High-temperature-resistant fast-curing glue as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of glue, and particularly relates to high-temperature-resistant fast-curing glue as well as a preparation method and application thereof. The epoxy resin composition comprises the following raw materials in parts by weight: 120-160 parts of epoxy resin and 4-8 parts of amino-modified carbon nitride, 5 to 9 parts of modified vermiculite nanosheets; 11-15 parts of isocyanate, 25-35 parts of a curing agent and 180-240 parts of ethylene glycol. The amino-modified carbon nitride is added, so that sufficient dispersion in the carbon nitride raw material can be promoted, chemical bonding of the raw material can be realized, the high temperature resistance and mechanical property of the glue can be improved, the dispersion of the vermiculite nanosheet in the raw material is improved through modification treatment of the vermiculite nanosheet, and the performance of the glue is further improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of adhesives. More specifically, it relates to a high-temperature resistant and fast-curing adhesive and its preparation method and application. Background Art

[0002] Epoxy resins have good mechanical properties, adhesion, and stability, and are widely used in the field of sealants. Epoxy resin sealants are composed of an epoxy matrix resin and a curing agent. When the curing reaction occurs between the two components, a three-dimensional polymer network with excellent mechanical properties can be formed, in which the cross-linking reaction is self-catalyzed by the formation of reactive hydroxyl groups during the reaction of epoxy groups. Nowadays, commonly used room-temperature fast-curing epoxy adhesives have disadvantages such as long surface drying time, low strength, and poor toughness. Therefore, there is an urgent need to develop an adhesive that can cure quickly at room temperature and has good thermal stability and other characteristics.

[0003] CN115926701A discloses a high-temperature resistant structural adhesive and its application, belonging to the technical field of organic adhesives. The high-temperature resistant structural adhesive is composed of the following components in parts by weight: 10-20 parts of vinyl acetamide, 5-15 parts of EVA resin, 15-25 parts of fluorenyl epoxy resin, 3-7 parts of sodium silicate, 4-8 parts of calcium formate, 5-15 parts of borax, 10-20 parts of lignin, 4-8 parts of quartz powder, and 1-5 parts of anhydride curing agent. The prepared high-temperature resistant structural adhesive has a long storage time, high bonding strength, convenient construction, high solid content, firm and durable, single-component, room-temperature curing, a wide range of bonding materials, good water resistance, acid resistance, and alkali resistance, and high strength, and is an ideal adhesive material for industrial and civil use.

[0004] CN113004810A discloses a high-temperature resistant structural adhesive, which is composed of the following components by type: vinyl acetamide, EVA resin, fluorenyl epoxy resin, sodium silicate, calcium formate, borax, lignin, quartz powder, and anhydride curing agent. The provided high-temperature resistant structural adhesive has a long storage time, high bonding strength, convenient construction, high solid content, firm and durable, single-component, room-temperature curing. It also has a wide range of bonding materials, good water resistance, acid resistance, and alkali resistance, and high strength, and is an ideal adhesive material for industrial and civil use.

[0005] CN119529718A discloses a high-temperature resistant and yellowing-resistant LED encapsulation glue, which includes A glue, B glue and C powder; the A glue includes epoxy resin, toughening agent, leveling agent, main antioxidant, auxiliary antioxidant, diluent, defoaming agent, silane coupling agent; among them, the main antioxidant is a hindered phenol antioxidant; the auxiliary antioxidant is a phosphite antioxidant; the B glue includes an acid anhydride curing agent and a promoter; the C powder includes a diffusion powder and a matte powder. In the present invention, the hindered phenol antioxidant and the phosphite antioxidant act synergistically, and the phosphite antioxidant reduces the oxidation product of the hindered phenol antioxidant, that is, the benzoquinone chromophore, thereby protecting the color of the system, ensuring the long-term stability of the material; improving the heat resistance, anti-aging, antioxidant and anti-UV performance of the encapsulation glue, making it not produce color change, protecting the color of the system, ensuring the long-term stability of the material, delaying the yellowing rate by more than 50%, and the high temperature resistance can reach 260°C.

[0006] In the existing glue, there are many added modified components, or the preparation raw materials are complex, the high temperature resistance is insufficient, and the bonding performance is poor, which is not conducive to use under high temperature conditions. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to overcome the defects and deficiencies of the existing technology, and provide a high-temperature resistant and fast-curing glue and its preparation method and application. By weight, it includes the following raw materials: 120-160 parts of epoxy resin E44, 4-8 parts of amino-modified carbon nitride; 5-9 parts of modified vermiculite nanosheets; 11-15 parts of isocyanate, 25-35 parts of curing agent, 180-240 parts of ethylene glycol. By adding amino-modified carbon nitride, the present invention can promote the full dispersion of the carbon nitride raw materials, and can achieve the chemical bonding of the raw materials, telling the high temperature resistance and mechanical properties of the glue. Through the modification treatment of vermiculite nanosheets, the dispersibility of vermiculite nanosheets in the raw materials is improved, and thus the performance of the glue is improved.

[0008] The purpose of the present invention is to provide a high-temperature resistant and fast-curing glue.

[0009] Another purpose of the present invention is to provide a preparation method of a high-temperature resistant and fast-curing glue.

[0010] Another purpose of the present invention is to provide an application of a high-temperature resistant and fast-curing glue in the bonding field.

[0011] The above purposes of the present invention are achieved through the following technical solutions:

[0012] A high-temperature resistant and fast-curing glue, by weight, includes the following raw materials: 120-160 parts of epoxy resin E44, 4-8 parts of amino-modified carbon nitride; 5-9 parts of modified vermiculite nanosheets; 11-15 parts of isocyanate, 25-35 parts of curing agent, 180-240 parts of ethylene glycol.

[0013] In a further embodiment, the isocyanate is isophorone diisocyanate or toluene diisocyanate; the curing agent is maleic anhydride or phthalic anhydride.

[0014] In the present invention, in a preferred embodiment, the preparation method of the amino-modified carbon nitride comprises the following steps:

[0015] (1) Melamine is calcined in a nitrogen atmosphere to obtain carbon nitride, and then thermal exfoliation is carried out to obtain carbon nitride nanosheets;

[0016] (2) The carbon nitride nanosheets obtained in step (1) are dispersed in ethylene glycol, then triethylenetetramine and urea are added, and stirring is continued. Then, it is transferred to a reaction kettle, sealed, and reacted. After cooling to room temperature, filtration, washing, and drying are carried out to obtain amino-modified carbon nitride.

[0017] In a further embodiment, in step (1), the calcination is carried out at 500 - 600 °C for 2 - 4 h; the conditions for thermal exfoliation are: thermal exfoliation is carried out at 450 - 550 °C for 3 - 5 h.

[0018] In a further embodiment, in step (2), the time for continued stirring is 30 - 50 min; the mass ratio of the carbon nitride nanosheets, triethylenetetramine, and urea is 1:0.2 - 0.8:0.6 - 1.2.

[0019] In a further preferred embodiment, in step (2), the reaction is carried out at 140 - 180 °C for 12 - 24 h; the drying is carried out at 60 - 100 °C for 10 - 14 h.

[0020] In the present invention, in a further preferred embodiment, the preparation method of the modified vermiculite nanosheets comprises the following steps:

[0021] Vermiculite nanosheets and glucose are ultrasonically dispersed in deionized water, and then hydrothermal reaction is carried out at 140 - 180 °C for 4 - 10 h to obtain carbon-coated vermiculite nanosheets. Then, the prepared carbon-coated vermiculite nanosheets, vinyltrimethoxysilane, and octadecyl dimethyl benzyl ammonium chloride are ultrasonically dispersed in ethanol water, and then stirred and reacted at 50 - 70 °C for 4 - 6 h. Filtration, washing, and drying at 70 - 100 °C for 8 - 12 h are carried out to obtain modified vermiculite nanosheets.

[0022] In a further embodiment, the mass ratio of the vermiculite nanosheets to glucose is 1:4 - 8; the volume ratio of ethanol to water is 1:1; the mass ratio of the vermiculite nanosheets to vinyltrimethoxysilane and octadecyl dimethyl benzyl ammonium chloride is 100:5 - 7:3 - 5.

[0023] Based on the above-mentioned method for preparing a high temperature resistant fast curing glue, the preparation method comprises the following steps:

[0024] The epoxy resin E44, amino-modified carbon nitride, modified vermiculite nanosheets, isocyanate and ethylene glycol are fully stirred and mixed, and then stirred at 55-65° C. for 6-10 hours, cooled to room temperature, and a curing agent is added and stirred fully to obtain a high temperature resistant fast curing glue.

[0025] Based on the application of the high temperature resistant fast curing glue described above in the bonding field.

[0026] The present invention has the following beneficial effects:

[0027] The present invention performs thermal exfoliation on carbon nitride to obtain carbon nitride nanosheets, and then performs amino modification by combining urea with triethylenetetramine, thereby effectively promoting the dispersion of carbon nitride in glue, and promoting the improvement of high temperature resistance and adhesion of the glue; the vermiculite nanosheets are carbon-coated and then modified, which can effectively promote the dispersion of the vermiculite nanosheets in raw materials, and improve the high temperature resistance and adhesion of the glue. The glue prepared by the present invention has a simple preparation process and a wide range of applications. DETAILED DESCRIPTION

[0028] 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.

[0029] Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0030] Example 1

[0031] A high temperature resistant fast curing glue, comprising the following raw materials by weight: 140 parts of epoxy resin E441, 6 parts of amino-modified carbon nitride; 7 parts of modified vermiculite nanosheets; 13 parts of isocyanate, 30 parts of curing agent, and 220 parts of ethylene glycol; the isocyanate is isophorone diisocyanate; the curing agent is maleic anhydride;

[0032] The preparation method of amino-modified carbon nitride comprises the following steps:

[0033] (1) 200 g of melamine was calcined at 550 °C for 3 h in a nitrogen atmosphere to obtain carbon nitride, and then thermally exfoliated at 500 °C for 4 h to obtain carbon nitride nanosheets;

[0034] (2) Disperse 10 g of the carbon nitride nanosheets obtained in step (1) into 150 mL of ethylene glycol, add 5 g of triethylenetetramine and 9 g of urea, continue stirring for 40 min, then transfer to a reactor, seal, react at 160 ° C for 18 h, cool to room temperature, filter, wash, and dry at 80 ° C for 12 h to obtain amino-modified carbon nitride.

[0035] The preparation method of the modified vermiculite nanosheets comprises the following steps:

[0036] 100 g of vermiculite nanosheets and 600 g of glucose were ultrasonically dispersed in 2000 mL of deionized water, and then hydrothermally reacted at 160 ° C for 8 h to obtain carbon-coated vermiculite nanosheets. Then, 100 g of the prepared carbon-coated vermiculite nanosheets, 6 g of vinyltrimethoxysilane and 4 g of octadecyldimethylbenzylammonium chloride were ultrasonically dispersed in 200 mL of ethanol water (the volume ratio of ethanol to water is 1:1), and then stirred at 60 ° C for 5 h, filtered, washed, and dried at 90 ° C for 10 h to obtain modified vermiculite nanosheets.

[0037] A method for preparing a high temperature resistant fast curing glue comprises the following steps:

[0038] The epoxy resin E44, amino-modified carbon nitride, modified vermiculite nanosheets, isocyanate and ethylene glycol were fully stirred and mixed, and then stirred at 60° C. for 8 hours, cooled to room temperature, and a curing agent was added and fully stirred to obtain a high temperature resistant fast curing glue.

[0039] Example 2

[0040] A high temperature resistant fast curing glue, comprising the following raw materials by weight: 160 parts of epoxy resin E441, 4 parts of amino-modified carbon nitride; 9 parts of modified vermiculite nanosheets; 11 parts of isocyanate, 35 parts of curing agent, and 240 parts of ethylene glycol; the isocyanate is toluene diisocyanate; the curing agent is phthalic anhydride;

[0041] The preparation method of amino-modified carbon nitride comprises the following steps:

[0042] (1) The same as step (1) in the method for preparing amino-modified carbon nitride in Example 1;

[0043] (2) Disperse 10 g of the carbon nitride nanosheets obtained in step (1) into 150 mL of ethylene glycol, add 8 g of triethylenetetramine and 6 g of urea, continue stirring for 50 min, then transfer to a reactor, seal, react at 180 ° C for 12 h, cool to room temperature, filter, wash, and dry at 100 ° C for 10 h to obtain amino-modified carbon nitride.

[0044] The preparation method of the modified vermiculite nanosheets comprises the following steps:

[0045] 100 g of vermiculite nanosheets and 800 g of glucose were ultrasonically dispersed in 2000 mL of deionized water, and then hydrothermally reacted at 180 °C for 4 h to obtain carbon-coated vermiculite nanosheets. Then, 100 g of the prepared carbon-coated vermiculite nanosheets, 7 g of vinyltrimethoxysilane, and 3 g of octadecyldimethylbenzylammonium chloride were ultrasonically dispersed in 200 mL of ethanol-water (volume ratio of ethanol to water is 1:1), and then stirred and reacted at 70 °C for 4 h, filtered, washed, and dried at 100 °C for 8 h to obtain modified vermiculite nanosheets.

[0046] The preparation method of a high-temperature resistant and rapid-curing glue is the same as that in Example 1.

[0047] Example 3

[0048] A high-temperature resistant and rapid-curing glue, by weight, comprises the following raw materials: 120 parts of epoxy resin E44, 8 parts of amino-modified carbon nitride; 5 parts of modified vermiculite nanosheets; 15 parts of isocyanate, 25 parts of curing agent, 180 parts of ethylene glycol; the isocyanate is isophorone diisocyanate; the curing agent is phthalic anhydride;

[0049] The preparation method of amino-modified carbon nitride comprises the following steps:

[0050] (1) It is the same as step (1) in the preparation method of amino-modified carbon nitride in Example 1;

[0051] (2) 10 g of the carbon nitride nanosheets obtained in step (1) were dispersed in 150 mL of ethylene glycol, then 2 g of triethylenetetramine and 12 g of urea were added, and stirring was continued for 30 min. Then, it was transferred to a reaction kettle, sealed, and reacted at 140 °C for 24 h, cooled to room temperature, filtered, washed, and dried at 60 °C for 14 h to obtain amino-modified carbon nitride.

[0052] The preparation method of modified vermiculite nanosheets comprises the following steps:

[0053] 100 g of vermiculite nanosheets and 400 g of glucose were ultrasonically dispersed in 2000 mL of deionized water, and then hydrothermally reacted at 140 °C for 10 h to obtain carbon-coated vermiculite nanosheets. Then, 100 g of the prepared carbon-coated vermiculite nanosheets, 5 g of vinyltrimethoxysilane, and 5 g of octadecyldimethylbenzylammonium chloride were ultrasonically dispersed in 200 mL of ethanol-water (volume ratio of ethanol to water is 1:1), and then stirred and reacted at 50 °C for 6 h, filtered, washed, and dried at 70 °C for 12 h to obtain modified vermiculite nanosheets.

[0054] The preparation method of a high-temperature resistant and rapid-curing glue is the same as that in Example 1.

[0055] Control Example 1

[0056] Comparative Example 1 is basically the same as Example 1, except that the preparation method of the amino-modified carbon nitride includes the following steps:

[0057] (1) Calcinate 200 g of melamine at 550 °C for 3 h in a nitrogen atmosphere to obtain carbon nitride, and then perform thermal exfoliation at 500 °C for 4 h to obtain carbon nitride nanosheets;

[0058] (2) Disperse 10 g of the carbon nitride nanosheets obtained in step (1) into 150 mL of ethylene glycol, add 14 g of urea, continue stirring for 40 min, then transfer to a reaction kettle, seal, react at 160 °C for 18 h, cool to room temperature, filter, wash, and dry at 80 °C for 12 h to obtain the amino-modified carbon nitride.

[0059] Comparative Example 2

[0060] Comparative Example 2 is basically the same as Example 1, except that the carbon nitride nanosheets are not amino-modified. The preparation method of the carbon nitride nanosheets is to calcinate 200 g of melamine at 550 °C for 3 h in a nitrogen atmosphere to obtain carbon nitride, and then perform thermal exfoliation at 500 °C for 4 h to obtain carbon nitride nanosheets.

[0061] Comparative Example 3

[0062] Comparative Example 3 is basically the same as Example 1, except that the preparation method of the modified vermiculite nanosheets includes the following steps:

[0063] Ultrasonically disperse 100 g of vermiculite nanosheets and 600 g of glucose into 2000 mL of deionized water, then perform hydrothermal reaction at 160 °C for 8 h to obtain carbon-coated vermiculite nanosheets. Then, ultrasonically disperse 100 g of the prepared carbon-coated vermiculite nanosheets and 10 g of octadecyldimethylbenzylammonium chloride into 200 mL of ethanol-water (volume ratio of ethanol to water is 1:1), then stir and react at 60 °C for 5 h, filter, wash, and dry at 90 °C for 10 h to obtain the modified vermiculite nanosheets.

[0064] Comparative Example 4

[0065] Comparative Example 4 is basically the same as Example 1, except that the preparation method of the modified vermiculite nanosheets includes the following steps:

[0066] Ultrasonically disperse 100 g of vermiculite nanosheets, 6 g of vinyltrimethoxysilane, and 4 g of octadecyldimethylbenzylammonium chloride into 200 mL of ethanol-water (volume ratio of ethanol to water is 1:1), then stir and react at 60 °C for 5 h, filter, wash, and dry at 90 °C for 10 h to obtain the modified vermiculite nanosheets.

[0067] Comparative Example 5

[0068] Comparative Example 5 is basically the same as Example 1, except that the modified vermiculite nanosheets are omitted, and 13 parts of amino-modified carbon nitride are used.

[0069] Test the performance of the adhesives prepared in Examples 1-3 and Comparative Examples 1-5, where

[0070] Tensile strength: Test according to GB / T 528-1998;

[0071] Shear strength: Test according to GB / T 7124 1986;

[0072] (1) Coat the adhesives obtained in each example and comparative example on a PCB board (100 mm × 25 mm × 2 mm) respectively, laminate with a PCB sheet, control the adhesive layer thickness with a 0.13 mm copper wire, the adhesive layer area is 25 mm × 4 mm, and cure at 120 °C for 4 h to fabricate test pieces; at room temperature, test the tensile strength and shear strength, and the test results are shown in Table 1.

[0073] (2) Fabricate test piece A according to the room temperature test, and heat-cure test piece A in an oven at 300 °C for 30 minutes to fabricate test piece B; test the retention rates of the tensile strength and shear strength of test piece B at high temperature, and the test results are shown in Table 1.

[0074] Table 1:

[0075]

[0076] As can be seen from Table 1, a high-temperature resistant and fast-curing adhesive prepared by the present invention has excellent high-temperature resistance and mechanical properties.

[0077] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. A high-temperature resistant and fast-curing glue, characterized in that: The raw materials include the following by weight: 120-160 parts of epoxy resin, 4-8 parts of amino-modified carbon nitride, 5-9 parts of modified vermiculite nanosheets, 11-15 parts of isocyanate, 25-35 parts of curing agent and 180-240 parts of ethylene glycol.

2. The high-temperature resistant and fast-curing glue according to claim 1, characterized in that: The isocyanate is isophorone diisocyanate or toluene diisocyanate; the curing agent is maleic anhydride or phthalic anhydride.

3. A high-temperature resistant and fast-curing glue according to claim 1, characterized in that: The preparation method of the amino-modified carbon nitride comprises the following steps: (1) calcining melamine in a nitrogen atmosphere to obtain carbon nitride, and then thermally exfoliating to obtain carbon nitride nanosheets; (2) dispersing the carbon nitride nanosheets obtained in step (1) into ethylene glycol, adding triethylenetetramine and urea, continuing stirring, and then transferring to a reaction kettle, sealing, reacting, cooling to room temperature, filtering, washing, and drying to obtain amino-modified carbon nitride.

4. A high-temperature resistant and fast-curing glue according to claim 3, wherein: In step (1), the calcination is performed at 500-600° C. for 2-4 hours; and the thermal stripping condition is performed at 450-550° C. for 3-5 hours.

5. The high-temperature resistant and fast-curing glue according to claim 3, characterized in that: In step (2), the stirring time is 30 to 50 minutes; the mass ratio of the carbon nitride nanosheets, triethylenetetramine and urea is 1:0.2 to 0.8:0.6 to 1.

2.

6. The heat-resistant and rapid-curing glue according to claim 3, characterized in that: In step (2), the reaction is carried out at 140-180° C. for 12-24 h; and the drying is carried out at 60-100° C. for 10-14 h.

7. The high-temperature resistant and fast-curing glue according to claim 1, characterized in that: The preparation method of the modified vermiculite nanosheets comprises the following steps: The vermiculite nanosheets and glucose are ultrasonically dispersed in deionized water, and then hydrothermally reacted at 140-180°C for 4-10 hours to obtain carbon-coated vermiculite nanosheets. The prepared carbon-coated vermiculite nanosheets, vinyltrimethoxysilane and octadecyldimethylbenzyl ammonium chloride are then ultrasonically dispersed in ethanol water, and then stirred at 50-70°C for 4-6 hours, filtered, washed, and dried at 70-100°C for 8-12 hours to obtain modified vermiculite nanosheets.

8. A high-temperature resistant and fast-curing glue according to claim 7, characterized in that: The mass ratio of the vermiculite nanosheets to glucose is 1:4-8; the volume ratio of the ethanol to water is 1:1; the mass ratio of the vermiculite nanosheets to vinyltrimethoxysilane and octadecyldimethylbenzyl ammonium chloride is 100:5-7:3-5.

9. The preparation method of a high-temperature resistant and rapid-curing glue according to any one of claims 1-8, characterized in that: The preparation method comprises the following steps: The epoxy resin, amino-modified carbon nitride, modified vermiculite nanosheets, isocyanate and ethylene glycol are fully stirred and mixed, and then stirred at 55-65° C. for 6-10 hours, cooled to room temperature, and a curing agent is added and fully stirred to obtain a high-temperature resistant fast-curing glue.

10. Application of the high temperature resistant fast curing glue according to any one of claims 1 to 8 in the field of bonding.

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