High-viscosity anti-aging coating rubber and preparation method thereof

Abstract

The invention relates to the technical field of automobile coating rubber, in particular to high-viscosity anti-aging coating rubber and a preparation method thereof.The high-viscosity anti-aging coating rubber comprises a main agent and a curing agent, preparation raw materials of the main agent at least comprise an HDI end-capped modified hydroxyl mixture and modified amine, and the curing agent is a combination of an HDI tripolymer and an isophorone diisocyanate end-capped hydroxyl compound; the HDI-terminated modified hydroxyl mixture is prepared by terminating a modified hydroxyl mixture with HDI, and the modified hydroxyl mixture at least comprises the following preparation raw materials in parts by weight: 45-70 parts of an alcohol-terminated prepolymer, 30-50 parts of poly (1, 4-butylene adipate) glycol and 2-5 parts of 2, 2-dimethylolpropionic acid. By adopting the specific modified hydroxyl mixture, the modified amine and the curing agent, the main agent and the curing agent have longer service time after being mixed, meanwhile, the 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] This invention relates to the field of automotive coating adhesive technology, specifically to a high-viscosity, aging-resistant coating adhesive and its preparation method. Background Technology

[0002] In the automotive interior sector, solvent-based polyurethane adhesives have long held a dominant market position due to their strong initial tack and fast drying. However, as the automotive industry moves towards low-VOC standards, environmental requirements for overcoating adhesives have emerged. For example, Chinese patent (publication number CN111072899A) discloses a waterborne polyurethane automotive interior overcoating adhesive and its preparation method, providing a waterborne polyurethane overcoating adhesive with good initial tack. This adhesive meets both the low-VOC requirement and the adhesion requirements between the automotive interior substrate and the overcoating material. However, its aging resistance in practical applications needs further improvement, limiting its widespread application. Chinese patent (publication number CN117165242A) discloses a high-temperature resistant overcoating adhesive, its preparation method, and its application. This mainly improves the heat resistance of the overcoating adhesive by introducing polydopamine-modified nano-silica and organosilicon-modified hydroxyl acrylate. However, automotive overcoating adhesives also face low-temperature environments in practical applications, and the lower adhesion performance of the overcoating adhesive under low-temperature conditions also affects its practical application. Summary of the Invention

[0003] To address the aforementioned issues, this invention employs a specific modified hydroxyl mixture, modified amine, and curing agent. Without requiring the addition of thickeners or water-soluble additives, the viscosity (at 25°C) of the prepared coating adhesive base and curing agent after mixing is 7000-8000 mPa·s. Simultaneously, the product exhibits excellent initial bond strength and low-temperature resistance, better meeting the needs of practical applications.

[0004] This invention provides a high-viscosity, aging-resistant coating adhesive, comprising 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 the 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 2-5 parts of 2,2-dimethylolpropionic acid. The alcohol-terminated prepolymer is a mixture of alcohol-terminated prepolymers 1, 2, and 3. Alcohol-terminated prepolymers 1, 2, and 3 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 diol, respectively.

[0005] Preferably, the mass ratio of the alcohol-terminated prepolymer, poly(1,4-butanediol adipate) and 2,2-dimethylolpropionic acid is (5-6):4:0.3, and more preferably 5.7:4:0.3.

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

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

[0008] As a preferred technical solution, the weight-average molecular weight of the poly(1,4-butanediol adipate) is 1000-3000, preferably 2000 (model PBA-2000, sourced from Greenlink (Jining) 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. Formula 1: , where R1 is .

[0010] As a preferred technical solution, the alcohol-terminated prepolymers 1, 2, and 3 have the structures shown in formulas 2, 3, and 4, respectively. Formula 2: Where R2 is R1 is .

[0011] Formula 3: , Among them, R3 is n=10-15, R2 is R1 is .

[0012] Formula 4: R4 is R2 is R1 is .

[0013] As a preferred technical solution, the preparation method of the alcohol-terminated prepolymer 1 is as follows: PEG-300 is first dehydrated under vacuum at 120°C, then MDI is added at 100°C for termination, and the reaction is carried out for 2 hours. Then 3MCPG 1450 (Lycra) is added for termination, and the reaction is continued at 100°C for 2 hours. The product generated is the alcohol-terminated prepolymer 1.

[0014] As a preferred technical solution, the preparation method of the alcohol-terminated prepolymer 2 is as follows: PEG-300 is first dehydrated under vacuum at 120℃, then MDI is added at 100℃ for end-capping, and the reaction is carried out for 2 hours. Then KRASOL_LBH2000 is added for end-capping, and the reaction is continued at 100℃ for 2 hours. The product generated is the alcohol-terminated prepolymer 2.

[0015] As a preferred technical solution, the preparation method of the alcohol-terminated prepolymer 3 is as follows: PEG-300 is first dehydrated under vacuum at 120°C, then MDI is added at 100°C 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°C for another 2 hours. The product generated is the alcohol-terminated prepolymer 3.

[0016] As a preferred technical solution, 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, preferably 28.1% by weight.

[0017] As a preferred technical solution, 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 (20-30):(2-4), preferably 25.2:2.9. Formula 5: Where n = 30 - 45, R6 is .

[0018] Formula 6: .

[0019] Preferably, 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 a -NH2-terminated compound A (see Formula 7). MAH-modified rubber (Ricon 130 MA8, Claywell, 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.

[0020] Formula 7: .

[0021] Formula 8: , where n = 30-45.

[0022] Preferably, the modified amine B is prepared by reacting pentaerythritol with acryloyl chloride overnight in an ice-salt bath, then adding hexamethylenediamine, using TEA as a catalyst, and reacting at 70°C for 4 hours to carry out a Michael addition reaction, the product of which is modified amine B.

[0023] As a preferred technical solution, the curing agent is a combination of HDI trimer, isoflurane diisocyanate-terminated hydroxyl compound A, and isoflurane diisocyanate-terminated hydroxyl compound B. Preferably, the mass ratio of the HDI trimer, isoflurane diisocyanate-terminated hydroxyl compound A, and isoflurane diisocyanate-terminated hydroxyl compound B is (2-3):(5-10):(0.8-1.2), more preferably 2.78:8.89:1.08.

[0024] Preferably, the isoflurone diisocyanate-terminated hydroxyl compound A is prepared by reacting hydroxyl-terminated polybutadiene and isoflurone diisocyanate, wherein the hydroxyl-terminated polybutadiene is preferably R45V (Crevelli).

[0025] Preferably, the method for preparing the isoflurane diisocyanate-terminated hydroxy compound B is as follows: glycerol is capped with HDI, then PEG-300 is added to synthesize the alcohol-terminated product, and then IPDI is used for capping.

[0026] This invention designs a two-component waterborne polyurethane overcoating adhesive whose main component is obtained by chain extension of a specific HDI-terminated modified hydroxyl mixture using a specific modified amine. On one hand, by optimizing the modified hydroxyl mixture, including alcohol-terminated prepolymers 1, 2, and 3, poly(1,4-butanediol adipate), and 2,2-dimethylolpropionic acid, the provided main component exhibits excellent water solubility without the need for additional water-soluble additives. Simultaneously, it effectively improves the adhesive strength, resilience, and low-temperature aging resistance of the mixed overcoating product, achieving a peel force >40N and cohesive failure equivalent to leather tearing. In particular, by controlling the mass ratio of each raw material in the modified hydroxyl mixture, the viscosity (25℃) of the mixed main component and curing agent is maintained at 7000-8000 mPa·s, while the overcoating adhesive maintains high peel force under thermal shock, meeting the practical application requirements under low-temperature conditions.

[0027] On the other hand, by optimizing the structure design of the modified amine, using modified amine A as shown in Formula 5 and modified amine B as shown in Formula 6, and further stating that the mass ratio of modified amine A to modified amine B is (20-30):(2-4), and combined with HDI-terminated modified hydroxyl mixture, the viscosity (25℃) of the main agent and curing agent after mixing is guaranteed to be 7000-8000 mPa·s, while ensuring that the service life of the main agent and curing agent after mixing is ≥4h and has excellent resistance to thermal shock.

[0028] Furthermore, by optimizing the curing agent to a combination of HDI trimer, isoflurane diisocyanate-terminated hydroxyl compound A, and isoflurane diisocyanate-terminated hydroxyl compound B in a mass ratio of (2-3):(5-10):(0.8-1.2), the service life after mixing with the main agent is improved, and the cohesive strength of the coating adhesive is enhanced.

[0029] Another aspect of the present invention provides a method for preparing a high-viscosity, aging-resistant coating adhesive: According to the weight proportions, an 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. A modified amine is diluted with acetone and 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 the high-viscosity, aging-resistant coating adhesive.

[0030] As a preferred technical solution, the mass ratio of the main agent to the curing agent is 20:1.

[0031] Beneficial effects 1. This invention, by using a specific modified hydroxyl mixture, modified amine and curing agent, achieves a viscosity (25℃) of 7000-8000 mPa·s after mixing the main agent and curing agent of the prepared coating adhesive without the need for additional thickening agents or water-soluble additives. At the same time, the product has excellent initial bond strength and low temperature resistance, better meeting the needs of practical applications.

[0032] 2. The main component of the two-component waterborne polyurethane overcoating adhesive of this invention is obtained by chain extension of a specific HDI-terminated modified hydroxyl mixture using a specific modified amine. On the one hand, by optimizing the modified hydroxyl mixture, including alcohol-terminated prepolymers 1, 2, and 3, poly(1,4-butanediol adipate) and 2,2-dimethylolpropionic acid, the provided main component has excellent water solubility without the need for additional water-soluble additives. At the same time, it effectively improves the adhesive strength, resilience, and low-temperature aging resistance of the mixed overcoating adhesive product, with a peel force >40N and cohesive failure equivalent to leather tearing.

[0033] 3. By controlling the mass ratio of each raw material in the modified hydroxyl mixture, this invention ensures that the viscosity (25℃) of the main agent and curing agent after mixing is 7000-8000 mPa·s, while the coating adhesive still maintains a high peel force under thermal shock, thus meeting the practical application requirements under low temperature conditions.

[0034] 4. This invention optimizes the structure design of the modified amine, using modified amine A as shown in Formula 5 and modified amine B as shown in Formula 6, and further stating that the mass ratio of modified amine A to modified amine B is (20-30):(2-4), and in combination with HDI-terminated modified hydroxyl mixture, ensures that the viscosity (25℃) of the main agent and curing agent after mixing is 7000-8000 mPa·s, while ensuring that the working time of the main agent and curing agent after mixing is ≥4h and has excellent resistance to thermal shock.

[0035] 5. By optimizing the curing agent to a combination of HDI trimer, isoflurane diisocyanate-terminated hydroxyl compound A, and isoflurane diisocyanate-terminated hydroxyl compound B in a mass ratio of (2-3):(5-10):(0.8-1.2), the working time after mixing with the main agent is improved, and the cohesiveness of the coating adhesive is enhanced. Detailed Implementation

[0036] Example 1 Example 1 of the present invention provides a high-viscosity, aging-resistant coating adhesive, comprising a main agent and a curing agent. The main agent is prepared from HDI-terminated modified hydroxyl mixture and modified amine. The curing agent is a combination of HDI trimer and isoflurane diisocyanate-terminated hydroxyl compound. The HDI-terminated modified hydroxyl mixture is prepared by end-capping the modified hydroxyl mixture with HDI. By weight, the raw materials for preparing the modified hydroxyl mixture include 57 parts of alcohol-terminated prepolymer, 40 parts of poly(1,4-butanediol adipate), and 3 parts of 2,2-dimethylolpropionic acid. The alcohol-terminated prepolymer is a mixture of alcohol-terminated prepolymers 1, 2, and 3. Alcohol-terminated prepolymers 1, 2, and 3 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 diol, respectively. The mass ratio of alcohol-terminated prepolymers 1, 2, and 3 is 25:25:7.

[0037] The mass ratio of HDI to the modified hydroxyl mixture is 100:41.

[0038] The weight-average molecular weight of the poly(1,4-butanediol adipate) diol is 2000 (model PBA-2000, sourced from Greenlink (Jining) Chemical Technology Co., Ltd.).

[0039] The polyethylene glycol is polyethylene glycol-300.

[0040] The hydroxyl-terminated prepolymer has the structure shown in Formula 1. Formula 1: , where R1 is .

[0041] The alcohol-terminated prepolymers 1, 2, and 3 have the structures shown in formulas 2, 3, and 4, respectively. Formula 2: Where R2 is R1 is .

[0042] Formula 3: , Among them, R3 is n=10-15, R2 is R1 is .

[0043] Formula 4: R4 is R2 is R1 is .

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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. Formula 5: Where n = 30 - 45, R6 is .

[0049] Formula 6: .

[0050] 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.

[0051] Formula 7: .

[0052] Formula 8: , where n = 30-45.

[0053] 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.

[0054] 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.

[0055] The isoflurane diisocyanate-terminated hydroxy compound A is prepared by reacting hydroxy-terminated polybutadiene and isoflurane diisocyanate, wherein the hydroxy-terminated polybutadiene is R45V (Crevelli), and the ratio of hydroxy-terminated polybutadiene to isoflurane diisocyanate is 100:13.3.

[0056] The method for preparing the isoflurane diisocyanate-terminated hydroxy compound B is as follows: glycerol is capped with HDI, then PEG-300 is added to synthesize the alcohol-terminated product, and then IPDI is used for capping. The ratio of glycerol, HDI and PEG-300 is 1.00:2.74:4.89, and the hydroxyl value of isoflurane diisocyanate-terminated hydroxy compound B is 38.9 mgKOH / g.

[0057] The HDI trimer is Wanhua HT-100.

[0058] Example 1 of the present invention provides a method for preparing a high-viscosity, aging-resistant coating adhesive: According to the weight proportions, an 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. A modified amine is diluted with acetone and mixed with the HDI-terminated modified hydroxyl mixture for reaction. Then, the acetone is 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 the high-viscosity, aging-resistant coating adhesive.

[0059] The mass ratio of the main agent to the curing agent is 20:1.

[0060] Comparative Example 1 Comparative Example 1 of the present invention provides a high-viscosity, aging-resistant coating adhesive and its preparation method. The specific implementation method is the same as that of Example 1, except that, by weight, the raw materials for preparing the modified hydroxyl mixture include 32 parts of alcohol-terminated prepolymer, 65 parts of poly(1,4-butanediol adipate), and 3 parts of 2,2-dimethylolpropionic acid. The alcohol-terminated prepolymer is a mixture of alcohol-terminated prepolymers 2 and 3, and the mass ratio of alcohol-terminated prepolymers 2 and 3 is 25:7. The mass ratio of HDI to the modified hydroxyl mixture is 100:45.

[0061] Comparative Example 2 Comparative Example 2 of the present invention provides a high-viscosity, aging-resistant coating adhesive and its preparation method. The specific implementation method is the same as that of Example 1, except that, by weight, the raw materials for preparing the modified hydroxyl mixture include 32 parts of alcohol-terminated prepolymer, 65 parts of poly(1,4-butanediol adipate), and 3 parts of 2,2-dimethylolpropionic acid. The alcohol-terminated prepolymer is a mixture of alcohol-terminated prepolymers 1 and 3, and the mass ratio of alcohol-terminated prepolymers 1 and 3 is 25:7. The mass ratio of HDI to the modified hydroxyl mixture is 100:46.

[0062] Comparative Example 3 Comparative Example 3 of the present invention provides a high viscosity aging-resistant coating adhesive and its preparation method. The specific implementation method is the same as that of Example 1, except that, based on the weight of the HDI-terminated modified hydroxyl mixture, the amount of modified amine added is 10.6%, and the mass ratio of modified amine A to modified amine B is 6.7:3.9.

[0063] Comparative Example 4 Comparative Example 4 of the present invention provides a high viscosity aging-resistant coating adhesive and its preparation method. The specific implementation method is the same as that of Example 1, except that the mass ratio of isoflurane diisocyanate end-capping curing agent 1, isoflurane diisocyanate end-capping curing agent 2 and hexamethylene diisocyanate end-capping curing agent 3 is 3.78:4.44:1.08.

[0064] Performance testing methods 1. The viscosity of the main agent and curing agent prepared in the test examples and comparative examples after mixing (25°C, Brookfield viscometer, rotor No. 27) is shown in Table 1.

[0065] 2. The usage time of the main agent and curing agent prepared in the test examples and comparative examples after mixing is shown in Table 1.

[0066] 3. 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. Afterward, 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. Test the 180° peel force (speed 50 mm / min, unit N / mm) after standing for 10 minutes and 72 hours. The results are recorded in Table 2. 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.

[0067] Table 1

[0068] Table 2

Claims

1. A high viscosity, age resistant, coverstock, characterized in that, The main agent and the curing agent, the preparation raw materials of the main agent at least include HDI end-capped modified hydroxyl mixture and modified amine, the curing agent is the combination of HDI trimer and isofuroleone diisocyanate end-capped hydroxyl compound; the HDI end-capped modified hydroxyl mixture is prepared by end-capping HDI to modified hydroxyl mixture, and the preparation raw materials of the modified hydroxyl mixture at least include alcohol end-capped prepolymer 45-70 parts, polyhexanedioate-1, 4-butanediol glycol 30-50 parts and 2, 2-dimethylol propionic acid 2-5 parts according to weight parts; the alcohol end-capped prepolymer is the mixture of alcohol end-capped prepolymers 1, 2 and 3; the alcohol end-capped prepolymers 1, 2 and 3 are prepared by reacting hydroxyl end-capped prepolymers respectively and co-polyether glycol, hydroxyl end-capped polybutadiene and dimer glycol, which are generated by polyethylene glycol and diphenyl methane diisocyanate chain extension; the mass ratio of the alcohol end-capped prepolymers 1, 2 and 3 is (20-30) : (20-30) : (5-10); the modified amine includes modified amine A shown in formula 5 and modified amine B shown in formula 6, Formula 5: where n = 30-45, R6 is ; Formula 6: , the mass ratio of the modified amine A and the modified amine B is (20-30):(2-4).

2. The high viscosity, age resistant encapsulant of claim 1, wherein, The mass ratio of the alcohol end-capped prepolymers 1, 2 and 3 is 25:25:

7.

3. The high viscosity, age resistant encapsulant of claim 2, wherein, The weight average molecular weight of the polyhexanedioate-1, 4-butanediol glycol is 1000-3000.

4. The high viscosity, age resistant encapsulant of claim 3, wherein, The added amount of the modified amine is 22-33% by weight, based on the total weight of the HDI end-capped modified hydroxyl mixture being 100% by weight.

5. The high viscosity, age resistant encapsulant of claim 4, wherein, The mass ratio of HDI and modified hydroxyl mixture is 100: (40-42).

6. The high viscosity, age resistant encapsulant of claim 5, wherein, The mass ratio of the modified amine A and the modified amine B is 25.2:2.

9.

7. The high viscosity, age resistant encapsulant of claim 6, wherein, The curing agent is the combination of HDI trimer, isofuroleone diisocyanate end-capped hydroxyl compound A and isofuroleone diisocyanate end-capped hydroxyl compound B; the isofuroleone diisocyanate end-capped hydroxyl compound A is prepared by the reaction of hydroxyl end-capped polybutadiene and isofuroleone diisocyanate; the preparation method of the isofuroleone diisocyanate end-capped hydroxyl compound B is: first, glycerol is end-capped with HDI, then PEG-300 is added to synthesize alcohol end-capped product, and then IPDI is used for end-capping.

8. The high viscosity, age resistant encapsulant of claim 7, wherein, The mass ratio of the HDI trimer, the isofuroleone diisocyanate end-capped hydroxyl compound A and the isofuroleone diisocyanate end-capped hydroxyl compound B is (2-3) : (5-10) : (0.8-1.2).

9. A process for the preparation of a high viscosity, age resistant, coated adhesive according to any one of claims 1 to 8, characterized in that, The preparation method at least includes the following steps: alcohol end-capped prepolymers, polyhexanedioate-1, 4-butanediol glycol and 2, 2-dimethylol propionic acid are mixed and vacuumized to remove water, then HDI is added for end-capping to obtain HDI end-capped modified hydroxyl mixture; the modified amine is diluted with acetone and mixed with the HDI end-capped modified hydroxyl mixture for reaction, then acetone is removed to obtain the main agent; HDI trimer and isofuroleone diisocyanate end-capped hydroxyl compound are mixed to obtain the curing agent; when used, the main agent and the curing agent are mixed in a mass ratio of (18-22) : 1 for curing to obtain high-viscosity aging-resistant coating glue.

10. The method for preparing the high-viscosity, aging-resistant coating adhesive according to claim 9, characterized in that, The mass ratio of the main agent and the curing agent is 20:1.

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