High viscosity, age resistant encapsulant and method of making same

Abstract

The application relates to the technical field of automobile coating glue, in particular to high-viscosity aging-resistant coating glue and a preparation method thereof, which comprises a main agent and a curing agent, the preparation raw materials of the main agent at least include HDI end-capped modified hydroxyl mixture and modified amine, and the curing agent is a combination of HDI trimer and isofuroline ketone diisocyanate end-capped hydroxyl compound; the HDI end-capped modified hydroxyl mixture is prepared by end-capping of HDI on a modified hydroxyl mixture, and the preparation raw materials of the modified hydroxyl mixture at least include alcohol end-capped prepolymer 45-70 parts, polyhexanedioic acid-1,4-butanediol ester diol 30-50 parts and 2,2-dimethylol propionic acid 2-5 parts according to weight parts; by adopting the specific modified hydroxyl mixture, the modified amine and the curing agent, the main agent and the curing agent have a long use time after being mixed, excellent initial bonding strength and low-temperature resistance of the product are ensured, and the actual application requirements are better met.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of automobile coating glue, in particular to high-viscosity anti-aging coating glue and a preparation method thereof. BACKGROUND

[0002] In the aspect of automobile interior, solvent-based polyurethane adhesive has always occupied the main market due to the advantages of strong initial adhesion and fast drying, but with the development of the automobile industry towards low VOC, environmental requirements are put forward for the coating glue, such as a water-based polyurethane automobile interior coating glue and a preparation method thereof disclosed in Chinese Patent (Publication No. CN111072899A), which provides a water-based polyurethane coating glue with good initial adhesion, which can meet the demand for low VOC and the requirement for the bonding force between the automobile interior base material and the coating material, but the anti-aging performance in the actual application process needs to be further improved, which limits its application and promotion. Chinese Patent (Publication No. CN117165242A) discloses a high-temperature-resistant coating glue and a preparation method and application thereof, which mainly introduces polydopamine-modified nano silicon dioxide and silicone-modified hydroxy acrylate to improve the heat resistance of the coating glue, but the automobile coating glue will also face low-temperature environments in actual application, and the low bonding performance of the coating glue under low-temperature conditions will also affect its actual application. SUMMARY

[0003] In order to solve the above problems, the application uses a specific modified hydroxyl mixture, a modified amine and a curing agent, so that the viscosity (25 DEG C) of the prepared coating glue main agent and curing agent is 7000-8000 mPa s without the need for additional addition of thickening aids and water-soluble aids, and the product has excellent initial bonding strength and low-temperature resistance, better meeting the actual application requirements.

[0004] The application provides a high-viscosity anti-aging coating glue, which comprises a main agent and a curing agent, the preparation raw materials of the main agent at least include an HDI end-capped modified hydroxyl mixture and a modified amine, and the curing agent is a combination of an HDI trimer and an isofuroline diisocyanate end-capped hydroxyl compound; the HDI end-capped modified hydroxyl mixture is prepared by end-capping of an HDI on a modified hydroxyl mixture, and the preparation raw materials of the modified hydroxyl mixture at least include alcohol end-capped prepolymer 45-70 parts, polyhexanedioic acid-1,4-butanediol ester diol 30-50 parts and 2,2-dimethylol propionic acid 2-5 parts according to weight parts; the alcohol end-capped prepolymer is a mixture of alcohol end-capped prepolymers 1, 2 and 3, and the alcohol end-capped prepolymers 1, 2 and 3 are respectively prepared by reaction end-capping of hydroxyl end-capped prepolymers generated by chain extension of polyethylene glycol and diphenyl methane diisocyanate on copolyether glycol, hydroxyl end-capped polybutadiene and dimer diol.

[0005] Preferably, the mass ratio of the alcohol-terminated prepolymer, polybutylene adipate glycol, and 2,2-dimethylol propionic acid is (5-6):4:0.3, preferably 5.7:4:0.3.

[0006] Preferably, the mass ratio of the alcohol-terminated prepolymer 1, 2, and 3 is (20-30):(20-30):(5-10), preferably 25:25:7.

[0007] Preferably, the mass ratio of HDI and modified hydroxyl mixture is 100:(40-42).

[0008] As a preferred technical solution, the weight average molecular weight of the polybutylene adipate glycol is 1000-3000, preferably 2000 (model PBA-2000, from Green Union (Jinan) Chemical Technology Co., Ltd.).

[0009] As a preferred technical solution, the number average molecular weight of the polyethylene glycol is 200-1000, preferably 200-400. Most preferably, the hydroxyl-terminated prepolymer has the structure shown in Formula 1,

[0010] Formula 1: wherein R1 is .

[0011] As a preferred technical solution, the alcohol-terminated prepolymer is alcohol-terminated prepolymer 1, 2, and 3, which has the structure shown in Formula 2, 3, and 4, respectively,

[0012] Formula 2: wherein R2 is , R1 is .

[0013] Formula 3: ,

[0014] wherein R3 is , n=10-15, R2 is , R1 is .

[0015] Formula 4: wherein R4 is , R2 is , R1 is .

[0016] As a preferred technical solution, the preparation method of the alcohol-terminated prepolymer 1 is: PEG-300 is first vacuumed at 120°C to remove water, then MDI is added at 100°C for end-capping, the reaction is continued for 2 hours, then 3MCPG 1450 (Lycra) is added for end-capping, the reaction is continued at 100°C for another 2 hours, and the product obtained is the alcohol-terminated prepolymer 1.

[0017] As a preferred technical solution, the preparation method of the alcohol-terminated prepolymer 2 is: PEG-300 is first vacuumed at 120°C to remove water, then MDI is added at 100°C for termination, and the reaction is continued for 2 hours, then KRASOL_LBH2000 (Kraton) is added for termination, and the reaction is continued at 100°C for 2 hours to generate the product, which is the alcohol-terminated prepolymer 2.

[0018] As a preferred technical solution, the preparation method of the alcohol-terminated prepolymer 3 is: PEG-300 is first vacuumed at 120°C to remove water, then MDI is added at 100°C for termination, and the reaction is continued for 2 hours, then RADIANOL 1990 (Olean) is added for termination, and the reaction is continued at 100°C for 2 hours to generate the product, which is the alcohol-terminated prepolymer 3.

[0019] As a preferred technical solution, the amount of the modified amine added is 22-33% by weight, preferably 28.1% by weight, based on 100% by weight of the total weight of the HDI-terminated modified hydroxyl mixture.

[0020] As a preferred technical solution, the modified amine includes modified amine A of formula 5 and modified amine B of formula 6, and the mass ratio of the modified amine A to the modified amine B is (20-30):(2-4), preferably 25.2:2.9.

[0021] Formula 5: wherein n = 30-45,

[0022] R6 is .

[0023] Formula 6:

[0024] .

[0025] Preferably, the preparation method of the modified amine A is: PEG-300 is first reacted with acryloyl chloride in an ice-salt bath overnight, then hexanediamine is added, TEA is used as a catalyst, and the Michael addition reaction is carried out at 70°C for 4 hours to obtain a -NH2-terminated compound A (see formula 7). MAH-modified rubber (Ricon 130 MA8, Kraton, see formula 8) and the -NH2 of the compound A are reacted at 60°C for 4 hours, and the triethylamine is vacuumed off, and the obtained product is the modified amine A.

[0026] Formula 7:

[0027] .

[0028] Formula 8: wherein n = 30-45.

[0029] Preferably, the preparation method of the modified amine B is that pentaerythritol is first reacted with acryloyl chloride in an ice salt bath overnight, then hexanediamine is added, TEA is used as a catalyst, and a Michael addition reaction is carried out at 70 DEG C for 4 hours, and the obtained product is modified amine B.

[0030] As a preferred technical solution, the curing agent is a combination of HDI trimer, isophorone diisocyanate-terminated hydroxyl compound A, and isophorone diisocyanate-terminated hydroxyl compound B. Preferably, the mass ratio of the HDI trimer, the isophorone diisocyanate-terminated hydroxyl compound A, and the isophorone diisocyanate-terminated hydroxyl compound B is (2-3):(5-10):(0.8-1.2), preferably 2.78:8.89:1.08.

[0031] Preferably, the isophorone diisocyanate-terminated hydroxyl compound A is prepared by reacting hydroxyl-terminated polybutadiene with isophorone diisocyanate, and the hydroxyl-terminated polybutadiene is preferably R45V (Kraytov).

[0032] Preferably, the preparation method of the isophorone diisocyanate-terminated hydroxyl compound B is that glycerol is terminated with HDI, then PEG-300 is added to synthesize an alcohol-terminated product, and then IPDI is used for termination.

[0033] The main agent of the two-component waterborne polyurethane coating adhesive is obtained by using a specific modified amine to chain-extend a specific HDI-terminated modified hydroxyl mixture. On the one hand, by optimizing the modified hydroxyl mixture including alcohol-terminated prepolymer 1, 2, and 3, poly-1,4-butanediol adipate diol, and 2,2-dimethylol propionic acid, the provided main agent has excellent water solubility without the need for additional water-soluble additives, and the bonding strength, resilience, and low-temperature aging resistance of the mixed coating adhesive product are effectively improved, the peeling force is >40 N, and the cohesive failure is leather tearing. Especially, by controlling the mass ratio of each raw material in the modified hydroxyl mixture, the viscosity (25 DEG C) of the main agent and the curing agent after mixing is 7000-8000 mPa·s, and the coating adhesive still maintains a high peeling force under cold and hot impact, meeting the actual application requirements under low-temperature conditions.

[0034] On the other hand, by optimizing the structure design of the modified amine, the modified amine A shown in formula 5 and the modified amine B shown in formula 6 are used, and the mass ratio of the modified amine A and the modified amine B is (20-30):(2-4), which is matched with the HDI-terminated modified hydroxyl mixture to ensure that the viscosity (25 DEG C) of the main agent and the curing agent after mixing is 7000-8000 mPa·s, the use time of the main agent and the curing agent after mixing is ≥4 h, and excellent cold and hot impact resistance is achieved.

[0035] Further, by optimizing the curing agent to be a combination of HDI trimer, isoflurone diisocyanate end-capped hydroxyl compound A, and isoflurone diisocyanate end-capped hydroxyl compound B in a mass ratio of (2-3):(5-10):(0.8-1.2), the use time after mixing with the main agent is improved, and the cohesion of the coating glue is improved.

[0036] Another aspect of the present application provides a preparation method of high-viscosity anti-aging coating glue: according to weight parts, alcohol end-capped prepolymer, poly-1,4-butanediol adipate diol, and 2,2-dimethylol propionic acid are mixed, vacuumized to remove water, and then HDI is added to end-cap to obtain an HDI end-capped modified hydroxyl mixture; the modified amine is diluted with acetone and then mixed with the HDI end-capped modified hydroxyl mixture to react, and then acetone is removed to obtain a main agent; the HDI trimer and the isoflurone diisocyanate end-capped hydroxyl compound are mixed to obtain a curing agent; and when used, the main agent and the curing agent are mixed in a mass ratio of (18-22):1 to be cured to obtain the high-viscosity anti-aging coating glue.

[0037] As a preferred technical solution, the mass ratio of the main agent to the curing agent is 20:1.

[0038] Advantages

[0039] 1. The present application uses a specific modified hydroxyl mixture, a modified amine, and a curing agent, so that the viscosity (25°C) of the prepared coating glue main agent and the curing agent mixed together is 7000-8000 mPa·s without the need for additional addition of thickening aids and water-soluble aids, and the product has excellent initial bonding strength and low-temperature resistance, better meeting the actual application requirements.

[0040] 2. The main agent of the two-component waterborne polyurethane coating glue is designed to use a specific modified amine to chain-extend a specific HDI end-capped modified hydroxyl mixture, which on the one hand optimizes the modified hydroxyl mixture including alcohol end-capped prepolymers 1, 2, and 3, poly-1,4-butanediol adipate diol, and 2,2-dimethylol propionic acid, so that the provided main agent has excellent water solubility without the need for additional addition of water-soluble aids, and effectively improves the bonding strength, resilience, and low-temperature aging resistance of the mixed coating glue product, with a peeling force >40 N and cohesive failure as leather tearing.

[0041] 3. The present application controls the mass ratio of each raw material in the modified hydroxyl mixture to ensure that the viscosity (25°C) of the main agent and the curing agent mixed together is 7000-8000 mPa·s while the coating glue still maintains a high peeling force under cold and hot impact, meeting the actual application requirements under low-temperature conditions.

[0042] 4、The application optimizes the structure design of modified amine, adopts modified amine A shown in formula 5 and modified amine B shown in formula 6, and further adopts the mass ratio of the modified amine A and the modified amine B (20-30):(2-4), and cooperates with HDI end-capped modified hydroxyl mixture to ensure that the viscosity (25 DEG C) of the main agent and the curing agent after mixing is 7000-8000 mPa s, the use time of the main agent and the curing agent after mixing is greater than or equal to 4 hours, and excellent cold and hot impact resistance is achieved.

[0043] 5、The application optimizes the curing agent to be the combination of HDI trimer, isoflurone diisocyanate end-capped hydroxyl compound A and isoflurone diisocyanate end-capped hydroxyl compound B with the mass ratio of (2-3):(5-10):(0.8-1.2), so that the use time after mixing with the main agent is improved, and the cohesion of the coating glue is improved. DETAILED DESCRIPTION

[0044] Embodiment 1

[0045] The embodiment 1 of the application provides a high-viscosity aging-resistant coating glue, which comprises a main agent and a curing agent, the preparation raw material of the main agent comprises HDI end-capped modified hydroxyl mixture and modified amine, and the curing agent is the combination of HDI trimer and isoflurone diisocyanate end-capped hydroxyl compound; the HDI end-capped modified hydroxyl mixture is prepared by end-capping of HDI on a modified hydroxyl mixture, and the preparation raw material of the modified hydroxyl mixture comprises, in terms of weight parts, alcohol end-capped prepolymer 57 parts, poly-1,4-butanediol adipate diol 40 parts and 2,2-dimethylol propionic acid 3 parts; the alcohol end-capped prepolymer is a mixture of alcohol end-capped prepolymers 1, 2 and 3, the alcohol end-capped prepolymers 1, 2 and 3 are prepared by reaction end-capping of hydroxyl end-capped prepolymers respectively generated by chain extension of polyethylene glycol and diphenyl methane diisocyanate on copolyether glycol, hydroxyl end-capped polybutadiene and dimer diol, and the mass ratio of the alcohol end-capped prepolymers 1, 2 and 3 is 25:25:7.

[0046] The mass ratio of HDI and the modified hydroxyl mixture is 100:41.

[0047] The weight average molecular weight of the poly-1,4-butanediol adipate diol is 2000 (model number PBA-2000, from Green Union (Jinan) Chemical Technology Co., Ltd.).

[0048] The polyethylene glycol is polyethylene glycol-300.

[0049] The hydroxyl end-capped prepolymer has the structure shown in formula 1,

[0050] Formula 1: In which R1 is .

[0051] The alcohol-terminated prepolymers 1, 2, and 3 have the structures shown in formulas 2, 3, and 4, respectively.

[0052] Formula 2: Where R2 is R1 is .

[0053] Formula 3: ,

[0054] Among them, R3 is n=10-15, R2 is R1 is .

[0055] Formula 4: R4 is R2 is R1 is .

[0056] The preparation method of the alcohol-terminated prepolymer 1 is as follows: PEG-300 (Jinan Aoxing) is first dehydrated under vacuum at 120℃, then MDI (Wanhua) is added at 100℃ for end-capping, and the reaction is carried out for 2 hours. Then 3MCPG 1450 (Lycra) is added for end-capping, and the reaction is continued at 100℃ for 2 hours. The product is alcohol-terminated prepolymer 1, wherein the molar ratio of PEG-300, MDI and 3MCPG 1450 is 1:2:2, and the hydroxyl value of alcohol-terminated prepolymer 1 is 30.3 mgKOH / g.

[0057] The preparation method of the alcohol-terminated prepolymer 2 is as follows: PEG-300 (Jinan Aoxing) is first dehydrated under vacuum at 120℃, then MDI (Wanhua) is added at 100℃ for end-capping, and the reaction is carried out for 2 hours. Then KRASOL_LBH2000 (Krayweili) is added for end-capping, and the reaction is continued at 100℃ for 2 hours. The product is alcohol-terminated prepolymer 2, wherein the molar ratio of PEG-300, MDI and KRASOL_LBH2000 is 1:2:2, and the hydroxyl value of alcohol-terminated prepolymer 1 is 23.4 mgKOH / g.

[0058] The preparation method of the alcohol-terminated prepolymer 3 is as follows: PEG-300 (Jinan Aoxing) is first dehydrated under vacuum at 120℃, then MDI (Wanhua) is added at 100℃ for end-capping, and the reaction is carried out for 2 hours. Then, RADIANOL 1990 (Olean) is added for end-capping, and the reaction is continued at 100℃ for 2 hours. The product is alcohol-terminated prepolymer 3, wherein the molar ratio of PEG-300, MDI and RADIANOL 1990 is 1:2:2, and the hydroxyl value of alcohol-terminated prepolymer 1 is 59.7 mgKOH / g.

[0059] The amount of the modified amine added is 28.1% by weight, based on the total weight of the HDI-terminated modified hydroxyl mixture as 100% by weight.

[0060] The modified amine includes modified amine A as shown in Formula 5 and modified amine B as shown in Formula 6, wherein the mass ratio of modified amine A to modified amine B is 25.2:2.9.

[0061] Formula 5: Where n = 30 - 45,

[0062] R6 is .

[0063] Formula 6: .

[0064] The modified amine A is prepared as follows: PEG-300 is first reacted with acryloyl chloride overnight in an ice-salt bath, then hexamethylenediamine is added, TEA is used as a catalyst, and the reaction is carried out at 70°C for 4 hours for Michael addition, and the product obtained is compound A with -NH2 end capping (see Formula 7). MAH-modified rubber (Ricon 130 MA8, Krewil, see Formula 8) and the -NH2 of compound A are reacted at 60°C for 4 hours, and triethylamine is removed under vacuum, and the product obtained is modified amine A, wherein the molar ratio of PEG-300, acryloyl chloride, hexamethylenediamine, and MAH-modified rubber is 1:2:2:0.2, and the amine value of modified amine A is 12.3 mgKOH / g.

[0065] Formula 7:

[0066] .

[0067] Formula 8: , where n = 30-45.

[0068] The modified amine B is prepared by reacting pentaerythritol with acryloyl chloride overnight in an ice-salt bath, followed by the addition of hexamethylenediamine, with TEA as a catalyst, and reacting at 70°C for 4 hours to carry out a Michael addition reaction. The product obtained is modified amine B, wherein the molar ratio of pentaerythritol, acryloyl chloride, and hexamethylenediamine is 1:4:4, and the amine value of modified amine B is 137.3 mgKOH / g.

[0069] The curing agent is a combination of HDI trimer, isoflurane diisocyanate-terminated hydroxyl compound A, and isoflurane diisocyanate-terminated hydroxyl compound B. The mass ratio of the HDI trimer, isoflurane diisocyanate-terminated hydroxyl compound A, and isoflurane diisocyanate-terminated hydroxyl compound B is 2.78:8.89:1.08.

[0070] The isoflurone diisocyanate-terminated hydroxyl compound A is prepared by reacting hydroxyl-terminated polybutadiene and isoflurone diisocyanate, the hydroxyl-terminated polybutadiene is R45V (Kraton), and the ratio of the feeding amount of the hydroxyl-terminated polybutadiene and the isoflurone diisocyanate is 100:13.3.

[0071] The preparation method of the isoflurone diisocyanate-terminated hydroxyl compound B is: after the glycerol is terminated with HDI, the alcohol-terminated product is synthesized by adding PEG-300, and then terminated with IPDI, wherein the ratio of the feeding amount of the glycerol, HDI and PEG-300 is 1.00:2.74:4.89, and the hydroxyl value of the isoflurone diisocyanate-terminated hydroxyl compound B is 38.9 mgKOH / g.

[0072] The HDI trimer is Wanhua HT-100.

[0073] The high-viscosity anti-aging coating adhesive provided by the embodiment 1 of the present application is prepared by mixing alcohol-terminated prepolymer, poly-1,4-butanediol adipate diol and 2,2-dimethylol propionic acid in a weight ratio of 32:65:3, vacuumizing and removing water, adding HDI to terminate, mixing the modified amine diluted with acetone with the HDI-terminated modified hydroxyl mixture to react, and then removing the acetone to obtain the main agent; the HDI trimer and the isoflurone diisocyanate-terminated hydroxyl compound are mixed to obtain the curing agent; and the main agent and the curing agent are mixed in a mass ratio of (18-22):1 to obtain the high-viscosity anti-aging coating adhesive after curing.

[0074] The mass ratio of the main agent and the curing agent is 20:1.

[0075] Comparative Example 1

[0076] The comparative example 1 of the present application provides a high-viscosity anti-aging coating adhesive and a preparation method thereof, and the specific embodiment is the same as that of the embodiment 1, except that the preparation raw materials of the modified hydroxyl mixture include alcohol-terminated prepolymer 32 parts, poly-1,4-butanediol adipate diol 65 parts and 2,2-dimethylol propionic acid 3 parts, the alcohol-terminated prepolymer is a mixture of alcohol-terminated prepolymers 2 and 3, the mass ratio of the alcohol-terminated prepolymers 2 and 3 is 25:7, and the mass ratio of HDI and the modified hydroxyl mixture is 100:45.

[0077] Comparative Example 2

[0078] The comparative example 2 of the present application provides a high viscosity anti-aging coating adhesive and a preparation method thereof, and the specific embodiment is the same as that of the example 1, except that the raw materials for preparing the modified hydroxyl mixture include 32 parts of alcohol-terminated prepolymer, 65 parts of polyhexanedioic acid-1, 4-butanediol ester diol, and 3 parts of 2, 2-dimethylol propionic acid by weight, the alcohol-terminated prepolymer is a mixture of alcohol-terminated prepolymer 1 and 3, the mass ratio of the alcohol-terminated prepolymer 1 and 3 is 25:7, and the mass ratio of HDI and the modified hydroxyl mixture is 100:46.

[0079] Comparative example 3

[0080] The comparative example 3 of the present application provides a high viscosity anti-aging coating adhesive and a preparation method thereof, and the specific embodiment is the same as that of the example 1, except that the addition amount of the modified amine is 10.6% by weight of the HDI-terminated modified hydroxyl mixture, and the mass ratio of the modified amine A and the modified amine B is 6.7:3.9.

[0081] Comparative example 4

[0082] The comparative example 4 of the present application provides a high viscosity anti-aging coating adhesive and a preparation method thereof, and the specific embodiment is the same as that of the example 1, except that the mass ratio of the isophorone diisocyanate-terminated curing agent 1, the isophorone diisocyanate-terminated curing agent 2, and the hexamethylene diisocyanate-terminated curing agent 3 is 3.78:4.44:1.08.

[0083] Performance test method

[0084] 1. The viscosity (25℃, Brookfield viscometer, No. 27 rotor) of the main agent and the curing agent mixed after the preparation of the test example and the comparative example, and the results are shown in Table 1.

[0085] 2. The use time of the main agent and the curing agent mixed after the preparation of the test example and the comparative example, and the results are shown in Table 1.

[0086] 3. After mixing the main agent and the curing agent prepared in the example and the comparative example, put them into a spray pot, and spray them onto leather and seat back plate (PP plate or ABS plate) under a pressure of 0.1 MPa (the glue thickness is 10μm dry thickness), then place the two parts in an oven at 45℃ for 30 minutes. Then perform hot pressing on the machine, the pressure is 0.5 MPa, the activation temperature is 70℃, then cool to 25±5℃ and stand still, test the 180° peeling force (speed 50mm / min, unit N / mm) after standing still for 10 minutes and 72 hours, and the results are recorded in Table 2.

[0087] 4. After mixing the main agent and curing agent prepared in the examples and comparative examples, place them in a spray bottle and spray them onto the leather and seat back panel (PP board or ABS board) under a pressure of 0.1 MPa (the adhesive thickness is 10 μm dry thickness). Then, place the two parts in an oven and dry them at 45°C for 30 minutes. After that, perform hot pressing on the machine at a pressure of 0.5 MPa and an activation temperature of 70°C. Then cool to 25±5°C and let stand for 72 hours to complete the curing. The resulting product is then subjected to high-temperature aging (105°C, 500 hours, 800 hours, 1000 hours) and thermal shock aging (placed at -40°C for 4 hours, then heated to 80°C for 4 hours, then placed at 80°C for 4 hours, then cooled to -40°C for 4 hours, the above is 1 round, 10 rounds, 15 rounds, 20 rounds). The peel strength after aging is tested, and the results are shown in Table 2.

[0088] Table 1

[0089]

[0090] Table 2

[0091]

Claims

1. A high-viscosity, aging-resistant coating adhesive, characterized in that, The mixture includes a main agent and a curing agent. The main agent is prepared from raw materials including at least an HDI-terminated modified hydroxyl mixture and a modified amine. The curing agent is a combination of an HDI trimer and an isoflurane diisocyanate-terminated hydroxyl compound. The HDI-terminated modified hydroxyl mixture is prepared by end-capping a modified hydroxyl mixture with HDI. By weight, the raw materials for preparing the modified hydroxyl mixture include at least 45-70 parts of an alcohol-terminated prepolymer, 30-50 parts of poly(1,4-butanediol adipate), and 2,2-dihydroxy... 2-5 parts of methylpropionic acid; the alcohol-terminated prepolymer is a mixture of alcohol-terminated prepolymers 1, 2, and 3, which are prepared by reacting hydroxyl-terminated prepolymers generated by chain extension of polyethylene glycol and diphenylmethane diisocyanate with copolyether glycol, hydroxyl-terminated polybutadiene, and dimer glycol, respectively, in a mass ratio of (20-30):(20-30):(5-10); the modified amine includes modified amine A as shown in Formula 5 and modified amine B as shown in Formula 6. Formula 5: Where n = 30 - 45, R6 is ; Formula 6: The mass ratio of modified amine A to modified amine B is (20-30):(2-4); based on the total weight of the HDI-terminated modified hydroxyl mixture as 100% by weight, the amount of modified amine added is 22-33% by weight. The curing agent is a combination of HDI trimer, isoflurane diisocyanate-terminated hydroxyl compound A, and isoflurane diisocyanate-terminated hydroxyl compound B. Isoflurane diisocyanate-terminated hydroxyl compound A is prepared by reacting hydroxyl-terminated polybutadiene with isoflurane diisocyanate. The preparation method of isoflurane diisocyanate-terminated hydroxyl compound B is as follows: glycerol is terminated with HDI, then PEG-300 is added to synthesize an alcohol-terminated product, which is then terminated with IPDI. The mass ratio of the HDI trimer, isoflurone diisocyanate-terminated hydroxyl compound A, and isoflurone diisocyanate-terminated hydroxyl compound B is (2-3):(5-10):(0.8-1.2).

2. The high-viscosity, aging-resistant coating adhesive according to claim 1, characterized in that, The mass ratio of the alcohol-terminated prepolymers 1, 2, and 3 is 25:25:

7.

3. The high-viscosity, aging-resistant coating adhesive according to claim 2, characterized in that, The weight-average molecular weight of the poly(1,4-butanediol adipate) diol is 1000-3000.

4. The high-viscosity, aging-resistant coating adhesive according to claim 1, characterized in that, The mass ratio of HDI to the modified hydroxyl mixture is 100:(40-42).

5. The high-viscosity, aging-resistant coating adhesive according to claim 1, characterized in that, The mass ratio of modified amine A to modified amine B is 25.2:2.

9.

6. A method for preparing a high-viscosity, aging-resistant coating adhesive according to any one of claims 1-5, characterized in that, The process includes at least the following steps: According to weight parts, the alcohol-terminated prepolymer, poly(1,4-butanediol adipate), and 2,2-dimethylolpropionic acid are mixed and then vacuum-dried to remove water. HDI is added for end-capping to obtain an HDI-terminated modified hydroxyl mixture. The modified amine is diluted with acetone and then mixed with the HDI-terminated modified hydroxyl mixture for reaction. The acetone is then removed to obtain the main agent. The HDI trimer and isoflurane diisocyanate-terminated hydroxyl compound are mixed to obtain the curing agent. When using, the main agent and curing agent are mixed at a mass ratio of (18-22):1 and cured to obtain a high-viscosity, aging-resistant coating adhesive.

7. The preparation method of the high viscosity aging-resistant coating adhesive according to claim 6, characterized in that, The mass ratio of the main agent to the curing agent is 20:1.

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