Amino bonding aid, its preparation method and application

Abstract

The present invention provides an amino bonding aid, a preparation method thereof and an application thereof. The bonding aid is mainly a macromolecule having 1 to 4 amino groups obtained by first polymerizing HDI biuret with a monoamino silane coupling agent and then reacting with diethylenetriamine and a small molecule diamine. When the above-mentioned bonding aid is applied to a polyurethane or epoxy adhesive, it not only participates in the chain extension reaction of the polyurethane and epoxy, reacts with a relatively large bonding group into the polyurethane segment or epoxy segment, and because it contains polyamino molecules, it can play a cross-linking role and improve the bulk strength of the final product; also, due to a large number of siloxane structures and ureido groups therein, it improves the bonding strength of the adhesive to substrates such as glass, stainless steel, anodized aluminum, etc. and the low-temperature initial adhesion performance, shortens the construction period, and even improves the construction quality. In addition, the viscosity of the polyether or epoxy adhesive applied with the above-mentioned amino bonding aid is relatively small, which is beneficial to improving its workability.

Description

Technical Field

[0001] The present invention relates to the technical field of adhesion aids, and particularly relates to an amino adhesion aid, a preparation method thereof, and an application thereof. Background Art

[0002] Adhesives are materials often used in production and life, including various systems such as silicone, epoxy, polyurethane, and acrylic. In the raw materials of existing adhesives, adhesion aids are usually added to improve their adhesion strength. For example, Chinese Patent Application CN 113667095A discloses an adhesion aid for foam plastics, a preparation method thereof, and an application thereof. The disclosed adhesion aid is directly added to the adhesive material and mixed with other components during the construction process, making the adhesion performance of the foam plastics more stable.

[0003] Two-component adhesives are often used in production due to their production process and some performance advantages. When in use, the two-component raw materials need to be mixed in proportion to achieve their adhesion function. For example, polyurethane adhesives and epoxy adhesives. When using two-component adhesives, a specific glue gun is usually required to simultaneously extrude and mix the two components. If the viscosity of the components is relatively high, users need to apply a greater force to extrude the components. Especially when constructing in winter or at a lower temperature environment, it increases the construction difficulty for users; moreover, when the viscosity of the components is relatively high, it is not conducive to the uniform mixing of the two components.

[0004] In addition, during the construction process of adhesives, their curing speed has a great relationship with the ambient temperature. During the construction process in winter or at a lower temperature environment, adhesives in systems such as epoxy and polyurethane often exhibit poor initial adhesion performance and low initial adhesion strength. Especially when polyurethane adheres to substrates such as glass, stainless steel, and anodized aluminum, it is more obvious, thus prolonging the construction period and even resulting in unqualified construction. Summary of the Invention

[0005] In view of this, it is necessary for the present invention to provide an amino adhesion aid, a preparation method thereof, and an application thereof.

[0006] Specifically, the technical solution provided by the present invention is: an amino adhesion aid, which is mainly a macromolecular adhesion aid with 1 to 4 amino groups obtained by first polymerizing HDI biuret with a monoamino silane coupling agent and then reacting with diethylenetriamine and a small molecule diamine. Among them, calculated in molar parts: 100 parts of HDI biuret, 150 - 250 parts of the monoamino silane coupling agent, 25 - 150 parts of diethylenetriamine, and 25 - 150 parts of the small molecule diamine.

[0007] Among them, "HDI biuret" herein refers to 1,6 - hexamethylene diisocyanate biuret. "Small molecule" herein refers to a substance with a molecular weight below 150.

[0008] Based on the above, n(HDI biuret)×3 = n(monoamino silane coupling agent) + n(diethylenetriamine) + n(small molecule diamine), where n(HDI biuret), n(monoamino silane coupling agent), n(diethylenetriamine), and n(small molecule diamine) respectively represent the molar amounts of the corresponding raw materials; since 1 molecule of HDI biuret contains 3 isocyanate groups, the amounts of the four are limited in this way, so that the isocyanate groups in HDI biuret are completely reacted and capped, and the prepared product contains molecules with 1 to 4 amino groups, among which the multi-amino molecules (molecules containing more than two amino groups) can play a cross-linking role, which is beneficial to improving the strength of the colloid itself in the future. At the same time, since the isocyanate groups are completely capped, its usage method also changes.

[0009] Based on the above, the monoamino silane coupling agent is one of bis(3-trimethoxysilylpropyl)amine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(phenylamino)propyltrimethoxysilane; preferably bis(3-trimethoxysilylpropyl)amine.

[0010] Based on the above, the small molecule diamine is ethylenediamine, 1,2-propanediamine, 1,3-propanediamine or pentanediamine.

[0011] The present invention provides a preparation method of the above amino adhesion promoter, including:

[0012] Under the condition of inert gas, first uniformly mix HDI biuret with the first solvent to form a first mixture, then gradually drop the monoamino silane coupling agent into the first mixture under stirring at 20°C to 25°C until the dropping is complete, and then continue to react for 30 to 60 minutes, and then raise the temperature to 50°C to 70°C and continue to react for 30 to 60 minutes to prepare a first prepolymer;

[0013] First uniformly mix the small molecule diamine, diethylenetriamine and the second solvent to form a second mixture, and then slowly drop the first prepolymer into the second mixture under the conditions of 20°C to 25°C, a rotation speed of 100 to 150 r / min and under the protection of inert gas until the reaction is complete and continue to react for 30 to 60 minutes, and then raise the temperature to 50°C to 70°C and continue to react for 30 to 60 minutes to obtain the amino adhesion promoter.

[0014] The solid content of the amino adhesion promoter is 34% to 36%; during its preparation, the solid content in the formula is calculated. If the solid content is below 34%, vacuum is used to remove the solvent and adjusted to 34% to 36%; if the solid content is above 36%, the second solvent is added to adjust the solid content to 34% to 36%.

[0015] Based on the above, the ratio of the total mass of the HDI biuret and the monoamino silane coupling agent to the first solvent is (50 - 100):100.

[0016] Based on the above, the mass ratio of the total mass of the small molecule diamine and diethylenetriamine to the second solvent is (5 - 20):100.

[0017] Based on the above, the first solvent is toluene or xylene, and the second solvent is toluene or xylene.

[0018] The present invention also provides an application of the above amino adhesion promoter in a polyurethane adhesive or an epoxy adhesive. Preferably, the adhesive is a low-density polyurethane adhesive or a low-density epoxy adhesive.

[0019] Based on the above application, the amino adhesion promoter is applied in the polyether component of the polyurethane adhesive or the epoxy curing agent component of the epoxy adhesive.

[0020] The polyurethane adhesive comprises raw materials in the following parts by mass:

[0021] Component A: PAPI (polymethylene polyphenyl isocyanate)

[0022] Component B, that is, the polyether component includes: 100 parts of polyether polyol, 0.5 - 5 parts of the above adhesion promoter, 5 - 30 parts of glass microspheres, 2 - 5 parts of fumed silica, 0.05 - 0.2 parts of catalyst.

[0023] Among them, the type of the polyether polyol is one or a combination of two of 303, 304, 305 and 330N, and the catalyst is dibutyltin dilaurate or dibutyltin dichloride.

[0024] Component B is mainly obtained by the following method: adding the polyether polyol to a dehydration kettle, dehydrating for 2 - 3 h under the conditions of lower than -0.095 MPa and 80°C - 100°C, then cooling to 30°C - 40°C and adding the amino adhesion promoter thereto, continuing to stir for 0.5 - 1 h under vacuum conditions to remove the solvent; adding the glass microspheres, fumed silica and catalyst after dehydration treatment thereto, and stirring for 10 - 20 min to obtain Component B.

[0025] Mixing Component A and Component B in the above polyurethane adhesive evenly according to the molar ratio of the isocyanate group in Component A to the active hydrogen in the polyether polyol in Component B being (0.98 - 1.05):1 can achieve curing.

[0026] The epoxy adhesive comprises raw materials in the following parts by mass:

[0027] Component A includes raw materials: 100 parts of epoxy resin, 5 - 10 parts of diluent, 5 - 20 parts of glass microspheres, and 2 - 10 parts of fumed silica;

[0028] Component B, namely the epoxy curing agent component, includes raw materials: 100 parts of curing agent, 5 - 20 parts of glass microspheres, 2 - 10 parts of fumed silica, 1 - 3 parts of accelerator, and 1 - 5 parts of adhesion aid.

[0029] Among them, the epoxy resin is E44 or E51, the epoxy diluent is trimethylolpropane triglycidyl ether or benzyl glycidyl ether, and the curing agent is one or more of 650, 651, and T31.

[0030] Component A of the epoxy adhesive is mainly prepared by stirring epoxy resin, diluent, and glass microspheres in a stirring kettle at a speed of 40 - 60 r / min for 2 - 3 min, then adding fumed silica and continuing to stir for 3 - 5 min before discharging from the kettle.

[0031] Component B of the epoxy adhesive is mainly prepared by stirring the curing agent and the adhesion aid at 30 - 50 °C under a condition of less than -0.095 MPa for 30 - 60 min to remove the solvent, then adding glass microspheres at normal temperature and pressure and stirring at a speed of 40 - 60 r / min for 2 - 3 min, and then adding fumed silica and accelerator and continuing to stir for 3 - 5 min before discharging from the kettle.

[0032] For Component A and Component B of the above epoxy adhesive, when the curing agent is 650, they are mixed evenly according to the mass ratio of the epoxy resin contained in Component A to the curing agent contained in Component B of 100:(80 - 110); when the curing agent is 651, they are mixed evenly according to the mass ratio of 100:(30 - 50); when the curing agent is T31, they are mixed evenly according to the mass ratio of 100:(20 - 35).

[0033] The glass microspheres used in the above polyurethane adhesive or epoxy adhesive are all hollow microspheres with a true density of 0.15 g / cm 3 ~0.70 g / cm 3 and a particle size D90 between 15 microns and 110 microns. Preferably, they are the glass microspheres produced by Zhengzhou Shenglaite Hollow Microsphere New Materials Co., Ltd.

[0034] If the above-mentioned adhesion promoter is added to component A, the binder component of the polyurethane adhesive, the amino groups contained in the adhesion promoter will react with the urethane in component A, resulting in an increase in its viscosity, an increase in the extrusion force during construction of component A, and an increase in the construction difficulty. If the above-mentioned adhesion promoter is added to component A, the binder component of the epoxy resin adhesive, the amino groups contained in the adhesion promoter will react with the epoxy functional groups in component A, causing epoxy chain extension, and also increasing the viscosity of component A and the construction difficulty. Therefore, the above-mentioned amino adhesion promoter should be added to component B, the polyether component of the polyurethane adhesive, or component B, the epoxy curing agent of the epoxy adhesive. The viscosity of this component does not change much, which is beneficial to improving the workability of the adhesive.

[0035] The above-mentioned amino adhesion promoter provided by the present invention is mainly prepared by reacting HDI biuret, monoamino silane coupling agent, diethylenetriamine and small molecule diamine. First, the monoamino silane coupling agent is used as a capping agent to cap HDI biuret, consuming some of the isocyanate groups therein. The isocyanate groups in the remaining HDI biuret respectively undergo capping reactions with small molecule diamine and diethylenetriamine. And because n(HDI biuret)×3 = n(monoamino silane coupling agent)+n(diethylenetriamine)+n(small molecule diamine), the monoamino silane coupling agent, small molecule diamine and diethylenetriamine act as capping agents for the isocyanate groups to completely react the isocyanate groups in HDI biuret, obtaining a macromolecular adhesion promoter with 1-4 amino groups. This macromolecular amino adhesion promoter contains a large number of siloxane structures and ureido groups that are beneficial for adhesion.

[0036] When the above-mentioned macromolecular adhesion promoter with 1-4 amino groups provided by the present invention is applied to adhesives in polyurethane or epoxy systems, on the one hand, it participates in the chain extension reactions of polyurethane and epoxy, reacting with a relatively large adhesion group into the polyurethane chain segment or epoxy chain segment, and because it contains multi-amino molecules, it can play a cross-linking role, thereby improving the bulk strength of the final product; on the other hand, because the adhesion promoter contains a large number of siloxane structures and a large number of ureido groups, it improves the bonding strength of the adhesive to substrates such as glass, stainless steel, anodized aluminum, etc. and the low-temperature initial adhesion performance, shortens the construction period, and even improves the construction quality. In addition, for the polyurethane adhesive or epoxy adhesive applying the above-mentioned amino adhesion promoter, on the premise of ensuring the adhesive performance of the adhesive, the viscosities of each component are relatively small and the workability is good. Detailed implementation modes

[0037] The technical solutions of the present invention will be further described in detail through the following detailed implementation modes.

[0038] Examples 1-5

[0039] The raw material ratios of the amino bonding aids provided in Examples 1-5 and Comparative Example 1 of the present invention are shown in Table 1 below:

[0040] Table 1 Molar ratio of raw materials of amino bonding aid

[0041] Sample HDI biuret Bis(3-trimethoxysilylpropyl)amine Diethylenetriamine 1,3-Propanediamine Example 1 100 200 25 75 Example 2 100 150 60 90 Example 3 100 180 30 60 Example 4 100 150 125 25 Example 5 100 250 25 25 Comparative Example 1 100 75 25 0

[0042] Among them, the amino bonding aids provided in Examples 1-5 are mainly prepared by the following steps:

[0043] First step: Mix HDI biuret with the first solvent toluene evenly under nitrogen protection to form a first mixture, and then gradually add bis(3-trimethoxysilylpropyl)amine dropwise to the first mixture under stirring at 25°C. After the dropping is complete, continue to react for 45 minutes, and then raise the temperature to 60°C and continue to react for 45 minutes to make bis(3-trimethoxysilylpropyl)amine react completely with HDI biuret, preparing a first prepolymer, and the ratio of toluene solvent to the total mass of HDI biuret and bis(3-trimethoxysilylpropyl)amine is 100:70;

[0044] Second step: Mix the second solvent toluene with diethylenetriamine and 1,3-propanediamine evenly to form a second mixture. Slowly add the first prepolymer dropwise to the second mixture at 25°C, a rotation speed of 120 r / min, and under nitrogen protection. After the dropping is complete, continue to react for 30 minutes, and then raise the temperature to 60°C and continue to react for 45 minutes to make the remaining isocyanate groups in HDI biuret react completely with diethylenetriamine and 1,3-propanediamine. Then adjust the solid content to 35% to obtain the above-mentioned amino bonding aid. The weight ratio of toluene solvent to the total mass of diethylenetriamine and 1,3-propanediamine is 100:12.

[0045] The amino bonding aid provided in Comparative Example 1 is mainly prepared by the following steps: 1) Dissolve diethylenetriamine in toluene at a temperature below 20°C to form a first dilution solution, and the mass ratio of toluene solvent to diethylenetriamine is 100:12; 2) Mix HDI biuret and toluene evenly to form a second dilution solution, and the ratio of toluene solvent to the total mass of HDI biuret and bis(3-trimethoxysilylpropyl)amine is 100:70; 3) Drop the first dilution solution in step 1) into the second dilution solution in step 2) under an inert atmosphere, the dropping temperature is below 20°C, the stirring rate during dropping is 300 r / min, after reacting for 20 minutes by dropping, raise the reaction temperature to 60°C, and continue to stir and react for 30 minutes, and the stirring speed is 300 r / min; 4) After the reaction in step 3) is completed, cool down to below 20°C, and continue to add bis(3-trimethoxysilylpropyl)amine to the mixed solution in step 2) in batches, keep the rotation speed unchanged and stir and react for 25 minutes, then raise the temperature to 60°C, continue to stir and react for 1 hour, and then adjust the solid content to 35% to obtain the bonding aid.

[0046] Applications of Examples 1 - 5

[0047] (1) Apply the amino adhesion aids provided in Examples 1 - 5 and Comparative Example 1 to polyurethane adhesives and epoxy adhesives respectively.

[0048] Among them, the raw materials of the polyurethane adhesive are as follows:

[0049] Component A: PAPI

[0050] Component B: By mass, it includes 20 parts of polyether polyol YD305, 80 parts of polyether polyol 330n, 3.5 parts of the adhesion aid shown in Table 1, 20 parts of glass microspheres HL38, 3 parts of fumed silica, and 0.07 parts of dibutyltin dilaurate. Among them, the treatment process of this Component B is: Add polyether polyols YD305 and 330n to a dehydration kettle, and dehydrate at a pressure below -0.095 MPa and a temperature of 100 °C for 2 h. Then cool down to 35 °C and add the adhesion aids provided in Examples 1 - 5 respectively, and continue to stir for 1 h under vacuum conditions to remove the solvent. Then add the dehydrated glass microspheres HL38, fumed silica, and dibutyltin dilaurate into it and stir for 10 min to obtain Component B.

[0051] The Component A and Component B in the polyurethane adhesive can be uniformly mixed in a mass ratio of 100:550 and then cured.

[0052] The raw materials of the epoxy adhesive are as follows:

[0053] Component A: 100 parts of epoxy resin E51, 5 parts of trimethylolpropane triglycidyl ether, 15 parts of glass microspheres (HL38), 3 parts of fumed silica; among them, the treatment process of this Component A is: Stir epoxy resin E51, trimethylolpropane triglycidyl ether, and glass microspheres HL38 in a stirring kettle at a speed of 60 r / min for 2 min, then add fumed silica and continue to stir for 5 min, and take out of the kettle to obtain Component A;

[0054] Component B: 100 parts of curing agent 651, 15 parts of glass microspheres HL38, 3 parts of fumed silica, 2 parts of DMP - 30, 3 parts of adhesion aid, among them, the treatment process of this Component B is: Stir the curing agent 651 and the adhesion aids provided in Examples 1 - 5 respectively under the conditions of 40 °C and a pressure below -0.095 MPa for 45 min to remove the solvent. Then add glass microspheres HL38 at normal temperature and normal pressure and stir at a speed of 50 r / min for 2 - 3 min, then add fumed silica and DMP - 30 and continue to stir for 4 min, and take out of the kettle to obtain Component B.

[0055] The A component and the B component in the epoxy adhesive can be cured by uniformly mixing them in a mass ratio of 100:50.

[0056] (2) Comparative Examples 2-3: The adhesion aids provided in Examples 1 and 2 were respectively added to the A component of the above polyurethane adhesive and epoxy adhesive, and not added to the B component, while other components and processes remained unchanged.

[0057] Examples 6-8

[0058] The raw material ratios of the amino adhesion aids provided in Examples 6-8 of the present invention are shown in Table 2:

[0059] Table 2 Molar ratio table of raw materials of amino adhesion aids

[0060]

[0061] The preparation methods of the amino adhesion aids provided in Examples 6-8 are basically the same as those of the amino adhesion aids provided in Examples 1-5, and the main differences are as follows:

[0062] In Example 6, the first solvent used is xylene, and its ratio to the total mass of HDI biuret and 3-aminopropyltrimethoxysilane is 100:80; the second solvent used is xylene, and its mass ratio to the total mass of diethylenetriamine and 1,2-propanediamine is 100:15.

[0063] In Example 7, the first solvent used is toluene, and its ratio to the total mass of HDI biuret and 3-aminopropyltriethoxysilane is 100:100; the second solvent used is toluene, and its mass ratio to the total mass of diethylenetriamine and pentanediamine is 100:10.

[0064] In Example 8, the first solvent used is toluene, and its ratio to the total mass of HDI biuret and 3-(phenylamino)propyltrimethoxysilane is 100:75; the second solvent used is toluene, and its mass ratio to the total mass of diethylenetriamine and ethylenediamine is 100:18.

[0065] Applications of Examples 6-8

[0066] The amino adhesion aids provided in Examples 6 and 7 were respectively applied to the preparation of polyurethane adhesives. Among them, the raw materials of the polyurethane adhesive include:

[0067] A component: PAPI

[0068] Component B: By mass, 10 parts of polyether polyol YD304, 90 parts of polyether polyol 330n, 4 parts of the adhesion promoter provided in Example 6, 18 parts of glass beads HL30, 4 parts of fumed silica, and 0.15 parts of dibutyltin dilaurate. The treatment process of Component B is basically the same as the corresponding treatment processes provided in Examples 1-5.

[0069] The polyurethane adhesive can be cured by uniformly mixing Component A and Component B in the polyurethane adhesive in a mass ratio of 100:705.

[0070] Apply the amino adhesion promoter provided in Example 8 to the preparation of the epoxy adhesive. Among them, the raw materials of the epoxy adhesive include:

[0071] Component A: 100 parts of epoxy resin E44, 8 parts of benzyl glycidyl ether, 15 parts of glass beads HL30, and 6 parts of fumed silica. The treatment process of Component A is basically the same as the corresponding treatment processes provided in Examples 1-5;

[0072] Component B: 100 parts of curing agent T31, 15 parts of glass beads HL30, 6 parts of fumed silica, 2 parts of DMP-30, and 3 parts of the above adhesion promoter. The treatment process of Component B is basically the same as the corresponding treatment processes provided in Examples 1-5.

[0073] The epoxy adhesive can be cured by uniformly mixing Component A and Component B in the epoxy adhesive in a mass ratio of 100:31.

[0074] Performance Test

[0075] Density measurement method: Cure the polyurethane sealants provided in Examples 1-8 and Comparative Examples 1-6 for 5 days under the standard conditions of 23°C * 50% RH, then mix them uniformly according to the mixing ratios of their respective Component A and Component B, and scrape them into thin slices of 2 mm × 40 mm × 40 mm. After curing for 7 days under the standard conditions of 23°C × 50% RH, measure their densities by the drainage method respectively. The results are shown in Table 3.

[0076] Viscosity measurement method: Seal and store the polyurethane or epoxy adhesives using the amino adhesion promoters provided in Examples 1-8 and Comparative Examples 1-3, and cure them for 24 hours under the standard conditions of 23°C * 50% RH respectively. Then, use a rotational viscometer to measure the viscosities of their Component A and Component B respectively, and measure the viscosity of Component A after curing for 10 days. The results are shown in Table 3.

[0077] Shearing strength measurement method: After curing the adhesives provided in the above Examples 1-8 and Comparative Examples 1-3 under the standard conditions of 23°C * 50% RH for 5 days, they were respectively mixed evenly according to the mixing ratios of their respective Component A and Component B, and the respective mixtures were used to coat a 1-mm-thick adhesive with a bonding area of 25 mm × 12.5 mm on the surface of an anodized aluminum sheet with dimensions of 25 mm × 100 mm × 2 mm treated with a toluene dilution of silane coupling agent KH550, and it was pasted onto an electrophoretic paint steel sheet with dimensions of 25 mm × 100 mm × 2 mm. At the same time, it was cured for 7 days under the standard conditions of 23°C * 50% RH and under the condition of low temperature at -5°C, and its shearing strength was tested. The results are shown in Table 3:

[0078] Table 3 Application performance results of amino bonding aids in adhesives

[0079]

[0080]

[0081] It can be seen from Table 3 that: Compared with the adhesives using the amino bonding aids provided in Comparative Example 1, the standard-condition shearing strength of the adhesives using the amino bonding aids provided in Examples 1-5 is relatively large. This shows that the adhesive aids provided in this example are beneficial to enhancing the bonding strength and bulk strength of the colloid.

[0082] Analyzing from the low-temperature shearing strength, the low-temperature shearing strength of the adhesives using the amino bonding aids provided in Examples 1-5 is much higher than that of Comparative Example 1. This shows that the adhesive aids provided in this example are beneficial to enhancing the initial adhesion strength of the colloid under low-temperature conditions, improving the construction performance in a low-temperature environment, and facilitating the shortening of the construction period.

[0083] Analyzing from the perspective of the viscosities of the components, the viscosities of Component A of the adhesives applying the amino bonding aids provided in Examples 1-5 and Comparative Example 1 basically do not change, but the viscosity of Component B of the adhesives applying the bonding aids in Examples 1-5 is much smaller than that of Component B of the adhesive applying Comparative Example 1. From this, it can be seen that the viscosities of the components of the adhesives applying the amino bonding aids provided in the examples of the present invention are relatively small, which is beneficial to construction. From the comparison of the viscosities of the components of the adhesives applying the bonding aids provided in Examples 1-2 and Comparative Examples 2-3, it can be known that when the amino bonding aids provided in the examples of the present invention are added to Component A of the adhesive, the viscosity of Component A will increase significantly, and it will cause the storage stability of Component A of the polyurethane to deteriorate; when added to Component B, the viscosity of Component B changes little. Therefore, for the low-density polyurethane adhesives or low-density epoxy adhesives applying the bonding aids provided in the examples of the present invention, on the premise of ensuring the bonding performance of the adhesive, the viscosities of the components are relatively small and the workability is good.

[0084] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them; although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that it is still possible to modify the specific implementation manners of the present invention or perform equivalent replacements for some technical features; without departing from the spirit of the technical solutions of the present invention, they should all be covered within the scope of the technical solutions claimed by the present invention.

Claims

1. An amino bonding aid, characterized in that: It is mainly a macromolecular bonding aid with 1-4 amino groups, siloxane structure and ureido groups prepared by first polymerizing HDI biuret with a monoamino silane coupling agent and then reacting with diethylenetriamine and a small molecule diamine to completely block the isocyanate groups therein. Among them, by mole fraction: 100 parts of HDI biuret, 150-250 parts of the monoamino silane coupling agent, 25-150 parts of diethylenetriamine, and 25-150 parts of the small molecule diamine.

2. The amino bonding aid according to claim 1, characterized in that: The amounts of substance of HDI biuret, the monoamino silane coupling agent, diethylenetriamine and the small molecule diamine are represented by n(HDI biuret), n(monoamino silane coupling agent), n(diethylenetriamine) and n(small molecule diamine) respectively, and n(HDI biuret)×3 = n(monoamino silane coupling agent) + n(diethylenetriamine) + n(small molecule diamine).

3. The amino bonding aid according to claim 1 or 2, characterized in that: The monoamino silane coupling agent is bis(3-trimethoxysilylpropyl)amine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane or 3-(phenylamino)propyltrimethoxysilane.

4. The amino bonding aid according to claim 1 or 2, characterized in that: The small molecule diamine is ethylenediamine, 1,2-propanediamine, 1,3-propanediamine or pentanediamine.

5. A preparation method of the amino bonding aid according to any one of claims 1-4, comprising: Under the condition of inert gas, first uniformly mix HDI biuret with a first solvent to form a first mixture, then gradually drop the monoamino silane coupling agent into the first mixture under stirring at 20°C - 25°C until the dropping is complete, then continue to react for 30 - 60 min, and then raise the temperature to 50°C - 70°C and continue to react for 30 - 60 min to prepare a first prepolymer; First uniformly mix the small molecule diamine, diethylenetriamine and a second solvent to form a second mixture, and then slowly drop the first prepolymer into the second mixture under the conditions of 20°C - 25°C, a rotation speed of 100 - 150 r / min and inert gas protection until the reaction is complete and continue to react for 30 - 60 min, and then raise the temperature to 50°C - 70°C and continue to react for 30 - 60 min to obtain the amino bonding aid.

6. The preparation method according to claim 5, characterized in that: The mass ratio of the total mass of HDI biuret and the monoamino silane coupling agent to the mass of the first solvent is (50 - 100) :

100.

7. The preparation method according to claim 5 or 6, characterized in that: The mass ratio of the total mass of the small molecule diamine and diethylenetriamine to the mass of the second solvent is (5 - 20) :

100.

8. The preparation method according to claim 7, characterized in that: Both the first solvent and the second solvent are toluene or xylene.

9. Use of the amino adhesion promoter according to any one of claims 1 to 4 in the preparation of a polyurethane adhesive or an epoxy adhesive.

10. The use according to claim 9, wherein: the amino adhesion promoter is used in the polyether component of the polyurethane adhesive or the epoxy curing agent component of the epoxy adhesive.

Images