A binder for large-size, radiation-resistant glass and its preparation process

Abstract

The invention relates to the field of adhesives, and specifically discloses an adhesive for large-size, radiation-resistant glass and a preparation process thereof. The preparation of the adhesive comprises the following steps: S1: taking hydroxy-terminated polybutadiene and polytetrahydrofuran diol, removing water, adding an organic bismuth catalyst, a polymerization inhibitor and ethyl acetate, mixing evenly, adding diisocyanate, heating and reacting for 2-3 hours under nitrogen protection, removing the solvent, and obtaining a prepolymer; adding 2,5-bis(allyloxy)terephthaloyl hydrazide, 5-allyl-3-methoxy salicylic acid methyl ester and an initiator, heating and stirring for 2-3 hours, and obtaining a polyurethane additive; S2: taking a multifunctional epoxy resin, N,N-dimethylformamide, toluene and modified silicone oil, heating and stirring for 4-6 hours under nitrogen protection, removing the solvent, adding a modified filler, and mixing evenly to obtain a modified epoxy resin; S3: mixing the modified epoxy resin, the polyurethane additive, a curing agent and an initiator evenly to obtain the adhesive.

Description

Technical Field

[0001] The invention relates to the field of adhesives, and in particular discloses an adhesive for large-size, radiation-resistant glass and a preparation process thereof. Background Art

[0002] Epoxy resin has good insulation, chemical stability and processing performance, and is widely used in adhesives, electronic packaging, high-performance coatings and other fields. However, when used as an adhesive, it has high cross-linking density and high internal stress after curing. When used as an adhesive, it has poor toughness and low peel strength, which needs to be solved urgently.

[0003] If epoxy resin is used to bond large-size, radiation-resistant glass, higher performance requirements are placed on it: the adhesive needs to have higher peel strength, higher tensile properties, and higher UV resistance; therefore, it is of great significance to prepare an adhesive with good toughness, good mechanical properties, high peel strength and radiation resistance. Summary of the invention

[0004] The object of the present invention is to provide an adhesive for large-size, radiation-resistant glass and a preparation process thereof, so as to solve the problems raised in the above-mentioned background technology.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions: A preparation process of an adhesive for large-size, radiation-resistant glass: comprising the following steps:

[0006] S1: Take terminal hydroxyl polybutadiene and polytetrahydrofuran diol, remove water, add organic bismuth catalyst, polymerization inhibitor (tert-butyl catechol), ethyl acetate, mix well, add diisocyanate (isophorone diisocyanate), heat and react for 2 to 3 hours under nitrogen protection, remove the solvent to obtain a prepolymer; add 2,5-bis(allyloxy)terephthaloyl hydrazide, 5-allyl-3-methoxysalicylic acid methyl ester, initiator (azobisisobutyronitrile), heat and stir for 2 to 3 hours to obtain a polyurethane additive;

[0007] S2: Take a multifunctional epoxy resin, N,N-dimethylformamide (DMF), toluene, and modified silicone oil, heat and stir for 4 to 6 hours under nitrogen protection, remove the solvent, add a modified filler, mix well, and obtain a modified epoxy resin;

[0008] S3: Evenly mix the modified epoxy resin, polyurethane additive, curing agent and initiator to obtain an adhesive.

[0009] Preferably, the polyurethane additive comprises the following raw materials, calculated by mass: 3 to 5 parts of terminal hydroxyl polybutadiene, 5 to 8 parts of polytetramethylene glycol, 6 to 8 parts of diisocyanate, 0.5 to 1 part of 2,5-bis(allyloxy)terephthaloyl hydrazide, and 1 to 1.5 parts of 5-allyl-3-methoxysalicylic acid methyl ester.

[0010] Preferably, the amount of the organic bismuth catalyst and the polymerization inhibitor added is 0.1% of the mass of isophorone diisocyanate.

[0011] Preferably, the modified epoxy resin comprises the following raw materials, calculated by mass: 100 parts of multifunctional epoxy resin and 25 to 35 parts of modified silicone oil.

[0012] Preferably, the adhesive comprises the following raw materials, calculated by mass: 100 parts of modified epoxy resin, 30-40 parts of polyurethane additive, 10-15 parts of curing agent, and 0.5-1 part of initiator.

[0013] Preferably, the preparation of the modified silicone oil comprises the following steps: taking high hydrogen silicone oil, oleyl alcohol, and diethylene glycol divinyl ether, heating, adding chloroplatinic acid as a catalyst, heating to 150-160° C. and reacting for 5-6 hours, heating to 170-180° C. and maintaining vacuum for 1 hour, and distilling under reduced pressure to obtain modified silicone oil.

[0014] Preferably, the modified silicone oil comprises the following raw materials, calculated by weight: 15 to 20 parts of high hydrogen silicone oil, 4 to 5 parts of oleyl alcohol, 1 to 2 parts of diethylene glycol divinyl ether, and 0.01 to 0.02% of the weight of the high hydrogen silicone oil in the amount of chloroplatinic acid catalyst.

[0015] Preferably, the preparation of the modified filler comprises the following steps: Step 1: depositing silicon dioxide on the surface of nano zinc sulfide;

[0016] Step 2: Take nano zinc sulfide with deposited silicon dioxide, add ethanol, water, and aminosilane coupling agent, stir at 40-50° C. for 3-4 hours, add glutaraldehyde, stir at 50-60° C. for 1-2 hours, filter, wash, and dry to obtain a modified filler.

[0017] Preferably, the modified filler comprises the following raw materials, by mass: 15-20 parts of nano zinc sulfide deposited with silicon dioxide, 60-80 parts of ethanol, 60-80 parts of water, and 2-3 parts of aminosilane coupling agent; the molar ratio of the aminosilane coupling agent to glutaraldehyde is 2:1.

[0018] Preferably, the specific steps of depositing silicon dioxide on the surface of nano zinc sulfide are as follows: S1: placing 0.4 parts of nano zinc sulfide in a vacuum dryer, and placing two small beakers in the vacuum dryer, adding 1 part of tetraethyl orthosilicate and 1 part of 30% ammonia water to the two small beakers respectively, sealing and evacuating;

[0019] S2: Put the vacuum dryer in step S1 into a 160° C. incubator for 6 hours, take it out, and obtain nano zinc sulfide with deposited silicon dioxide.

[0020] Preferably, the curing agent is a small molecule curing agent, including m-xylylenediamine.

[0021] Preferably, the curing agent is m-xylylenediamine.

[0022] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: the binder includes modified epoxy resin, polyurethane additive, m-xylylenediamine and initiator; pure epoxy resin has high crosslinking density and large internal stress after curing, and has the problems of poor toughness and low peel strength when used as an adhesive, therefore, modified silicone oil is used for modification; silicone oil can increase the toughness of epoxy resin and improve mechanical properties, and silicone oil has good ultraviolet resistance and can improve the radiation resistance of epoxy resin; the present invention uses high hydrogen silicone oil, and then adds oleyl alcohol and diethylene glycol divinyl ether for modification, oleyl alcohol can not only improve the mechanical properties of epoxy resin, but also the presence of hydroxyl groups improves the compatibility of modified silicone oil and epoxy resin; diethylene glycol divinyl ether introduces double bonds into epoxy resin so that it can participate in the double bond crosslinking curing reaction in the subsequent steps;

[0023] Modified fillers are added to the modified epoxy resin, and the nano zinc sulfide with deposited silica modified by aminosilane coupling agent and glutaraldehyde is obtained; zinc sulfide and silica can improve the radiation resistance of the epoxy resin, and the aminosilane coupling agent and glutaraldehyde with a molar ratio of 2:1 are added to modify the epoxy resin, so that it has good compatibility with the epoxy resin matrix, and the aldehyde group can react with 2,5-bis(allyloxy)terephthaloylhydrazide in the polyurethane additive to obtain a Schiff base group, which further improves the ultraviolet absorption performance;

[0024] The modified silicone oil and silicon dioxide contained in the modified epoxy resin improve its surface compatibility with the silicon-based substrate, making the adhesive more suitable for glass bonding;

[0025] The polyurethane additive forms an interpenetrating network structure with the epoxy resin to improve the peel strength and overall mechanical properties. The double bonds in the terminal hydroxyl polybutadiene can participate in the double bond cross-linking curing reaction in the subsequent step. 5-allyl-3-methoxy salicylic acid methyl ester improves the radiation resistance. 2,5-bis(allyloxy)terephthaloyl hydrazide can react with the aldehyde group in the modified epoxy resin to obtain a Schiff base group, further improving the ultraviolet absorption performance. The end group of the polyurethane additive can react with the epoxy group to assist in curing and strengthen the mechanical properties of the adhesive. Since the curing rate of the macromolecule is slow, a small molecule curing agent, meta-phenylenediamine, is also introduced to increase the curing speed of the adhesive and have good mechanical properties.

[0026] During the curing process of the adhesive, there is also a cross-linking reaction of double bonds. Various curing methods can reduce curing stress and improve tensile strength and peel strength. At the same time, there is a reaction between 2,5-bis(allyloxy)terephthaloylhydrazide in the polyurethane additive and the aldehyde group in the modified epoxy resin, which assists the curing and improves the radiation resistance. DETAILED DESCRIPTION

[0027] The following is a preferred implementation of the embodiment of the present invention. Obviously, the described embodiment is only a part of the embodiment of the present invention, not all of the embodiments. For ordinary technicians in this technical field, all other embodiments obtained by ordinary technicians in this field without creative work without departing from the principle of the embodiment of the present invention are within the scope of protection of the present invention.

[0028] The following parts are by mass unless otherwise specified;

[0029] Example 1: 100 parts of modified epoxy resin, 35 parts of polyurethane additive, 12 parts of curing agent and 0.8 parts of initiator were mixed evenly to obtain an adhesive;

[0030] The preparation method of the polyurethane additive is as follows: 4 parts of hydroxy-terminated polybutadiene and 6 parts of polytetrahydrofuran diol are taken, after removing water, an organic bismuth catalyst, a polymerization inhibitor, and 25 parts of ethyl acetate are added, mixed evenly, 7 parts of isophorone diisocyanate are added, the temperature is raised to 60° C. under nitrogen protection for reaction for 3 hours, and the solvent is removed to obtain a prepolymer; 1 part of 2,5-bis(allyloxy)terephthaloyl hydrazide, 1 part of 5-allyl-3-methoxysalicylic acid methyl ester, and an initiator of 0.05% by weight of the prepolymer are added, and the mixture is stirred at 75° C. for 3 hours to obtain the polyurethane additive;

[0031] The preparation method of the modified epoxy resin is as follows: 100 parts of multifunctional epoxy resin, 70 parts of DMF, 30 parts of toluene, and 30 parts of modified silicone oil are taken, stirred at 100° C. for 5 hours under nitrogen protection, the solvent is removed, 25 parts of modified filler are added, and mixed evenly to obtain the modified epoxy resin;

[0032] The preparation method of the modified silicone oil is as follows: add 18 parts of high hydrogen silicone oil, 4 parts of oleyl alcohol, and 2 parts of diethylene glycol divinyl ether, heat to 90°C, add 0.01% of chloroplatinic acid by weight of the high hydrogen silicone oil as a catalyst, heat to 160°C and react for 6 hours, heat to 180°C and keep vacuum at -0.1MPa for 1 hour, and perform reduced pressure distillation to obtain the modified silicone oil;

[0033] The preparation method of the modified filler is as follows: take 18 parts of nano zinc sulfide with deposited silica, add 60 parts of ethanol, 80 parts of water, and 3 parts of aminosilane coupling agent, stir at 50°C for 4 hours, add glutaraldehyde, stir at 60°C for 2 hours, filter, wash, and dry to obtain the modified filler; the molar ratio of aminosilane coupling agent to glutaraldehyde is 2:1.

[0034] Example 2: 100 parts of modified epoxy resin, 40 parts of polyurethane additive, 10 parts of curing agent and 1 part of initiator were mixed evenly to obtain an adhesive;

[0035] The preparation method of the polyurethane additive is as follows: 5 parts of hydroxy-terminated polybutadiene and 5 parts of polytetrahydrofuran diol are taken, after removing water, an organic bismuth catalyst, a polymerization inhibitor, and 25 parts of ethyl acetate are added, mixed evenly, 6 parts of isophorone diisocyanate are added, the temperature is raised to 60° C. under nitrogen protection for reaction for 3 hours, and the solvent is removed to obtain a prepolymer; 0.5 parts of 2,5-bis(allyloxy)terephthaloyl hydrazide, 1 part of 5-allyl-3-methoxysalicylic acid methyl ester, and an initiator of 0.05% by weight of the prepolymer are added, and the mixture is stirred at 75° C. for 3 hours to obtain the polyurethane additive;

[0036] The preparation method of the modified epoxy resin is as follows: 100 parts of multifunctional epoxy resin, 70 parts of DMF, 30 parts of toluene, and 25 parts of modified silicone oil are taken, stirred at 100° C. for 5 hours under nitrogen protection, the solvent is removed, 25 parts of modified filler are added, and mixed evenly to obtain the modified epoxy resin;

[0037] The preparation method of the modified silicone oil is as follows: add 15 parts of high hydrogen silicone oil, 4 parts of oleyl alcohol, and 1 part of diethylene glycol divinyl ether, heat to 90°C, add 0.01% of chloroplatinic acid by mass of the high hydrogen silicone oil as a catalyst, heat to 160°C and react for 6 hours, heat to 180°C and keep vacuum -0.1MPa for 1 hour, and distill under reduced pressure to obtain the modified silicone oil;

[0038] The preparation method of the modified filler is as follows: take 15 parts of nano zinc sulfide with deposited silicon dioxide, add 60 parts of ethanol, 80 parts of water, and 2-3 parts of aminosilane coupling agent, stir at 50°C for 4 hours, add glutaraldehyde, stir at 60°C for 2 hours, filter, wash, and dry to obtain the modified filler; the molar ratio of aminosilane coupling agent to glutaraldehyde is 2:1.

[0039] Example 3: 100 parts of modified epoxy resin, 30 parts of polyurethane additive, 15 parts of curing agent and 1 part of initiator were mixed evenly to obtain an adhesive;

[0040] The preparation method of the polyurethane additive is as follows: 5 parts of hydroxy-terminated polybutadiene and 8 parts of polytetrahydrofuran diol are taken, after removing water, an organic bismuth catalyst, a polymerization inhibitor, and 25 parts of ethyl acetate are added, mixed evenly, 8 parts of isophorone diisocyanate are added, the temperature is raised to 60° C. under nitrogen protection for reaction for 3 hours, and the solvent is removed to obtain a prepolymer; 1 part of 2,5-bis(allyloxy)terephthaloyl hydrazide, 1.5 parts of 5-allyl-3-methoxysalicylic acid methyl ester, and an initiator of 0.05% by weight of the prepolymer are added, and the mixture is stirred at 75° C. for 3 hours to obtain the polyurethane additive;

[0041] The preparation method of the modified epoxy resin is as follows: 100 parts of multifunctional epoxy resin, 70 parts of DMF, 30 parts of toluene, and 35 parts of modified silicone oil are taken, stirred at 100° C. for 5 hours under nitrogen protection, the solvent is removed, 25 parts of modified filler are added, and mixed evenly to obtain the modified epoxy resin;

[0042] The preparation method of the modified silicone oil is as follows: add 20 parts of high hydrogen silicone oil, 5 parts of oleyl alcohol, and 1 part of diethylene glycol divinyl ether, heat to 90°C, add 0.01% of chloroplatinic acid by mass of the high hydrogen silicone oil as a catalyst, heat to 160°C and react for 6 hours, heat to 180°C and keep vacuum -0.1MPa for 1 hour, and distill under reduced pressure to obtain the modified silicone oil;

[0043] The preparation method of the modified filler is as follows: take 20 parts of nano zinc sulfide with deposited silica, add 60 parts of ethanol, 80 parts of water, and 3 parts of aminosilane coupling agent, stir at 50°C for 4 hours, add glutaraldehyde, stir at 60°C for 2 hours, filter, wash, and dry to obtain the modified filler; the molar ratio of aminosilane coupling agent to glutaraldehyde is 2:1.

[0044] Comparative Example 1 (the preparation method of the polyurethane additive is changed, and the other method steps are consistent with Example 1): 100 parts of modified epoxy resin, 35 parts of polyurethane additive, 12 parts of curing agent, and 0.8 parts of initiator are mixed uniformly to obtain a binder;

[0045] The preparation method of the polyurethane additive is as follows: 4 parts of hydroxy-terminated polybutadiene and 6 parts of polytetrahydrofuran diol are taken, and after removing water, an organic bismuth catalyst, a polymerization inhibitor, and 25 parts of ethyl acetate are added, mixed evenly, 7 parts of isophorone diisocyanate are added, the temperature is raised to 60° C. under nitrogen protection, and the reaction is carried out for 3 hours, and the solvent is removed to obtain the polyurethane additive;

[0046] The preparation method of the modified epoxy resin is as follows: 100 parts of multifunctional epoxy resin, 70 parts of DMF, 30 parts of toluene, and 30 parts of modified silicone oil are taken, stirred at 100° C. for 5 hours under nitrogen protection, the solvent is removed, 25 parts of modified filler are added, and mixed evenly to obtain the modified epoxy resin;

[0047] The preparation method of the modified silicone oil is as follows: add 18 parts of high hydrogen silicone oil, 4 parts of oleyl alcohol, and 2 parts of diethylene glycol divinyl ether, heat to 90°C, add 0.01% of chloroplatinic acid by weight of the high hydrogen silicone oil as a catalyst, heat to 160°C and react for 6 hours, heat to 180°C and keep vacuum at -0.1MPa for 1 hour, and perform reduced pressure distillation to obtain the modified silicone oil;

[0048] The preparation method of the modified filler is as follows: take 18 parts of nano zinc sulfide with deposited silica, add 60 parts of ethanol, 80 parts of water, and 3 parts of aminosilane coupling agent, stir at 50°C for 4 hours, add glutaraldehyde, stir at 60°C for 2 hours, filter, wash, and dry to obtain the modified filler; the molar ratio of aminosilane coupling agent to glutaraldehyde is 2:1.

[0049] Comparative Example 2 (the preparation method of the modified epoxy resin is changed, and the other method steps are consistent with Example 1): 100 parts of the modified epoxy resin, 35 parts of the polyurethane additive, 12 parts of the curing agent, and 0.8 parts of the initiator are mixed uniformly to obtain a binder;

[0050] The preparation method of the polyurethane additive is as follows: 4 parts of hydroxy-terminated polybutadiene and 6 parts of polytetrahydrofuran diol are taken, after removing water, an organic bismuth catalyst, a polymerization inhibitor, and 25 parts of ethyl acetate are added, mixed evenly, 7 parts of isophorone diisocyanate are added, the temperature is raised to 60° C. under nitrogen protection for reaction for 3 hours, and the solvent is removed to obtain a prepolymer; 1 part of 2,5-bis(allyloxy)terephthaloyl hydrazide, 1 part of 5-allyl-3-methoxysalicylic acid methyl ester, and an initiator of 0.05% by weight of the prepolymer are added, and the mixture is stirred at 75° C. for 3 hours to obtain the polyurethane additive;

[0051] The preparation method of the modified epoxy resin is as follows: 100 parts of multifunctional epoxy resin, 70 parts of DMF, 30 parts of toluene, and 30 parts of high hydrogen silicone oil are taken, stirred at 100° C. for 5 hours under nitrogen protection, the solvent is removed, 25 parts of modified filler are added, and mixed evenly to obtain the modified epoxy resin;

[0052] The preparation method of the modified filler is as follows: take 18 parts of nano zinc sulfide with deposited silica, add 60 parts of ethanol, 80 parts of water, and 3 parts of aminosilane coupling agent, stir at 50°C for 4 hours, add glutaraldehyde, stir at 60°C for 2 hours, filter, wash, and dry to obtain the modified filler; the molar ratio of aminosilane coupling agent to glutaraldehyde is 2:1.

[0053] Comparative Example 3 (changing the amount of components added in the binder, and the other method steps are consistent with Example 1): 100 parts of modified epoxy resin, 25 parts of polyurethane additive, 20 parts of curing agent, and 0.8 parts of initiator are mixed uniformly to obtain a binder;

[0054] The preparation method of the polyurethane additive is as follows: 4 parts of hydroxy-terminated polybutadiene and 6 parts of polytetrahydrofuran diol are taken, after removing water, an organic bismuth catalyst, a polymerization inhibitor, and 25 parts of ethyl acetate are added, mixed evenly, 7 parts of isophorone diisocyanate are added, the temperature is raised to 60° C. under nitrogen protection for reaction for 3 hours, and the solvent is removed to obtain a prepolymer; 1 part of 2,5-bis(allyloxy)terephthaloyl hydrazide, 1 part of 5-allyl-3-methoxysalicylic acid methyl ester, and an initiator of 0.05% by weight of the prepolymer are added, and the mixture is stirred at 75° C. for 3 hours to obtain the polyurethane additive;

[0055] The preparation method of the modified epoxy resin is as follows: 100 parts of multifunctional epoxy resin, 70 parts of DMF, 30 parts of toluene, and 30 parts of modified silicone oil are taken, stirred at 100° C. for 5 hours under nitrogen protection, the solvent is removed, 25 parts of modified filler are added, and mixed evenly to obtain the modified epoxy resin;

[0056] The preparation method of the modified silicone oil is as follows: add 18 parts of high hydrogen silicone oil, 2 parts of oleyl alcohol, and 3 parts of diethylene glycol divinyl ether, heat to 90°C, add 0.01% of chloroplatinic acid by weight of the high hydrogen silicone oil as a catalyst, heat to 160°C and react for 6 hours, heat to 180°C and maintain vacuum -0.1MPa for 1 hour, and perform reduced pressure distillation to obtain the modified silicone oil;

[0057] The preparation method of the modified filler is as follows: take 18 parts of nano zinc sulfide with deposited silica, add 60 parts of ethanol, 80 parts of water, and 3 parts of aminosilane coupling agent, stir at 50°C for 4 hours, add glutaraldehyde, stir at 60°C for 2 hours, filter, wash, and dry to obtain the modified filler; the molar ratio of aminosilane coupling agent to glutaraldehyde is 2:1.

[0058] Comparative Example 4 (replacing the curing agent m-xylylenediamine with polyetheramine D-2000, and the remaining method steps are consistent with Example 1): 100 parts of modified epoxy resin, 35 parts of polyurethane additive, 12 parts of curing agent, and 0.8 parts of initiator are mixed uniformly to obtain a binder;

[0059] The preparation method of the polyurethane additive is as follows: 4 parts of hydroxy-terminated polybutadiene and 6 parts of polytetrahydrofuran diol are taken, after removing water, an organic bismuth catalyst, a polymerization inhibitor, and 25 parts of ethyl acetate are added, mixed evenly, 7 parts of isophorone diisocyanate are added, the temperature is raised to 60° C. under nitrogen protection for reaction for 3 hours, and the solvent is removed to obtain a prepolymer; 1 part of 2,5-bis(allyloxy)terephthaloyl hydrazide, 1 part of 5-allyl-3-methoxysalicylic acid methyl ester, and an initiator of 0.05% by weight of the prepolymer are added, and the mixture is stirred at 75° C. for 3 hours to obtain the polyurethane additive;

[0060] The preparation method of the modified epoxy resin is as follows: 100 parts of multifunctional epoxy resin, 70 parts of DMF, 30 parts of toluene, and 30 parts of modified silicone oil are taken, stirred at 100° C. for 5 hours under nitrogen protection, the solvent is removed, 25 parts of modified filler are added, and mixed evenly to obtain the modified epoxy resin;

[0061] The preparation method of the modified silicone oil is as follows: add 18 parts of high hydrogen silicone oil, 2 parts of oleyl alcohol, and 3 parts of diethylene glycol divinyl ether, heat to 90°C, add 0.01% of chloroplatinic acid by weight of the high hydrogen silicone oil as a catalyst, heat to 160°C and react for 6 hours, heat to 180°C and maintain vacuum -0.1MPa for 1 hour, and perform reduced pressure distillation to obtain the modified silicone oil;

[0062] The preparation method of the modified filler is as follows: take 18 parts of nano zinc sulfide with deposited silica, add 60 parts of ethanol, 80 parts of water, and 3 parts of aminosilane coupling agent, stir at 50°C for 4 hours, add glutaraldehyde, stir at 60°C for 2 hours, filter, wash, and dry to obtain the modified filler; the molar ratio of aminosilane coupling agent to glutaraldehyde is 2:1.

[0063] In the above examples, the test methods used are conventional methods unless otherwise specified; the raw materials used are commercially available unless otherwise specified, and the sources of the raw materials are as follows: isophorone diisocyanate (CAS: 4098-71-9); ethanol (CAS: 64-17-5); tert-butylcatechol (CAS: 98-29-3); m-xylylenediamine (CAS: 1477-55-0); azobisisobutyronitrile (CAS: 78-67-1); hydroxy-terminated polybutadiene (Type II, Tianyuan Aerospace Yingkou Technology Co., Ltd. Co., Ltd.); polytetrahydrofuran diol (PTMG1000, Shandong Jiaying Chemical Technology Co., Ltd.); organic bismuth catalyst (JD200326093411, Shanghai Jiader Chemical Technology Co., Ltd.); ethyl acetate (CAS: 141-78-6); 2,5-bis(allyloxy)terephthaloyl hydrazide (CAS: 2227151-69-9); 5-allyl-3-methoxysalicylic acid methyl ester (A0614433, Henan Weitixi Chemical Technology Co., Ltd.); multifunctional epoxy resin (Tactix 556, Guangzhou Taiji New Materials Co., Ltd.); DMF (CAS: 68-12-2); toluene (CAS: 108-88-3); high hydrogen silicone oil (IOTA 202, Anhui IOTA Silicone Oil Co., Ltd.); oleyl alcohol (CAS: 143-28-2); diethylene glycol divinyl ether (S67963, Shanghai Yuanye); chloroplatinic acid (H721046, Wuhan Xinxin Jiali Biotechnology Co., Ltd.); nano zinc sulfide (AM-ZnS-001-1, Yamei Nano); tetraethyl orthosilicate (CAS: 562-90-3); aminosilane coupling agent (KH550, 919-30-2); glutaraldehyde (CAS: 111-30-8); polyetheramine D-2000 (M29442, Shanghai Myril Biochemical Technology Co., Ltd.).

[0064] Experiment: Take the adhesive prepared in Examples 1 to 3 and Comparative Examples 1 to 4; (1) apply to an aluminum alloy plate with a coating thickness of 0.2 mm, cure at 65°C for 2 h, and cure at 120°C for 2 h to obtain an adhesive film; test the peel strength with reference to GB / T 7122-1996; (2) cure according to the above curing method, take the adhesive film, and test the tensile strength with reference to GB / T 1040.1-2018; (3) refer to GB / T14522-2008 for artificial accelerated aging, and the parameters of one cycle are set as: UVB-313 ultraviolet irradiation + temperature of 60°C, treatment for 4 h, ultraviolet irradiation + spray water, treatment for 4 h; after 168 h of circulation, take the adhesive film and test the tensile strength; see the table below for specific data;

[0065]

[0066] Conclusion: Comparative Example 1 changes the preparation method of the polyurethane additive, and does not add 2,5-bis(allyloxy)terephthaloyl hydrazide and 5-allyl-3-methoxy salicylic acid methyl ester, and the performance is reduced; Comparative Example 2 changes the preparation method of the modified epoxy resin, that is, when the unmodified high hydrogen silicone oil is used, the performance is reduced; Comparative Example 3 changes the amount of components added in the adhesive, and the performance is not as good as the example, which shows that the ratio is of great significance; Comparative Example 4 replaces the curing agent m-phenylenediamine with polyetheramine D-2000, and the performance is not as good as the example. In summary, the adhesive prepared by the present invention has high peel strength, good tensile strength, and good UV resistance.

[0067] Finally, it should be noted that the above is only a preferred embodiment of the present invention, but the protection scope of this application is not limited thereto. Any changes or substitutions that can be easily thought of by any technician familiar with the technical field within the spirit and principle of the present invention and within the technical scope disclosed in this application should be included in the protection scope of this application; in the absence of conflict, the embodiments of this application and the features in the embodiments can be combined with each other. Therefore, the protection scope of this application shall be based on the protection scope of the claims.

Claims

1. A process for preparing an adhesive for large-size, radiation-resistant glass, characterized in that: The following steps are involved: S1: Take terminal hydroxyl polybutadiene and polytetrahydrofuran diol, remove water, add organic bismuth catalyst, inhibitor, ethyl acetate, mix well, add diisocyanate, heat and react for 2-3 hours under nitrogen protection, remove solvent to obtain prepolymer; add 2,5-bis(allyloxy)terephthaloyl hydrazide, 5-allyl-3-methoxysalicylic acid methyl ester, initiator, heat and stir for 2-3 hours to obtain polyurethane additive; S2: Take multifunctional epoxy resin, N,N-dimethylformamide, toluene, and modified silicone oil, heat and stir for 4-6 hours under nitrogen protection, remove the solvent, add modified filler, mix well, and obtain modified epoxy resin; S3: uniformly mixing the modified epoxy resin, the polyurethane additive, the curing agent and the initiator to obtain a binder; The polyurethane additive comprises the following raw materials, calculated by weight: 3-5 parts of terminal hydroxyl polybutadiene, 5-8 parts of polytetramethylene glycol, 6-8 parts of diisocyanate, 0.5-1 parts of 2,5-bis(allyloxy)terephthaloyl hydrazide, and 1-1.5 parts of 5-allyl-3-methoxy salicylic acid methyl ester; the modified epoxy resin comprises the following raw materials, calculated by weight: 100 parts of multifunctional epoxy resin and 25-35 parts of modified silicone oil; the binder comprises the following raw materials, calculated by weight: 100 parts of modified epoxy resin, 30-40 parts of polyurethane additive, 10-15 parts of curing agent, and 0.5-1 part of initiator; The preparation of the modified silicone oil comprises the following steps: taking high hydrogen silicone oil, oleyl alcohol, and diethylene glycol divinyl ether, heating, adding chloroplatinic acid as a catalyst, heating to 150-160° C. and reacting for 5-6 hours, heating to 170-180° C. and maintaining vacuum for 1 hour, and performing reduced pressure distillation to obtain the modified silicone oil; The modified silicone oil comprises the following raw materials, calculated by weight: 15-20 parts of high hydrogen silicone oil, 4-5 parts of oleyl alcohol, 1-2 parts of diethylene glycol divinyl ether, and 0.01-0.02% of the weight of the high hydrogen silicone oil as a chloroplatinic acid catalyst; The preparation of the modified filler comprises the following steps: Step 1: depositing silicon dioxide on the surface of nano zinc sulfide; Step 2: Take nano zinc sulfide with deposited silicon dioxide, add ethanol, water, and aminosilane coupling agent, stir at 40-50° C. for 3-4 hours, add glutaraldehyde, stir at 50-60° C. for 1-2 hours, filter, wash, and dry to obtain a modified filler; The modified filler comprises the following raw materials, calculated by weight: 15-20 parts of nano zinc sulfide deposited with silicon dioxide, 60-80 parts of ethanol, 60-80 parts of water, and 2-3 parts of aminosilane coupling agent; the molar ratio of the aminosilane coupling agent to glutaraldehyde is 2:1; The curing agent is a small molecule curing agent, including meta-xylylenediamine.

2. The adhesive obtained according to the preparation process of an adhesive for large-size, radiation-resistant glass according to claim 1.

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