High-temperature-resistant and yellowing-resistant monomer as well as preparation method and application thereof
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- WUXI SHUNXUAN PHOTOELECTRIC TECH CO LTD
- Filing Date
- 2025-12-26
- Publication Date
- 2026-04-24
AI Technical Summary
Existing high-temperature resistant acrylic adhesives have insufficient heat resistance or are prone to yellowing at high temperatures, which limits their application in outdoor and transparent environments.
The high-temperature resistant monomer HT-1 series is generated by reacting triglycidyl isocyanate with acrylic monomers, and then reacted with monoisocyanate monomers to generate HT-2 series monomers. A dense cross-linking network is formed with carboxyl groups through a closed yellowing-resistant curing agent, thereby increasing the cross-linking density at high temperatures.
It achieves ultra-high temperature resistance and yellowing resistance, making it suitable for pressure-sensitive adhesive applications in outdoor and transparent environments.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of high-temperature resistant acrylic pressure-sensitive adhesive technology, specifically relating to a high-temperature resistant and yellowing-resistant monomer, its preparation method, and its application. Background Technology
[0002] Acrylic pressure-sensitive adhesives are the most widely used and consumed type of pressure-sensitive adhesive. Their main component is acrylate polymer, primarily obtained by free radical copolymerization of various acrylate monomers with other vinyl monomers. Free radical polymerization is simple to operate, the reaction is easy to control, and the molecular structure of the copolymer can be designed by adjusting the types and ratios of monomers to prepare products with different properties. Acrylic pressure-sensitive adhesives also have relatively low prices, high transparency, and a wide range of adhesive properties. Due to these advantages, acrylic pressure-sensitive adhesives have seen rapid development and occupy a large market share.
[0003] Currently, most high-temperature resistant acrylic adhesives are prepared by adding high-temperature resistant monomers, such as vinylpyrrolidone, heterocyclic monomers, nitrogen-containing monomers, and benzene-containing monomers. However, these methods often suffer from insufficient temperature resistance (150℃ or a maximum of 220℃) or a tendency to yellow, limiting their application. Similarly, modified high-temperature resistant monomers, such as those modified with TGIC and AA, have been used to synthesize high-temperature resistant adhesives, but these methods also fail to achieve sufficient temperature resistance (Jun HuaChen. Improvement in mechanical properties and thermal stability of solvent-based pressure-sensitive adhesives based on triazine heterocyclic monomer. Sci. 2016). Therefore, this invention synthesizes higher-performance high-temperature resistant monomers to prepare high-temperature resistant adhesives that are also resistant to yellowing, meeting the needs of outdoor and transparent high-temperature applications. Summary of the Invention
[0004] The first technical problem to be solved by this invention is to provide a high-temperature resistant and yellowing-resistant monomer that can improve the rigidity of pressure-sensitive adhesives and enhance the crosslinking degree of the closed yellowing-resistant curing agent at high temperatures. The second technical problem to be solved by this invention is to provide a method for preparing a high-temperature resistant and yellowing-resistant monomer that can improve temperature resistance, achieve higher crosslinking density, and achieve ultra-high temperature resistance and yellowing resistance. The third technical problem to be solved by this invention is to provide the application of this monomer in the preparation of pressure-sensitive adhesives.
[0005] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows:
[0006] A method for preparing a high-temperature resistant and yellowing-resistant monomer includes the following steps:
[0007] 1) Triglycidyl isocyanurate, catalyst and polymerization inhibitor are added to an organic solvent and heated to react. Then acrylic monomers and organic solvent are added, the solvent is removed under reduced pressure, and the mixture is purified by alkaline alumina column to obtain the high-temperature resistant monomer HT-1 series.
[0008] 2) Dissolve the high-temperature resistant monomer HT-1 series obtained in step 1) in an organic solvent and react with monoisocyanate monomers. Then add polymerization inhibitors and catalysts, and extract the solvent under reduced pressure, wash and dry to obtain the high-temperature resistant monomer HT-2 series.
[0009] Further, in step 1), the molar ratio of triglycidyl isocyanurate to acrylic monomer is 1:1~3; the reaction temperature is 70-80℃.
[0010] Further, in step 1), the acrylic monomer is selected from one of acrylic acid, methacrylic acid, itaconic acid, and maleic acid.
[0011] Further, in step 2), the monoisocyanate monomer is selected from one of n-butyl isocyanate, octadecyl isocyanate, and cyclohexyl isocyanate.
[0012] Further, in steps 1) and 2), the polymerization inhibitor is selected from one or more of p-hydroxyanisole, p-benzoquinone, 2,5-dihydroxytoluene, 4-methoxyphenol, and tert-butylhydroquinone.
[0013] Furthermore, in steps 1) and 2), the catalyst is selected from one or more of triethylamine, benzyltriethylammonium chloride, triphenylphosphine, triphenylantimony, and zinc acetylacetonate.
[0014] Further, in steps 1) and 2), the organic solvent is selected from one or more of ethyl acetate, methyl acetate, toluene, xylene, dimethyl carbonate, isopropanol, butyl acetate, dimethyl sulfoxide, and acetone.
[0015] Furthermore, the high-temperature resistant and yellowing-resistant monomer prepared by the aforementioned method is a high-temperature resistant and yellowing-resistant monomer.
[0016] Furthermore, the application of the high-temperature resistant and yellowing-resistant monomer in the preparation of pressure-sensitive adhesives.
[0017] Furthermore, the application of the high-temperature resistant and yellowing-resistant monomer in the preparation of pressure-sensitive adhesives includes the following steps:
[0018] 1) Weigh the soft monomer, hard monomer, functional monomer, and high-temperature resistant and yellowing-resistant monomer and add them to the solvent for heating and reaction. Purge with nitrogen to maintain the temperature. After the temperature maintenance is completed, use a peristaltic pump to inject a thermal initiator solution to prepare a prepolymer containing cross-linking groups. Then add the soft monomer, hard monomer, functional monomer, amide monomer, high-temperature resistant and yellowing-resistant monomer, and initiator. Add the heating initiator and then add an aliphatic blocked isocyanate curing agent to obtain an acrylic-based high-temperature resistant acrylate adhesive.
[0019] 2) Add the adhesive obtained in step 1) to an aliphatic epoxy curing agent, apply it directly to a high-temperature resistant CPI substrate using a small coating machine, and dry and cure it in an oven to obtain a high-temperature resistant and yellowing-resistant pressure-sensitive tape.
[0020] Compared with the prior art, the present invention has the following advantages:
[0021] This invention utilizes a self-made high-temperature resistant monomer to improve the rigidity of the pressure-sensitive adhesive, and a closed, yellowing-resistant curing agent to improve the degree of crosslinking at high temperatures. The yellowing-resistant epoxy group curing agent forms a dense crosslinking network with carboxyl groups, improving temperature resistance while ensuring certain pressure-sensitive properties. At the same time, when the pressure-sensitive adhesive is subjected to high temperature, it crosslinks and cures with the unsealed isocyanate and hydroxyl groups, further improving the temperature resistance and achieving a higher crosslinking density, thus achieving ultra-high temperature resistance and yellowing resistance. Detailed Implementation
[0022] The present invention will be further illustrated below with reference to specific embodiments. These embodiments are implemented based on the technical solutions of the present invention, and it should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention.
[0023] In the following examples, TGIC is triglycidyl isocyanurate (Aladdin), HEMQ is p-hydroxyanisole (Aladdin), AA is acrylic acid (Aladdin), EHA is 2-ethylhexyl acrylate (Aladdin), IBOMA is isobornyl methacrylate (Aladdin), HDI is hexamethylene diisocyanate (Aladdin), AIBN is azobisisobutyronitrile (Aladdin), MAA is methacrylic acid (Aladdin); ZD0579 Jusheng epoxy resin is commercially available.
[0024] The acid value determination method in the following examples is based on GB / T 6743-2008 Determination of acid value and total acid value of the base component of polyester resins for plastics, paints and varnishes.
[0025] The method for determining the hydroxyl value in the following examples is based on HG / T 2709-1995, "Determination of hydroxyl value in polyester polyols".
[0026] In the following examples, the isocyanate determination method is based on GB / T 12009.4-2016.
[0027] The general formula of acrylic monomers used in the following examples is:
[0028] Wherein, R1 and R2 are H, -CH3, and -(CH2), respectively. n -COOH, where n is the number of carbon atoms from 0 to 10.
[0029] For example, when R1 and R2 are both H atoms, acrylic acid: H2C=CH-COOH;
[0030] When R1 is -CH3 and R2 is H-methacrylic acid: H2C=C(CH3)-COOH;
[0031] When R1 is -COOH and R2 is H, itaconic acid is: HOOC-C(=CH2)-COOH;
[0032] When R1 is H and R2 is -COOH, maleic acid is: HOOC-CH=CH-COOH.
[0033] The general structural formula for monoisocyanates is: R3-N=C=O
[0034] Among them, R3 is CH3-(CH2) n -A group where n is a number from 0 to 17.
[0035] When R3 is CH3-(CH2)3-n-butyl isocyanate: CH3-(CH2)3-N=C=O
[0036] Cyclohexyl isocyanate:
[0037] Octadecyl isocyanate: CH3-(CH2)17-N=C=O
[0038] T copies of IC:
[0039] High-temperature resistant monomer synthesis reaction equation:
[0040] The general reaction formula for the reaction of TGIC with acrylic monomers to form the high-temperature resistant monomer HT-1 series is as follows:
[0041]
[0042] When HT-1 series monomers react with monoisocyanates in an equimolar ratio, the general formula is:
[0043]
[0044] Step 1: Acrylic acid – TGIC (1:1 mol) reaction equation:
[0045]
[0046] TH-1-AA reacts with n-butyl isocyanate in an equimolar ratio at room temperature:
[0047]
[0048] TH-1-AA reacts with isocyanate in an equimolar ratio at room temperature, and then an equimolar ratio of n-butyl isocyanate is added and reacted at high temperature:
[0049]
[0050] The reaction equation for acrylic acid—TGIC—n-butyl isocyanate (1:3 mol) is as follows:
[0051]
[0052] Methacrylic acid-TGIC (1:1 mol)
[0053]
[0054] TH-1-MAA
[0055]
[0056] HT-1-MAA and n-butyl isocyanate (1:2 mol)
[0057]
[0058] HT-1-MAA and n-butyl isocyanate (1:3 mol)
[0059]
[0060] Example 1
[0061] (1) 29.73 parts of TGIC monomer were added to 29.73 parts of dimethyl sulfoxide solution, along with 0.2 parts of triethylamine and 0.5 parts of HEMQ. The mixture was heated to 70-80℃ and protected with nitrogen gas. After the temperature was reached, 7.2 parts of AA and 7.2 parts of dimethyl sulfoxide solution were slowly added dropwise over a period of 2 hours. After the addition was completed, the reaction was maintained at the same temperature until the acid value of the test system was lower than 5 mg / g KOH, at which point the reaction was stopped. The solvent was removed under reduced pressure, and the mixture was purified by passing it through an alkaline alumina column to obtain the high-temperature resistant monomer HT-101.
[0062] (2) 18.5 parts of the high-temperature resistant monomer HT-101 were added to 18.5 parts of toluene solution, and 0.05 parts of dibutyltin dilaurate were added. Under stirring at room temperature, 5 parts of n-butyl isocyanate and 5 parts of toluene solution were added rapidly. The mixture was stirred for 3 hours, and the hydroxyl value of the system was measured. When the hydroxyl value was less than 5 mg / g KOH, the temperature was raised to 80℃, and 0.2 parts of triphenylphosphine catalyst and 0.55 parts of HEMQ polymerization inhibitor were added. Nitrogen gas was introduced for protection, and 5 parts of n-butyl isocyanate and 5 parts of toluene solution were added dropwise over 1 hour. The mixture was kept at this temperature for 2 hours. The isocyanate content of the system was tested to be <0.2%, and the reaction was stopped. The solvent was removed by vacuum extraction and washed with 5% sodium hydroxide solution to remove the polymerization inhibitor HEMQ and excess isocyanate. The mixture was washed with distilled water until neutral and dried with anhydrous sodium sulfate to obtain the high-temperature resistant monomer HT-201.
[0063] (3) Weigh 36 parts of EHA, 6.5 parts of IBOMA, 2.5 parts of acrylic acid, 4 parts of hydroxyethyl acrylate, and 50 parts of ethyl acetate and put them into the reactor. Heat to 73°C and keep warm with nitrogen for 10 min. After the heat preservation is completed, use a peristaltic pump to inject 20 parts of a 1% thermal initiator solution of azobisisobutyronitrile. Keep the reaction for 2 h to obtain a viscous prepolymer. Start to drop a mixture containing 40 parts of EHA, 6.5 parts of IBOMA, 2 parts of hydroxyethyl acrylate, 2 parts of epoxy acrylate, 2 parts of acrylamide, 0.2 parts of azobisisobutyronitrile, and 50 parts of ethyl acetate. Control the dropping time to 3 h. Keep the reaction for 2 h. Drop 1.5 parts of high-temperature resistant monomer HT-201, 10 parts of toluene solution and 0.05 parts of AIBN initiator. Drop the dropping time to 30 min. Keep the reaction for 1 h. Cool to 50°C and add IPDI blocking curing agent to obtain acrylic high-temperature resistant and yellowing resistant adhesive.
[0064] (4) Weigh 100 parts of acrylic high temperature and yellowing resistant adhesive, add 0.5 parts of ZD0579 Jusheng epoxy resin, mix evenly and defoam, and directly coat it on a 50um high temperature resistant CPI substrate using a small coating machine. The adhesive thickness is 25um. Place it in an oven at 110℃ to dry for 2 minutes, and then cure at 70℃ for 24 hours to obtain a yellowing and high temperature resistant pressure-sensitive tape.
[0065] Example 2
[0066] (1) 29.73 parts of TGIC monomer were added to 29.73 parts of dimethyl sulfoxide solution, along with 0.2 parts of triethylamine and 0.5 parts of HEMQ. The mixture was heated to 70-80℃ and protected with nitrogen gas. After the temperature was reached, 8.6 parts of MAA and 8.6 parts of dimethyl sulfoxide solution were slowly added dropwise over a period of 2 hours. After the addition was completed, the reaction was maintained at this temperature until the acid value of the test system was lower than 5 mg / g KOH, at which point the reaction was stopped. The solvent was removed under reduced pressure. The mixture was then purified by passing it through an alkaline alumina column to obtain the high-temperature resistant monomer HT-102.
[0067] (2) 19.6 parts of the high-temperature resistant monomer HT-102 were added to 19.6 parts of toluene solution, along with 0.05 parts of dibutyltin dilaurate. 3.2 parts of cyclohexyl isocyanate and 5 parts of toluene solution were rapidly added under stirring at room temperature. The mixture was stirred for 3 hours, and the hydroxyl value of the system was measured. When the hydroxyl value was less than 5 mg / g KOH, the temperature was raised to 80℃, and 0.2 parts of triphenylphosphine catalyst and 0.55 parts of HEMQ polymerization inhibitor were added. Nitrogen gas was introduced for protection, and 3.2 parts of cyclohexyl isocyanate and 5 parts of toluene solution were added dropwise over 1 hour. The mixture was kept at this temperature for 2 hours. The isocyanate content of the system was tested to be <0.2%, and the reaction was stopped. The solvent was removed by vacuum extraction, and the mixture was washed with 5% sodium hydroxide solution to remove the polymerization inhibitor HEMQ and excess isocyanate. The mixture was washed with distilled water until neutral and dried with anhydrous sodium sulfate to obtain the high-temperature resistant monomer HT-202.
[0068] (3) Weigh 36 parts of EHA, 6.5 parts of IBOMA, 2.5 parts of acrylic acid, 4 parts of hydroxyethyl acrylate, and 50 parts of ethyl acetate and put them into the reactor. Heat to 73°C and keep warm with nitrogen for 10 min. After the heat preservation is completed, use a peristaltic pump to inject 20 parts of a 1% thermal initiator solution of azobisisobutyronitrile. Keep the reaction for 2 h to obtain a viscous prepolymer. Start to drop a mixture containing 40 parts of EHA, 6.5 parts of IBOMA, 2 parts of hydroxyethyl acrylate, 2 parts of epoxy acrylate, 2 parts of acrylamide, 0.2 parts of azobisisobutyronitrile, and 50 parts of ethyl acetate. Control the dropping time to 3 h. Keep the reaction for 2 h. Drop 1.5 parts of high-temperature resistant monomer HT-202, 10 parts of toluene solution and 0.05 parts of AIBN initiator. Drop 30 min. Keep the reaction for 1 h. Cool to 50°C and add IPDI blocking curing agent to obtain acrylic high-temperature resistant and yellowing resistant adhesive.
[0069] (4) Weigh 100 parts of acrylic high temperature and yellowing resistant adhesive, add 0.5 parts of ZD0579 Jusheng epoxy resin, mix evenly and defoam, and directly coat it on a 50um high temperature resistant CPI substrate using a small coating machine. The adhesive thickness is 25um. Place it in an oven at 110℃ to dry for 2 minutes, and then cure at 70℃ for 24 hours to obtain a yellowing and high temperature resistant pressure-sensitive tape.
[0070] Example 3
[0071] (1) 114.86 parts of TGIC monomer were added to 29.73 parts of dimethyl sulfoxide solution, along with 0.2 parts of triethylamine and 0.5 parts of HEMQ. The mixture was heated to 70-80℃ and protected with nitrogen gas. After the temperature was reached, 7.2 parts of AA and 7.2 parts of dimethyl sulfoxide solution were slowly added dropwise over a period of 2 hours. After the addition was completed, the reaction was maintained at the same temperature until the acid value of the test system was lower than 5 mg / g KOH, at which point the reaction was stopped. The solvent was removed under reduced pressure, and the mixture was purified by passing it through an alkaline alumina column to obtain the high-temperature resistant monomer HT-103.
[0072] (2) 18.5 parts of the high-temperature resistant monomer HT-103 were added to 18.5 parts of toluene solution, and 0.05 parts of dibutyltin dilaurate were added. Under stirring at room temperature, 5 parts of n-butyl isocyanate and 5 parts of toluene solution were added rapidly. The mixture was stirred for 3 hours, and the hydroxyl value of the system was measured. When the hydroxyl value was less than 5 mg / g KOH, the temperature was raised to 80℃, and 0.2 parts of triphenylphosphine catalyst and 0.55 parts of HEMQ polymerization inhibitor were added. Nitrogen gas was introduced for protection, and 5 parts of n-butyl isocyanate and 5 parts of toluene solution were added dropwise over 1 hour. The mixture was kept at this temperature for 1.5 hours. The isocyanate content of the system was tested to be <0.2%, and the reaction was stopped. The solvent was removed by vacuum extraction, and the mixture was washed with 5% sodium hydroxide solution to remove the polymerization inhibitor and excess isocyanate. The mixture was washed with distilled water until neutral and dried with anhydrous sodium sulfate to obtain the high-temperature resistant monomer HT-203.
[0073] (3) Weigh 36 parts of EHA, 6.5 parts of IBOMA, 2.5 parts of acrylic acid, 4 parts of hydroxyethyl acrylate, and 50 parts of ethyl acetate and put them into the reactor. Heat to 73°C and keep warm with nitrogen for 10 min. After the heat preservation is completed, use a peristaltic pump to inject 20 parts of a 1% thermal initiator solution of azobisisobutyronitrile. Keep the reaction for 2 h to obtain a viscous prepolymer. Start to drop a mixture containing 40 parts of EHA, 6.5 parts of IBOMA, 2 parts of hydroxyethyl acrylate, 2 parts of epoxy acrylate, 2 parts of acrylamide, 0.2 parts of azobisisobutyronitrile, and 50 parts of ethyl acetate. Control the dropping time to 3 h. Keep the reaction for 2 h. Drop 1.5 parts of high-temperature resistant monomer HT-203, 10 parts of toluene solution and 0.05 parts of AIBN initiator. Drop 30 min. Keep the reaction for 1 h. Cool to 50°C and add IPDI blocking curing agent to obtain acrylic high-temperature resistant and yellowing resistant adhesive.
[0074] (4) Weigh 100 parts of acrylic high temperature and yellowing resistant adhesive, add 0.5 parts of ZD0579 Jusheng epoxy resin, mix evenly and defoam, and directly coat it on a 50um high temperature resistant CPI substrate using a small coating machine. The adhesive thickness is 25um. Place it in an oven at 110℃ to dry for 2 minutes, and then cure at 70℃ for 24 hours to obtain a yellowing and high temperature resistant pressure-sensitive tape.
[0075] Comparative Example 1
[0076] 1) Add 29.73 parts of TGIC monomer to 29.73 parts of dimethyl sulfoxide solution, along with 0.2 parts of triethylamine and 0.5 parts of HEMQ. Heat to 70-80℃ and purge with nitrogen for protection. Once the temperature is reached, slowly add 7.2 parts of AA and 7.2 parts of dimethyl sulfoxide solution dropwise over 2 hours. After the addition is complete, maintain the reaction temperature until the acid value of the test system is below 5 mg / g KOH, at which point the reaction is stopped. Remove the solvent under reduced pressure and purify the product using an alkaline alumina column to obtain the high-temperature resistant monomer HT-101.
[0077] 2) Weigh 36 parts EHA, 6.5 parts IBOMA, 2.5 parts acrylic acid, 4 parts hydroxyethyl acrylate, and 50 parts ethyl acetate and add them to the reactor. Heat to 73°C and maintain the temperature with nitrogen for 10 minutes. After the temperature maintenance, use a peristaltic pump to inject a mixed thermal initiator solution of 2 parts azobisisobutyronitrile and 20 parts ethyl acetate. Maintain the temperature for 2 hours to obtain a viscous prepolymer. Start by adding a mixture containing 40 parts EHA, 6.5 parts IBOMA, 2 parts hydroxyethyl acrylate, 2 parts epoxy acrylate, 2 parts acrylamide, 0.2 parts azobisisobutyronitrile, and 50 parts ethyl acetate. Control the adding time to 2 hours. After maintaining the temperature for 2 hours, add 1.5 parts of HT-101 monomer from Example 1, 10 parts toluene solution, and 0.05 parts AIBN initiator. The adding time is 30 minutes. After maintaining the temperature for 1 hour, cool to 50°C and add HDI blocking curing agent to obtain acrylic high-temperature resistant and yellowing-resistant adhesive.
[0078] 3) Dilute the adhesive with ethyl acetate to a solid content of 30%, add 0.5 parts of ZD0579 Jusheng epoxy resin, and directly coat it onto a 50µm high-temperature resistant CPI substrate using a small coating machine. The coating thickness is 25µm. Dry it in an oven at 110℃ for 2 minutes and cure it at 70℃ for 24 hours to obtain a pressure-sensitive tape that is resistant to yellowing and high temperature.
[0079] Comparative Example 2
[0080] 1) Weigh 36 parts EHA, 6.5 parts IBOMA, 2.5 parts acrylic acid, 4 parts hydroxyethyl acrylate, and 50 parts ethyl acetate and add them to a reaction vessel. Heat to 73°C and maintain the temperature with nitrogen for 10 minutes. After the temperature maintenance, use a peristaltic pump to inject 20 parts of a 1% azobisisobutyronitrile thermal initiator solution and maintain the temperature for 2 hours to obtain a viscous prepolymer. Start adding a mixture containing 40 parts EHA, 6.5 parts IBOMA, 2 parts hydroxyethyl acrylate, 2 parts epoxy acrylate, 2 parts acrylamide, 0.2 parts azobisisobutyronitrile, and 50 parts ethyl acetate dropwise. Control the dropwise addition time to 3 hours and maintain the temperature for 3 hours. Add a small amount of thermal initiator, raise the temperature to 80°C, maintain the temperature for 3 hours, lower the temperature to 50°C, add HDI blocking curing agent, and unblock at 135°C to obtain acrylate adhesive.
[0081] 2) Dilute the adhesive with ethyl acetate to a solid content of 30%, and apply it directly to a 50µm high-temperature resistant CPI substrate using a small coating machine. The coating thickness is 25µm. Dry it in an oven at 110℃ for 2 minutes, and then cure it at room temperature for 3 days to obtain acrylic pressure-sensitive tape.
[0082] The high-temperature resistant pressure-sensitive tapes prepared in Examples 1-3 and Comparative Examples 1-2 were subjected to performance tests. The temperature resistance test included the following steps: The coated CPI substrate tape (25µm PI + 25µm PSA) was bonded to a steel plate, placed in a preheated oven at a set temperature, baked for a specified time, removed, cooled to room temperature, and the presence of bubbles was observed. The tape was then peeled open to check for any adhesive residue. If no bubbles were found, the result was AF (Average Quality); if bubbles were found, the result was NG (Not Approved). (b) Before high-temperature testing... and after 260℃ b Performance tests were conducted according to ASTM E 313; shear failure temperature tests were conducted according to B / T 36794-2018; and 180° peel strength tests were conducted according to BT 2792-1981, the method for determining the 180° peel strength of pressure-sensitive adhesive tapes. Results are shown in Table 1.
[0083] Table 1. Performance tests of the high-temperature pressure-sensitive adhesive tapes prepared in Examples 1-3 and Comparative Examples 1-2
[0084]
[0085] As shown in Table 1:
[0086] (1) As can be seen from Comparative Example 2 and Comparative Example 1, the high temperature resistant monomer HT-101 is a preliminarily modified high temperature resistant monomer, and its temperature resistance is improved compared with the pressure-sensitive adhesive without high temperature resistant monomer.
[0087] (2) As can be seen from Comparative Example 2, Comparative Example 1 and Example 1, HT-201 is a further improved high-temperature resistant monomer. Its chain segment movement is more difficult at high temperatures, so its high-temperature resistance is better than that of HT-101.
[0088] (3) As can be seen from Comparative Example 2, Example 1 and Example 2, the HT-202 monomer has better temperature resistance due to the introduction of MAA with higher Tg and better temperature resistance.
[0089] (4) As can be seen from Example 3, the main reason for the gel gel is the molar ratio of AA to TGIC, which causes the system to form a difunctional monomer, which is easy to gel in solution polymerization, accelerates crosslinking and causes the system to gel, making it unusable.
[0090] (5) By b The values show that the temperature resistance of HT-202 monomer is sufficient. At 260℃ / 30min, the colloid did not break down or decompose, demonstrating better temperature resistance and resistance to yellowing than HT-201 and HT-101 monomers. Furthermore, as shown in Example 1 and Comparative Example 1, the HT-2 series monomer b... Value compared to HT-1 series monomer b A lower value results in better resistance to yellowing.
[0091] Therefore, the HT-2 series of high-temperature resistant monomers can improve the high-temperature resistance and yellowing resistance of pressure-sensitive adhesives, and can be used to solve outdoor transparent application scenarios, etc.
[0092] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A method for preparing a high-temperature resistant and yellowing-resistant monomer, characterized in that: Includes the following steps: 1) Triglycidyl isocyanurate, catalyst and polymerization inhibitor are added to an organic solvent and heated to react. Then acrylic monomers and organic solvent are added, the solvent is removed under reduced pressure, and the mixture is purified by alkaline alumina column to obtain the high-temperature resistant monomer HT-1 series. 2) Dissolve the high-temperature resistant monomer HT-1 series obtained in step 1) in an organic solvent and react with monoisocyanate monomers. Then add polymerization inhibitors and catalysts, and extract the solvent under reduced pressure, wash and dry to obtain the high-temperature resistant monomer HT-2 series.
2. The method for preparing the high-temperature resistant and yellowing-resistant monomer according to claim 1, characterized in that: In step 1), the molar ratio of triglycidyl isocyanurate to acrylic monomer is 1:1~3; the reaction temperature is 70-80℃.
3. The method for preparing the high-temperature resistant and yellowing-resistant monomer according to claim 1, characterized in that: In step 1), the acrylic monomer is selected from one of acrylic acid, methacrylic acid, itaconic acid, and maleic acid.
4. The method for preparing the high-temperature resistant and yellowing-resistant monomer according to claim 1, characterized in that: In step 2), the monoisocyanate monomer is selected from one of n-butyl isocyanate, octadecyl isocyanate, and cyclohexyl isocyanate.
5. The method for preparing the high-temperature resistant and yellowing-resistant monomer according to claim 1, characterized in that: In steps 1) and 2), the polymerization inhibitor is selected from one or more of p-hydroxyanisole, p-benzoquinone, 2,5-dihydroxytoluene, 4-methoxyphenol, and tert-butylhydroquinone.
6. The method for preparing the high-temperature resistant and yellowing-resistant monomer according to claim 1, characterized in that: In steps 1) and 2), the catalyst is selected from one or more of triethylamine, benzyltriethylammonium chloride, triphenylphosphine, triphenylantimony, and zinc acetylacetonate.
7. The method for preparing the high-temperature resistant and yellowing-resistant monomer according to claim 1, characterized in that: In steps 1) and 2), the organic solvent is selected from one or more of ethyl acetate, methyl acetate, toluene, xylene, dimethyl carbonate, isopropanol, butyl acetate, dimethyl sulfoxide, and acetone.
8. The high-temperature resistant and yellowing-resistant monomer prepared by the preparation method according to any one of claims 1 to 7.
9. The application of the high-temperature resistant and yellowing-resistant monomer according to claim 8 in the preparation of pressure-sensitive adhesives.
10. The application of the high-temperature resistant and yellowing-resistant monomer according to claim 9 in the preparation of pressure-sensitive adhesives, characterized in that, Includes the following steps: 1) Weigh the soft monomer, hard monomer, functional monomer, and high-temperature resistant and yellowing-resistant monomer and add them to the solvent for heating and reaction. Purge with nitrogen to maintain the temperature. After the temperature maintenance is completed, use a peristaltic pump to inject a thermal initiator solution to prepare a prepolymer containing cross-linking groups. Then add the soft monomer, hard monomer, functional monomer, amide monomer, high-temperature resistant and yellowing-resistant monomer, and initiator. Add the heating initiator and then add an aliphatic blocked isocyanate curing agent to obtain an acrylic-based high-temperature resistant acrylate adhesive. 2) Add the adhesive obtained in step 1) to an aliphatic epoxy curing agent, apply it directly to a high-temperature resistant CPI substrate using a small coating machine, and dry and cure it in an oven to obtain a high-temperature resistant and yellowing-resistant pressure-sensitive tape.