (1), and continuing to stir for 40 to 80 minutes; then adding sodium selenate, continuing to stir for 1 to 3 hours, aging overnight, centrifuging, washing, and vacuum drying at 60 to 80° C. for 10 to 20 hours to obtain vermiculite nanosheets loaded with magnesium hydroxystannate.

6. The flame retardant and high temperature resistant epoxy resin sealant according to claim 5, characterized in that: In step (1), the ultrasonic power is 600-1000w, and the drying temperature is 60-80°C.

7. The flame retardant and high temperature resistant epoxy resin sealant according to claim 5, characterized in that: The magnesium salt is one of magnesium nitrate, magnesium chloride and magnesium acetate; the ratio of the magnesium salt to triethylamine is 1mmol:100-140mL; the ratio of the magnesium salt to vermiculite nanosheets is: 1mmol:0.2-0.4g; the molar ratio of the magnesium salt to sodium selenate is 1:

1.

8. The flame retardant and high temperature resistant epoxy resin sealant according to claim 1, characterized in that: In component B, the curing agent is at least one of triethylamine, triethylenetetramine, and maleic anhydride; the curing accelerator is at least one of pyridine, triethanolamine, and diethyltetramethylimidazole; and the silane coupling agent is one of KH-550, KH-560, and KH-570.

9. The method for preparing a flame retardant and high temperature resistant epoxy resin sealant according to any one of claims 1 to 8, characterized in that: The preparation method comprises the following steps: Preparation of component A: epoxy resin, diluent, dispersant, leveling agent, silane coupling agent, Ce-H6L metal organic framework and vermiculite nanosheets loaded with magnesium hydroxystannate are mixed at 65-75° C. for 80-120 minutes; cooled to room temperature to obtain component A; Preparation of component B: Add the curing agent, curing accelerator and coupling agent into a kneader in sequence, fully knead at 65-75° C. for 80-120 min, and cool to room temperature to obtain component B.

10. Use of the flame retardant and high temperature resistant epoxy resin sealant according to any one of claims 1 to 8 in the field of building materials.