Cationic modified layered filler, preparation method thereof and adhesive

Abstract

The invention belongs to the technical field of adhesives, and particularly relates to a cation modified layered filler, a preparation method thereof and an adhesive. The preparation method of the cationic initiator intercalation modified layered filler comprises the following steps: S1, dispersing a layered filler into an organic solvent to obtain a first mixed solution; s2, mixing and dispersing a cationic initiator and the first mixed solution to obtain a second mixed solution; s3, washing and drying the second mixed solution to obtain a primary intercalation product; s4, mixing and dispersing the primary intercalation product and anion pairing salt in an alcohol solvent to obtain the cationic initiator intercalation modified layered filler. The laminated filler and the cationic initiator are subjected to compound modification, so that the curing efficiency and the storage stability of the adhesive are remarkably improved, and meanwhile, the water vapor permeability is reduced, so that the adhesive has excellent barrier property and wide application prospects.

Description

Technical Field

[0001] The invention belongs to the technical field of adhesives, and particularly relates to a cationic modified layered filler, a preparation method thereof, and a light-curing adhesive. Background Art

[0002] Photocuring and thermal curing are the two core curing methods for cationic polymerization systems. Photocuring uses ultraviolet or visible light to initiate the reaction, offering advantages such as rapid curing, energy conservation, and environmental protection. Thermal curing, on the other hand, uses heat to trigger the decomposition of the initiator, making it suitable for applications with limited light exposure or thick coatings.

[0003] However, existing cationic curing systems (whether light-curing or heat-curing) all face the following common technical difficulties: (1) Ion migration and corrosion problems: During the polymerization initiation reaction, strong acid ions are generated and migrate freely in the cured product to the surface of the adhesive material, causing corrosion to the substrate, especially the metal substrate, and affecting the final physical and chemical properties. (2) System sensitivity: Traditional cationic initiators are sensitive to the acidity and alkalinity of the system. When alkaline substances such as ethers are present in the system, they will capture the cationic active centers due to their nucleophilicity, causing the initiator to be deactivated, greatly affecting the curing efficiency. In addition, the surface of unmodified fillers is prone to enrichment of hydroxyl groups and thus presents weak alkalinity. Therefore, the activity of cationic initiators in filler systems is also prone to decrease. (3) Initiator loss problem. After long-term storage, cationic initiators are attacked by alkaline substances (ethers, fillers, etc.) in the system or nucleophilic substances (water) outside the system, resulting in initiator loss, reduced active centers, and reduced initiation activity. (4) In order to improve the barrier properties of adhesives, the industry usually adopts the method of adding lamellar fillers; however, the traditional physical blending process has obvious defects: the fillers are prone to agglomeration and sedimentation, and the dispersion uniformity is poor; the parallel stacking of lamellar layers cannot maximize the barrier effect; more importantly, the surface alkalinity of unmodified fillers will further aggravate the initiator deactivation problem.

[0004] Common improvements currently include solvent cleaning of fillers or the addition of stabilizers, but these only partially address the problem. While solvent cleaning can reduce the filler's surface alkalinity, it cannot completely prevent initiator deactivation; simply adding stabilizers may affect other adhesive properties. None of these approaches fundamentally address the dual challenges of initiator stability and filler dispersion.

[0005] Therefore, developing a new modification technology that can simultaneously protect the activity of the initiator and achieve nano-scale dispersion of the filler has become the key to breaking through the performance bottleneck of cationic curing adhesives; this can not only significantly improve the storage stability of the product, but also optimize its barrier properties, and has important industrial application value. Summary of the Invention

[0006] In order to solve the above technical problems, the present invention proposes to provide a cationic modified lamellar filler, which is composite-modified with a cationic initiator to significantly improve the curing efficiency and storage stability of the adhesive.

[0007] The present invention provides a method for preparing a cationic initiator intercalation-modified layered filler, comprising the following steps:

[0008] S1, dispersing the layered filler in an organic solvent to obtain a first mixed solution;

[0009] S2, mixing and dispersing a cationic initiator with the first mixed solution to obtain a second mixed solution;

[0010] S3, washing and drying the second mixed solution to obtain a primary intercalation product;

[0011] S4. Mixing and dispersing the primary intercalation product and the negative ion paired salt in an alcohol solvent to obtain a cationic initiator intercalation modified layered filler.

[0012] In the present invention, the layered filler is at least one selected from kaolin, bentonite, montmorillonite, and hydrotalcite.

[0013] In some specific embodiments of the present invention, the layered filler is at least one of kaolin and bentonite.

[0014] In the present invention, the cationic initiator includes a cationic photoinitiator and a cationic thermal initiator;

[0015] In some specific embodiments of the present invention, the cationic photoinitiator is at least one selected from aromatic iodonium salts, aromatic sulfonium salts, aromatic diazonium salts, aromatic phosphonium salts, and aromatic ferrocenium salts.

[0016] In some specific embodiments of the present invention, the cationic initiator is selected from at least one of triaryl sulfonium hexafluoroantimonate, triaryl sulfonium hexafluorophosphate, triaryl sulfonium tetrakis(pentafluorophenyl)borate, diaryl iodonium hexafluoroantimonate, diaryl iodonium hexafluorophosphate, and diaryl iodonium tetrakis(pentafluorophenyl)borate.

[0017] In the present invention, the negative ion paired salt is selected from at least one of sodium hexafluorophosphate, potassium hexafluorophosphate, sodium tetrafluoroborate, potassium tetrafluoroborate, sodium hexafluoroantimonate, potassium hexafluoroantimonate, sodium hexafluoroarsenate, potassium hexafluoroarsenate, sodium tetraphenylborate, potassium tetraphenylborate, sodium tetrakis(pentafluorophenyl)borate, potassium tetrakis(pentafluoromethylphenyl)borate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, sodium perfluorobutylsulfonate, potassium perfluorobutylsulfonate, sodium p-toluenesulfonate and potassium p-toluenesulfonate.

[0018] In some specific embodiments of the present invention, the anion paired salt is selected from at least one of sodium hexafluoroantimonate and sodium hexafluorophosphate.

[0019] In the present invention, the mass ratio of the cationic initiator to the lamellar filler is 0.6 to 2:1.

[0020] In the present invention, the mass ratio of the primary intercalation product to the anion pairing salt in step S4 is 1:0.05-0.2.

[0021] In some specific embodiments of the present invention, the organic solvent is selected from one or more of 1,4-butyrolactone and 1,2-propylene glycol carbonate.

[0022] In the present invention, the dispersion temperature in step S1 is 50-70°C and the dispersion time is 1-3 hours; the dispersion temperature in step S2 is 50-70°C and the dispersion time is 12-24 hours; and the dispersion temperature in step S4 is 40-60°C and the dispersion time is 1-3 hours.

[0023] The present invention provides a cationic initiator intercalation-modified layered filler obtained by the above-mentioned preparation method.

[0024] The present invention also provides an adhesive containing the cationic initiator intercalation-modified layered filler described above.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] (1) The cationic initiator is intercalated between the lamellar filler layers to avoid being attacked by nucleophilic substances and causing a decrease in activity, which can effectively protect the cationic initiator active center;

[0027] (2) Organic matter modified inorganic fillers can effectively improve the compatibility between fillers and resins, improve the storage stability of fillers in adhesive formulations, and avoid sedimentation and stratification during long-term storage;

[0028] (3) Extend the storage period of cationic epoxy adhesives to avoid the reduction of initiation efficiency and performance degradation caused by the consumption of cationic initiators after long-term storage;

[0029] (4) After being triggered by light or heat, the initiator cleaves and initiates epoxy polymerization in situ. The lamellar filler peels off the nanosheet layer to form an organic / inorganic nanosheet layer composite. Compared with the traditional filler mixing and curing, the distribution of the nanosheet layer is more disordered, which can significantly extend the water vapor permeation channel and improve the barrier performance of the film. DETAILED DESCRIPTION

[0030] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely for the purpose of explaining the present invention and are not intended to limit the present invention. All features disclosed in this specification, or steps in all methods or processes disclosed, except for mutually exclusive features and / or steps, can be combined in any manner.

[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0032] In the invention, "first", "second", etc. are only used to distinguish the objects being described and do not have any order or technical meaning.

[0033] In the present invention, the adhesive further comprises epoxy resin, diluent, coupling agent and cationic initiator.

[0034] Epoxy resins include, but are not limited to, bisphenol A epoxy resins, bisphenol F epoxy resins, novolac epoxy resins, resorcinol diglycidyl ether, and alicyclic epoxy resins.

[0035] The diluent includes, but is not limited to, alkenyl ether diluents, epoxy diluents, epoxidized triglyceride diluents, and oxetane diluents.

[0036] The coupling agent includes, but is not limited to, a silane coupling agent (such as A-187, KH-570), a titanate coupling agent, or an aluminate coupling agent.

[0037] Cationic initiators include cationic photoinitiators and cationic thermal initiators.

[0038] Example 1

[0039] Preparation of cationic initiator modified lamellar filler composites:

[0040] (1) Weigh 5 g of kaolin and add it to 250 g of 1,4-butyrolactone, ultrasonically disperse it for 30 min, and then stir and disperse it at 60°C for 2 h to obtain a mixed solution A;

[0041] (2) Weigh 9 g of UVI6976 (cationic photoinitiator) and dissolve it in 90 g of 1,4-butyrolactone, then add it dropwise to mixed solution A. Stir and disperse at 60° C. for 24 h to obtain mixed solution B.

[0042] (3) The mixture was cooled to room temperature, the solvent was removed by centrifugation, and the precipitate was washed with acetone three times by centrifugation. The resulting precipitate was dried in an oven at 50°C for 6 h to obtain a mixture C.

[0043] (4) 3 g of mixture C and 0.3 g of sodium hexafluoroantimonate were weighed and dispersed in 50 ml of ethanol. The mixture was stirred and dispersed at 50°C for 2 h. The mixture was centrifuged and washed twice with ethanol. The resulting precipitate was dried in an oven at 50°C for 6 h to obtain a cationic initiator intercalated modified lamellar filler composite.

[0044] Example 2

[0045] Preparation of cationic initiator modified lamellar filler composites:

[0046] (1) 5 g of bentonite was added to 250 g of 1,4-butyrolactone, and ultrasonically dispersed for 30 min. Then, stirred and dispersed at 60°C for 2 h to obtain a mixed solution A.

[0047] (2) Weigh 3.5 g of SI-100 (cationic thermal initiator) and dissolve it in 50 g of 1,4-butyrolactone, then add it dropwise to mixed solution A. Stir and disperse at 60°C for 24 h to obtain mixed solution B.

[0048] (3) The mixture was cooled to room temperature, the solvent was removed by centrifugation, and the precipitate was washed with acetone three times by centrifugation. The resulting precipitate was dried in an oven at 50°C for 6 h to obtain a mixture C.

[0049] (4) 3 g of mixture C and 0.3 g of sodium hexafluoroantimonate were weighed and dispersed in 50 ml of ethanol. The mixture was stirred and dispersed at 50°C for 2 h. The mixture was centrifuged and washed twice with ethanol. The resulting precipitate was dried in an oven at 50°C for 6 h to obtain a cationic initiator intercalated modified lamellar filler composite.

[0050] Example 3

[0051] Preparation of cationic initiator modified lamellar filler composites:

[0052] (1) Weigh 5 g of kaolin and add it to 250 g of 1,4-butyrolactone, ultrasonically disperse it for 30 min, and then stir and disperse it at 60°C for 2 h to obtain a mixed solution A;

[0053] (2) Weigh 4.1 g of TR-PAG-30201 (cationic photoinitiator) and dissolve it in 60 g of 1,4-butyrolactone, then add it dropwise to the mixed solution A. Stir and disperse at 60° C. for 24 h to obtain a mixed solution B.

[0054] (3) The mixture was cooled to room temperature, the solvent was removed by centrifugation, and the precipitate was washed with acetone three times by centrifugation. The resulting precipitate was dried in an oven at 50°C for 6 h to obtain a mixture C.

[0055] (4) 3 g of mixture C and 0.46 g of sodium hexafluorophosphate were weighed and dispersed in 50 ml of ethanol. The mixture was stirred and dispersed at 50°C for 2 h. The mixture was centrifuged and washed twice with ethanol. The resulting precipitate was dried in an oven at 50°C for 6 h to obtain a cationic initiator intercalated modified lamellar filler composite.

[0056] Example 4

[0057] Preparation of cationic initiator modified lamellar filler composites:

[0058] (1) 5 g of kaolin was added to 350 g of 1,2-propylene glycol carbonate, and ultrasonically dispersed for 30 min, followed by stirring and dispersion at 60°C for 2 h to obtain a mixed solution A;

[0059] (2) Weigh 9 g of UVI6976 (cationic photoinitiator) and dissolve it in 110 g of 1,2-propylene glycol carbonate, then add it dropwise to mixed solution A. Stir and disperse at 60° C. for 24 h to obtain mixed solution B.

[0060] (3) The mixture was cooled to room temperature, the solvent was removed by centrifugation, and the precipitate was washed with acetone three times by centrifugation. The resulting precipitate was dried in an oven at 50°C for 6 h to obtain a mixture C.

[0061] (4) 3 g of mixture C and 0.3 g of sodium hexafluoroantimonate were weighed and dispersed in 50 ml of ethanol. The mixture was stirred and dispersed at 50°C for 2 h. The mixture was centrifuged and washed twice with ethanol. The resulting precipitate was dried in an oven at 50°C for 6 h to obtain a cationic initiator intercalated modified lamellar filler composite.

[0062] Example 5

[0063] Preparation of cationic epoxy system high barrier sealing adhesive:

[0064] According to the weight percentage of each raw material in the total weight of the raw materials, 20 parts of the cationic initiator modified lamellar filler composite prepared in Example 1, 40 parts of bisphenol A epoxy resin Epikote828, 10 parts of toughened epoxy resin MX154, 19 parts of epoxy diluent CELLOXIDE 2021P, 10 parts of oxetane OXT-221, and 1 part of coupling agent A-187 were weighed and mixed evenly, vacuum degassed, filtered and packaged to obtain a finished adhesive.

[0065] Example 6

[0066] Preparation of cationic epoxy system high barrier sealing adhesive:

[0067] According to the weight percentage of each raw material in the total weight of the raw materials, 20 parts of the cationic initiator modified lamellar filler composite prepared in Example 2, 40 parts of bisphenol A epoxy resin Epikote828, 10 parts of toughened epoxy resin MX154, 19 parts of epoxy diluent CELLOXIDE 2021P, 10 parts of oxetane OXT-221, and 1 part of coupling agent A-187 were weighed and mixed evenly, vacuum degassed, filtered and packaged to obtain a finished adhesive.

[0068] Example 7

[0069] Preparation of cationic epoxy system high barrier sealing adhesive:

[0070] According to the weight percentage of each raw material in the total weight of the raw materials, 20 parts of the cationic initiator modified lamellar filler composite prepared in Example 3, 40 parts of bisphenol A epoxy resin Epikote828, 10 parts of toughened epoxy resin MX154, 19 parts of epoxy diluent CELLOXIDE 2021P, 10 parts of oxetane OXT-221, and 1 part of coupling agent A-187 were weighed and mixed evenly, vacuum degassed, filtered and packaged to obtain a finished adhesive.

[0071] Example 8

[0072] Preparation of cationic epoxy system high barrier sealing adhesive:

[0073] According to the weight percentage of each raw material in the total weight of the raw materials, 20 parts of the cationic initiator modified lamellar filler composite prepared in Example 4, 40 parts of bisphenol A epoxy resin Epikote828, 10 parts of toughened epoxy resin MX154, 19 parts of epoxy diluent CELLOXIDE 2021P, 10 parts of oxetane OXT-221, and 1 part of coupling agent A-187 were weighed and mixed evenly, vacuum degassed, filtered and packaged to obtain a finished adhesive.

[0074] Comparative Example 1

[0075] Preparation of lamellar fillers:

[0076] (1) Weigh 5 g of kaolin and add it to 350 g of 1,2-propylene glycol carbonate. Ultrasonic dispersion is performed for 30 min, and then stirred and dispersed at 60 °C for 2 h.

[0077] (2) Stir and disperse at 60°C for 24 hours;

[0078] (3) Cooling to room temperature, centrifuging to remove the solvent, washing with acetone three times, and drying the resulting precipitate in a 50°C oven for 6 hours to obtain a treated lamellar filler.

[0079] Comparative Example 2

[0080] Preparation of lamellar fillers:

[0081] (1) Weigh 5 g of bentonite and add it to 350 g of 1,2-propylene glycol carbonate. Ultrasonic dispersion is performed for 30 min, and then stirred and dispersed at 60 °C for 2 h.

[0082] (2) Stir and disperse at 60°C for 24 hours;

[0083] (3) The mixture was cooled to room temperature, centrifuged to remove the solvent, and washed with acetone three times by centrifugation. The resulting precipitate was placed in a 50°C oven and dried for 6 h to obtain a treated lamellar filler.

[0084] Comparative Example 3

[0085] Preparation of cationic initiator modified lamellar filler composites:

[0086] (1) Weigh 5 g of kaolin and add it to 250 g of 1,4-butyrolactone, ultrasonically disperse it for 30 min, and then stir and disperse it at 60°C for 2 h to obtain a mixed solution A;

[0087] (2) Weigh 9 g of UVI6976 (cationic photoinitiator) and dissolve it in 90 g of 1,4-butyrolactone, then add it dropwise to mixed solution A. Stir and disperse at 60° C. for 24 h to obtain mixed solution B.

[0088] (3) The mixture was cooled to room temperature, and the solvent was removed by centrifugation. The precipitate was washed with acetone three times by centrifugation. The obtained precipitate was dried in an oven at 50°C for 6 h to obtain a mixture.

[0089] Comparative Example 4

[0090] According to the weight percentage of each raw material in the total weight of the raw materials, 15 parts of kaolin treated in Comparative Example 1, 40 parts of bisphenol A epoxy resin Epikote828, 10 parts of toughened epoxy resin MX154, 19 parts of epoxy diluent CELLOXIDE 2021P, 10 parts of oxetane OXT-221, 5 parts of cationic initiator UVI6976, and 1 part of coupling agent A-187 were weighed, mixed and stirred evenly, vacuum degassed, filtered and packaged to obtain a finished adhesive.

[0091] Comparative Example 5

[0092] According to the weight percentage of each raw material in the total weight of the raw materials, 15 parts of bentonite treated in Comparative Example 2, 40 parts of bisphenol A epoxy resin Epikote828, 10 parts of toughened epoxy resin MX154, 19 parts of epoxy diluent CELLOXIDE 2021P, 10 parts of oxetane OXT-221, 5 parts of cationic initiator SI-100 (previously dissolved in 1,2-propylene glycol carbonate in a ratio of 1:1), and 1 part of coupling agent A-187 were weighed, mixed and stirred evenly, vacuum degassed, filtered and packaged to obtain a finished adhesive.

[0093] Comparative Example 6

[0094] According to the weight percentage of each raw material to the total weight of the raw materials, 20 parts of kaolin treated in Comparative Example 3, 40 parts of bisphenol A epoxy resin Epikote828, 10 parts of toughened epoxy resin MX154, 19 parts of epoxy diluent CELLOXIDE 2021P, 10 parts of oxetane OXT-221, and 1 part of coupling agent A-187 were weighed, mixed and stirred evenly, vacuum degassed, filtered and packaged to obtain a finished adhesive.

[0095] Comparative Example 7

[0096] Calculated by the weight of each raw material to the total weight of the raw materials, 15 parts of untreated kaolin, 40 parts of bisphenol A epoxy resin Epikote828, 10 parts of toughened epoxy resin MX154, 19 parts of epoxy diluent CELLOXIDE 2021P, 10 parts of oxetane OXT-221, 5 parts of cationic initiator UVI6976, and 1 part of coupling agent A-187 were weighed, mixed and stirred evenly, vacuum degassed, filtered and packaged to obtain a finished adhesive.

[0097] Comparative Example 8

[0098] Calculated by the weight of each raw material relative to the total weight of the raw materials, 15 parts of untreated bentonite, 40 parts of bisphenol A epoxy resin Epikote828, 10 parts of toughened epoxy resin MX154, 19 parts of epoxy diluent CELLOXIDE 2021P, 10 parts of oxetane OXT-221, 5 parts of cationic initiator SI-100 (previously dissolved in 1,2-propylene glycol carbonate in a ratio of 1:1), and 1 part of coupling agent A-187 were weighed, mixed and stirred evenly, vacuum degassed, filtered, and packaged to obtain a finished adhesive.

[0099] Test Example 1

[0100] The adhesives prepared in Examples 5-8 and Comparative Examples 4-8 were subjected to various performance tests, including film hardness, curing efficiency, and water vapor transmission rate. The test results are shown in Table 1.

[0101] 1. Film hardness

[0102] Take 1g of glue sample, control the glue layer thickness to 0.5mm, and apply 3000mJ / cm 2 The samples were irradiated with 365nm UV-LED light with high energy, then placed in a 100℃ oven for 1 hour, left for 1 hour to cool to room temperature, and then tested for hardness using a D-type Shore hardness tester.

[0103] 2. Curing efficiency test

[0104] Take 0.1g of the gel sample respectively and test the examples 5, 7, 8 and comparative examples 4, 6, 7 at 100mW / cm 2 The light intensity was 365nm UV-LED irradiation, and the illumination time required for the surface of the glue sample to be completely dry was counted; for Example 6 and Comparative Examples 5 and 8, 0.1g of the glue sample was placed in a 100℃ oven, and the debonding of the glue sample was measured every 30 seconds, and the required heating time was counted.

[0105] 3. Post-placement curing efficiency test

[0106] Curing efficiency test: 5g of the glue sample was placed in an opaque syringe and stored at 25℃. 0.1g of the sample was taken on the 1st, 3rd, 7th, 14th and 21st day respectively. The curing efficiency of Examples 5, 7, 8 and Comparative Examples 4, 6 and 7 was tested at 100mW / cm 2 The light intensity was 365nm UV-LED irradiation, and the illumination time required for the surface of the glue sample to be completely dry was counted; for Example 6 and Comparative Examples 5 and 8, 0.1g of the glue sample was placed in an oven at 100°C, and the heating time required for the surface of the glue sample to be debonded was counted.

[0107] 4. Water vapor transmission rate test

[0108] According to ASTM E96 / E96M-24a "Standard Test Method for Water Vapor Transmission Rate of Materials by Gravimetric Method", take 2g of glue sample, control the glue thickness to 0.5mm, and cure under 365nm UV-LED light 3000mJ / cm 2 , then cure at 100℃ for 1h; test temperature: (40±1)℃; test humidity: (90±2)%RH.

[0109] Table 1

[0110]

[0111] According to the test data in Table 1, the cationic initiator-modified lamellar filler composite of the present invention is applied to the adhesive formulation, and the influence of the nucleophilic substances in the formulation on the adhesive is greatly reduced, and the curing is not affected. Comparative Examples 7 and 8 use untreated lamellar fillers, and the curing is greatly affected. Comparative Examples 4 and 5 have a reduced effect due to the modification treatment to reduce some basic groups. Comparative Example 6 uses a modified filler composite without negative ion pairing, and the initiation activity is greatly reduced, and the curing effect is significantly reduced. In terms of storage performance, the cationic initiator-modified lamellar filler composite of the present invention performs excellently when applied to the adhesive formulation. After long-term storage, it is not affected by the nucleophilic substances in the adhesive, and the curing efficiency does not decrease. In the comparative example, the curing efficiency decreases significantly with increasing storage time, indicating that the cationic initiation activity is inactivated by the nucleophilic substances. In terms of water vapor transmission rate testing, the adhesive formulation using the cationic initiator-modified lamellar filler composite of the present invention has a lower water vapor transmission rate, indicating that the organic / nano lamellar filler composite film after curing according to the formulation of the present invention has better water vapor barrier properties.

[0112] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A method for preparing a cationic initiator intercalated modified layered filler, characterized in that: The steps include: S1, dispersing the layered filler in an organic solvent to obtain a first mixed solution; S2, mixing and dispersing a cationic initiator with the first mixed solution to obtain a second mixed solution; S3, washing and drying the second mixed solution to obtain a primary intercalation product; S4. Mixing and dispersing the primary intercalation product and the negative ion paired salt in an alcohol solvent to obtain a cationic initiator intercalation modified layered filler.

2. The preparation method according to claim 1, characterized in that The layered filler is at least one selected from kaolin, bentonite, montmorillonite, and hydrotalcite; further, the layered filler is at least one selected from kaolin and bentonite.

3. The preparation method according to claim 1, characterized in that The cationic initiator includes a cationic photoinitiator and a cationic thermal initiator; Furthermore, the cationic initiator is at least one selected from aromatic iodonium salts, aromatic sulfonium salts, aromatic diazonium salts, aromatic phosphonium salts, and aromatic ferrocenium salts; Furthermore, the cationic initiator is selected from at least one of triaryl sulfonium hexafluoroantimonate, triaryl sulfonium hexafluorophosphate, triaryl sulfonium tetrakis(pentafluorophenyl)borate, diaryl iodonium hexafluoroantimonate, diaryl iodonium hexafluorophosphate, and diaryl iodonium tetrakis(pentafluorophenyl)borate.

4. The preparation method according to claim 1, characterized in that The negative ion paired salt is selected from at least one of sodium hexafluorophosphate, potassium hexafluorophosphate, sodium tetrafluoroborate, potassium tetrafluoroborate, sodium hexafluoroantimonate, potassium hexafluoroantimonate, sodium hexafluoroarsenate, potassium hexafluoroarsenate, sodium tetraphenylborate, potassium tetraphenylborate, sodium tetrakis(pentafluorophenyl)borate, potassium tetrakis(pentafluoromethylphenyl)borate, potassium tetrakis(pentafluoromethylphenyl)borate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, sodium perfluorobutylsulfonate, potassium perfluorobutylsulfonate, sodium p-toluenesulfonate and potassium p-toluenesulfonate; further, the negative ion paired salt is selected from at least one of sodium hexafluoroantimonate and sodium hexafluorophosphate.

5. The preparation method according to claim 1, characterized in that The mass ratio of the cationic initiator to the lamellar filler is 0.6 to 2:

1.

6. The preparation method according to claim 1, characterized in that The mass ratio of the primary intercalation product to the anion pairing salt in step S4 is 1:0.05-0.

2.

7. The preparation method according to claim 1, characterized in that The organic solvent is selected from one or more of 1,4-butyrolactone and 1,2-propylene glycol carbonate.

8. The preparation method according to claim 1, characterized in that In step S1, the dispersion temperature is 50-70° C. and the dispersion time is 1-3 hours; in step S2, the dispersion temperature is 50-70° C. and the dispersion time is 12-24 hours; in step S4, the dispersion temperature is 40-60° C. and the dispersion time is 1-3 hours.

9. A cationic initiator intercalation-modified layered filler obtained by the preparation method according to any one of claims 1 to 8.

10. An adhesive, characterized in that: Contains the cationic initiator intercalation modified layered filler according to claim 9.

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