A high-performance pressure-sensitive adhesive based on modified methyl MQ resin and preparation method thereof

Abstract

The present invention relates to the technical field of pressure-sensitive adhesives, and specifically to a high-performance pressure-sensitive adhesive based on modified methyl MQ resin and a preparation method thereof, which is used to solve the problem that the existing pressure-sensitive adhesive is prone to thermal oxidation degradation and erosion hydrolysis reaction under high temperature and high humidity environment, resulting in a significant decrease in its viscosity and mechanical properties, or even complete failure; the high-performance pressure-sensitive adhesive has excellent bonding strength, and at the same time, excellent adaptability and stability, so that it can maintain excellent bonding performance in both high temperature and humid environments, so that it can be better applied to different fields such as electronic components, mobile phone screen lamination, and automobile interiors, effectively solving the problem that the original pressure-sensitive adhesive is prone to failure under high temperature and humid environments. In addition, the preparation method is simple to operate and low in cost, can meet the needs of large-scale production, provides new possibilities for the innovation and development of pressure-sensitive adhesives, and greatly improves production efficiency and product quality.

Description

Technical Field

[0001] The invention relates to the technical field of pressure-sensitive adhesives, and in particular to a high-performance pressure-sensitive adhesive based on modified methyl MQ resin and a preparation method thereof. Background Art

[0002] Pressure-sensitive adhesive is a pressure-sensitive adhesive widely used in electronic components, mobile phone screen bonding, automotive interior and other fields. Traditional pressure-sensitive adhesives are mostly made of materials such as polyisobutylene, polyacrylate and polysiloxane. However, these materials generally have problems such as low peel strength and insufficient substrate adhesion. Silicone rubber-based pressure-sensitive adhesive is a material with special properties. Its main component is a silicon-oxygen chain composed of silicon atoms and oxygen atoms. This structure gives silicone rubber-based pressure-sensitive adhesive good bonding properties, plasticity and softness, and can quickly adhere to various surfaces. However, its heat resistance and weather resistance are poor, which makes silicone rubber-based pressure-sensitive adhesive prone to thermal oxidation degradation and erosion and hydrolysis reactions in high temperature and high humidity environments, which can easily lead to a significant decrease in its viscosity and mechanical properties, or even complete failure, limiting its application in high-performance fields.

[0003] Therefore, it is of great significance to develop a high-performance pressure-sensitive adhesive based on modified methyl MQ resin and a preparation method thereof. Summary of the invention

[0004] In order to overcome the above-mentioned technical problems, the purpose of the present invention is to provide a high-performance pressure-sensitive adhesive based on modified methyl MQ resin and a preparation method thereof, which solves the problem that the existing pressure-sensitive adhesive is prone to thermal oxidation degradation and corrosion and hydrolysis reaction under high temperature and high humidity environment, resulting in a significant decrease in its viscosity and mechanical properties, or even complete failure.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A high-performance pressure-sensitive adhesive based on modified methyl MQ resin comprises the following components in parts by weight:

[0007] 10 parts of silicone rubber, 0.8-5.2 parts of modified methyl MQ resin, 9-13 parts of toluene and 0.05-0.15 parts of dibenzoyl peroxide;

[0008] Wherein, the modified methyl MQ resin is prepared by the following steps:

[0009] Step a1: Add 2,6-dimethylbromobenzene, perfluorohexylethanol, anhydrous potassium carbonate and anhydrous acetone into a three-necked flask equipped with a stirrer, a thermometer and an air guide tube, introduce nitrogen protection, stir and react for 20-30 minutes at a temperature of 25-30° C. and a stirring rate of 300-400 r / min, then heat to 95-100° C. and continue stirring and reacting for 3-4 hours. After the reaction is completed, the reaction product is cooled to room temperature, then vacuum filtered, and the filtrate is rotary evaporated to remove the solvent to obtain intermediate 1;

[0010] Step a2: Add intermediate 1, sodium hydroxide, 2-methyl-2-propanol and deionized water to a three-necked flask equipped with a stirrer, a thermometer and an air guide tube, introduce nitrogen protection, stir and react for 20-30 minutes at a temperature of 25-30° C. and a stirring rate of 300-400 r / min, then add potassium permanganate and continue to stir and react for 10-15 hours under the condition of heating to 70-75° C., then add sodium sulfite and continue to stir and react for 1-1.5 hours, then filter while hot, cool the filtrate to below 5° C., then adjust the pH to 1-2 with hydrochloric acid solution, then vacuum filter, place the filter cake in a vacuum drying oven, and dry it at a temperature of 50-55° C. for 2-3 hours to obtain intermediate 2;

[0011] Step a3: Add intermediate 2, 2-mercaptoethanol, p-toluenesulfonic acid and cyclohexane to a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, introduce nitrogen protection, stir and react for 20-30 minutes at a temperature of 25-30° C. and a stirring rate of 300-400 r / min, then heat to 90-95° C. and continue stirring and reacting for 6-7 hours. After the reaction is completed, the reaction product is cooled to room temperature, and then the solvent is removed by rotary evaporation to obtain a resin modifier;

[0012] Step a4: add hexamethyldisiloxane, tetramethyldivinyldisiloxane, deionized water, anhydrous ethanol and hydrochloric acid solution to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a constant pressure dropping funnel, introduce nitrogen protection, stir and react for 20-30 minutes at a temperature of 25-30°C and a stirring rate of 300-400r / min, then add tetraethoxysilane dropwise while stirring, and control the dropping rate to 1-2 drops / s. After the dropwise addition is completed, continue to stir and react for 2-3 hours at a temperature of 40-45°C, then add a resin modifier and continue to stir and react for 2-3 hours. After the reaction is completed, cool the reaction product to room temperature, then extract it with toluene 2-3 times, combine the extracts and rotary evaporate them to remove the solvent, then place them in a vacuum drying oven, and dry them at a temperature of 50-55°C for 2-3 hours to obtain a modified methyl MQ resin.

[0013] As a further solution of the present invention: the usage ratio of the 2,6-dimethylbromobenzene, perfluorohexylethanol, anhydrous potassium carbonate and anhydrous acetone in step a1 is 10 mmol: 10 mmol: 15-20 mmol: 70-80 mL.

[0014] As a further scheme of the present invention: the usage ratio of the intermediate 1, sodium hydroxide, 2-methyl-2-propanol, deionized water, potassium permanganate and sodium sulfite in step a2 is 10 mmol: 25-30 mmol: 30-35 mL: 30-35 mL: 10-15 g: 6-10 g.

[0015] As a further solution of the present invention: the mass fraction of the hydrochloric acid solution in step a2 is 25-30%.

[0016] As a further solution of the present invention: the usage ratio of the intermediate 2, 2-mercaptoethanol, p-toluenesulfonic acid and cyclohexane in step a3 is 10 mmol: 20 mmol: 0.02-0.04 g: 70-80 mL.

[0017] As a further scheme of the present invention: the dosage ratio of the hexamethyldisiloxane, tetramethyldivinyldisiloxane, deionized water, anhydrous ethanol, hydrochloric acid solution, tetraethoxysilane and resin modifier in step a4 is 3.5-6.5g:1.2-4.8g:8-12mL:15-21mL:0.5-1.5mL:7-11g:0.3-1.9g.

[0018] As a further solution of the present invention: the mass fraction of the hydrochloric acid solution in step a4 is 25-30%.

[0019] As a further solution of the present invention: a method for preparing a high-performance pressure-sensitive adhesive based on modified methyl MQ resin comprises the following steps:

[0020] Step 1: Weigh 10 parts of silicone rubber, 0.8-5.2 parts of modified methyl MQ resin, 9-13 parts of toluene and 0.05-0.15 parts of dibenzoyl peroxide according to weight, and set aside;

[0021] Step 2: Add silicone rubber, modified methyl MQ resin and toluene to a three-necked flask equipped with a stirrer, a thermometer and an air duct, introduce nitrogen protection, stir and react for 20-30 minutes at a temperature of 25-30°C and a stirring rate of 300-400r / min, then heat to 50-55°C and continue stirring and reacting for 2-3 hours, then add dibenzoyl peroxide and continue stirring and reacting for 2-3 hours, and after the reaction is completed, cool the reaction product to room temperature to obtain a high-performance pressure-sensitive adhesive based on modified methyl MQ resin.

[0022] As a further solution of the present invention: the silicone rubber is methyl vinyl silicone rubber with a model number of 110-5S.

[0023] Beneficial effects of the present invention:

[0024] The present invention discloses a high-performance pressure-sensitive adhesive based on modified methyl MQ resin and a preparation method thereof. The method comprises the steps of stirring silicone rubber, modified methyl MQ resin and toluene, and then adding dibenzoyl peroxide and continuing stirring the reaction, so as to obtain a high-performance pressure-sensitive adhesive based on modified methyl MQ resin. The high-performance pressure-sensitive adhesive has excellent bonding strength, and at the same time, excellent adaptability and stability, so that it can maintain excellent bonding performance in both high temperature and humid environments, so that it can be better applied to different fields such as electronic components, mobile phone screen bonding, and automobile interiors, and effectively solves the problem that the original pressure-sensitive adhesive is easy to fail in high temperature and humid environments. In addition, the preparation method is easy to operate and has low cost, and can meet the needs of large-scale production, providing new possibilities for the innovation and development of pressure-sensitive adhesives, and greatly improving production efficiency and product quality.

[0025] In the process of preparing a high-performance pressure-sensitive adhesive based on modified methyl MQ resin, a modified methyl MQ resin is first prepared, 2,6-dimethylbromobenzene and perfluorohexylethanol are reacted, the bromine atom on 2,6-dimethylbromobenzene reacts with the hydroxyl group on perfluorohexylethanol, a large number of CF bonds are introduced, and intermediate 1 is obtained. Then, potassium permanganate is used to oxidize the methyl group on intermediate 1 into a carboxyl group to obtain intermediate 2. Then, intermediate 2 and 2-mercaptoethanol are reacted, the carboxyl group on intermediate 2 and the hydroxyl group on 2-mercaptoethanol undergo an esterification reaction, and a mercapto group is introduced to obtain a resin modifier. Then, hexamethyldisiloxane, tetramethyldivinyldisiloxane and tetraethoxysilane are used as polymerization monomers for polymerization. A methyl MQ resin containing alkenyl groups is formed, and a click chemical reaction is carried out between the mercapto group on the resin modifier and the alkenyl group on the methyl MQ resin containing alkenyl groups to form a cross-linked network to obtain a modified methyl MQ resin. Finally, the silicone rubber is modified by the modified methyl MQ resin, and further cross-linked under the initiation of dibenzoyl peroxide to obtain a high-performance pressure-sensitive adhesive based on the modified methyl MQ resin. The modified methyl MQ resin can greatly improve the high temperature resistance and water and chemical resistance of the pressure-sensitive adhesive by introducing a large number of CF bonds, and can improve the density of the pressure-sensitive adhesive by improving the cross-linking degree of the pressure-sensitive adhesive, and can further improve the comprehensive performance of the pressure-sensitive adhesive, so that the pressure-sensitive adhesive can meet the application requirements in the high-performance field. DETAILED DESCRIPTION

[0026] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] Example 1: This example is a method for preparing a high-performance pressure-sensitive adhesive based on modified methyl MQ resin, comprising the following steps:

[0028] Step S1: 10 mmol 2,6-dimethylbromobenzene, 10 mmol perfluorohexylethanol, 15 mmol anhydrous potassium carbonate and 70 mL anhydrous acetone were added to a three-necked flask equipped with a stirrer, a thermometer and an air guide tube, and nitrogen was introduced for protection. The mixture was stirred at 25° C. and a stirring rate of 300 r / min for 20 min, and then the temperature was raised to 95° C. and the stirring reaction was continued for 3 h. After the reaction was completed, the reaction product was cooled to room temperature, and then vacuum filtered, and the filtrate was rotary evaporated to remove the solvent to obtain intermediate 1;

[0029] Step S2: 10 mmol of intermediate 1, 25 mmol of sodium hydroxide, 30 mL of 2-methyl-2-propanol and 30 mL of deionized water are added to a three-necked flask equipped with a stirrer, a thermometer and an air guide tube, and nitrogen is introduced for protection. The mixture is stirred and reacted for 20 min at a temperature of 25° C. and a stirring rate of 300 r / min. Then, 10 g of potassium permanganate is added and the mixture is heated to 70° C. and the stirring reaction is continued for 10 h. Then, 6 g of sodium sulfite is added and the stirring reaction is continued for 1 h. Then, the mixture is filtered while hot, and the filtrate is cooled to below 5° C., and then the pH value is adjusted to 1 with a hydrochloric acid solution having a mass fraction of 25%, and then vacuum filtered. The filter cake is placed in a vacuum drying oven and dried at a temperature of 50° C. for 2 h to obtain intermediate 2;

[0030] Step S3: 10 mmol of intermediate 2, 20 mmol of 2-mercaptoethanol, 0.02 g of p-toluenesulfonic acid and 70 mL of cyclohexane were added to a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at 25° C. and a stirring rate of 300 r / min for 20 min, and then the temperature was raised to 90° C. and the stirring reaction was continued for 6 h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation to obtain a resin modifier;

[0031] Step S4: 3.5 g of hexamethyldisiloxane, 1.2 g of tetramethyldivinyldisiloxane, 8 mL of deionized water, 15 mL of anhydrous ethanol and 0.5 mL of a 25% hydrochloric acid solution were added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a constant pressure dropping funnel, and nitrogen was introduced for protection. The mixture was stirred for reaction at a temperature of 25° C. and a stirring rate of 300 r / min for 20 min, and then 7 g of tetraethoxysilane was added dropwise while stirring, and the dropping rate was controlled to be 1 drop / s. After the addition was completed, the mixture was heated to 40° C. and continued to stir for reaction for 2 h, and then 0.3 g of a resin modifier was added and continued to stir for reaction for 2 h. After the reaction was completed, the reaction product was cooled to room temperature, and then extracted with toluene twice. The extracts were combined and rotary evaporated to remove the solvent, and then placed in a vacuum drying oven and dried at a temperature of 50° C. for 2 h to obtain a modified methyl MQ resin;

[0032] Step S5: 10 parts of silicone rubber, 0.8 parts of modified methyl MQ resin, 9 parts of toluene and 0.05 parts of dibenzoyl peroxide are weighed in parts by weight for later use; the silicone rubber is 110-5S methyl vinyl silicone rubber;

[0033] Step S6: Add silicone rubber, modified methyl MQ resin and toluene into a three-necked flask equipped with a stirrer, a thermometer and an air duct, introduce nitrogen protection, stir and react for 20 minutes at a temperature of 25°C and a stirring rate of 300r / min, then heat to 50°C and continue stirring and reacting for 2 hours, then add dibenzoyl peroxide and continue stirring and reacting for 2 hours, and after the reaction is completed, cool the reaction product to room temperature to obtain a high-performance pressure-sensitive adhesive based on modified methyl MQ resin.

[0034] Example 2: This example is a method for preparing a high-performance pressure-sensitive adhesive based on modified methyl MQ resin, comprising the following steps:

[0035] Step S1: 10 mmol 2,6-dimethylbromobenzene, 10 mmol perfluorohexylethanol, 18 mmol anhydrous potassium carbonate and 75 mL anhydrous acetone were added to a three-necked flask equipped with a stirrer, a thermometer and an air guide tube, and nitrogen was introduced for protection. The mixture was stirred at 28° C. and a stirring rate of 350 r / min for 25 min, and then the mixture was heated to 98° C. and stirred for 3.5 h. After the reaction was completed, the reaction product was cooled to room temperature, and then vacuum filtered, and the filtrate was rotary evaporated to remove the solvent to obtain intermediate 1;

[0036] Step S2: 10 mmol of intermediate 1, 28 mmol of sodium hydroxide, 32 mL of 2-methyl-2-propanol and 32 mL of deionized water were added to a three-necked flask equipped with a stirrer, a thermometer and an air guide tube, and nitrogen was introduced for protection. The mixture was stirred for reaction at a temperature of 28° C. and a stirring rate of 350 r / min for 25 min. Then, 12 g of potassium permanganate was added and the mixture was heated to 72° C. and the stirring reaction was continued for 12 h. Then, 8 g of sodium sulfite was added and the stirring reaction was continued for 1 h. Then, the mixture was filtered while hot, and the filtrate was cooled to below 5° C., and then the pH value was adjusted to 1.5 with a hydrochloric acid solution having a mass fraction of 28%, and then vacuum filtered. The filter cake was placed in a vacuum drying oven and dried at a temperature of 52° C. for 2.5 h to obtain intermediate 2;

[0037] Step S3: 10 mmol of intermediate 2, 20 mmol of 2-mercaptoethanol, 0.03 g of p-toluenesulfonic acid and 75 mL of cyclohexane were added to a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at 28° C. and a stirring rate of 350 r / min for 25 min, and then the mixture was heated to 92° C. and stirred for 6.5 h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation to obtain a resin modifier;

[0038] Step S4: 5 g of hexamethyldisiloxane, 3 g of tetramethyldivinyldisiloxane, 10 mL of deionized water, 19 mL of anhydrous ethanol and 1 mL of a 28% hydrochloric acid solution were added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a constant pressure dropping funnel, and nitrogen was introduced for protection. The mixture was stirred for reaction at a temperature of 28° C. and a stirring rate of 350 r / min for 25 min, and then 9 g of tetraethoxysilane was added dropwise while stirring, and the dropping rate was controlled to be 1 drop / s. After the addition was completed, the mixture was heated to 42° C. and continued to stir for reaction for 2.5 h. Then 1.1 g of a resin modifier was added and continued to stir for reaction for 2.5 h. After the reaction was completed, the reaction product was cooled to room temperature, and then extracted with toluene twice. The extracts were combined and rotary evaporated to remove the solvent, and then placed in a vacuum drying oven and dried at a temperature of 52° C. for 2.5 h to obtain a modified methyl MQ resin;

[0039] Step S5: 10 parts of silicone rubber, 3 parts of modified methyl MQ resin, 11 parts of toluene and 0.1 parts of dibenzoyl peroxide are weighed in parts by weight for later use; the silicone rubber is 110-5S methyl vinyl silicone rubber;

[0040] Step S6: Add silicone rubber, modified methyl MQ resin and toluene into a three-necked flask equipped with a stirrer, a thermometer and an air duct, introduce nitrogen protection, stir and react for 25 minutes at a temperature of 28°C and a stirring rate of 350 r / min, then raise the temperature to 52°C and continue to stir and react for 2.5 hours, then add dibenzoyl peroxide and continue to stir and react for 2.5 hours. After the reaction, cool the reaction product to room temperature to obtain a high-performance pressure-sensitive adhesive based on modified methyl MQ resin.

[0041] Example 3: This example is a method for preparing a high-performance pressure-sensitive adhesive based on modified methyl MQ resin, comprising the following steps:

[0042] Step S1: 10 mmol 2,6-dimethylbromobenzene, 10 mmol perfluorohexylethanol, 20 mmol anhydrous potassium carbonate and 80 mL anhydrous acetone were added to a three-necked flask equipped with a stirrer, a thermometer and an air guide tube, and nitrogen was introduced for protection. The mixture was stirred at 30° C. and a stirring rate of 400 r / min for 30 min, and then the mixture was heated to 100° C. and the stirring reaction was continued for 4 h. After the reaction was completed, the reaction product was cooled to room temperature, and then vacuum filtered, and the filtrate was rotary evaporated to remove the solvent to obtain intermediate 1;

[0043] Step S2: 10 mmol of intermediate 1, 30 mmol of sodium hydroxide, 35 mL of 2-methyl-2-propanol and 35 mL of deionized water were added to a three-necked flask equipped with a stirrer, a thermometer and an air guide tube, and nitrogen was introduced for protection. The mixture was stirred and reacted for 30 min at a temperature of 30° C. and a stirring rate of 400 r / min. Then, 15 g of potassium permanganate was added and the temperature was raised to 75° C. and the stirring reaction was continued for 15 h. Then, 10 g of sodium sulfite was added and the stirring reaction was continued for 1.5 h. Then, the mixture was filtered while hot, and the filtrate was cooled to below 5° C., and then the pH was adjusted to 2 with a hydrochloric acid solution with a mass fraction of 30%, and then vacuum filtered. The filter cake was placed in a vacuum drying oven and dried at a temperature of 55° C. for 3 h to obtain intermediate 2;

[0044] Step S3: 10 mmol of intermediate 2, 20 mmol of 2-mercaptoethanol, 0.04 g of p-toluenesulfonic acid and 80 mL of cyclohexane were added to a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at a temperature of 30° C. and a stirring rate of 400 r / min for 30 min, and then the temperature was raised to 95° C. and the stirring reaction was continued for 7 h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation to obtain a resin modifier;

[0045] Step S4: 6.5 g of hexamethyldisiloxane, 4.8 g of tetramethyldivinyldisiloxane, 12 mL of deionized water, 21 mL of anhydrous ethanol and 1.5 mL of a 30% hydrochloric acid solution were added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a constant pressure dropping funnel, and nitrogen was introduced for protection. The mixture was stirred for reaction at a temperature of 30° C. and a stirring rate of 400 r / min for 30 min, and then 11 g of tetraethoxysilane was added dropwise while stirring, and the dropping rate was controlled to be 2 drops / s. After the addition was completed, the mixture was heated to 45° C. and continued to stir for reaction for 3 h, and then 1.9 g of a resin modifier was added and continued to stir for reaction for 3 h. After the reaction was completed, the reaction product was cooled to room temperature, and then extracted with toluene 3 times. The extracts were combined and rotary evaporated to remove the solvent, and then placed in a vacuum drying oven and dried at a temperature of 55° C. for 3 h to obtain a modified methyl MQ resin;

[0046] Step S5: 10 parts of silicone rubber, 5.2 parts of modified methyl MQ resin, 13 parts of toluene and 0.15 parts of dibenzoyl peroxide are weighed in parts by weight for later use; the silicone rubber is 110-5S methyl vinyl silicone rubber;

[0047] Step S6: Add silicone rubber, modified methyl MQ resin and toluene into a three-necked flask equipped with a stirrer, a thermometer and an air duct, introduce nitrogen protection, stir and react for 30 minutes at a temperature of 30°C and a stirring rate of 400r / min, then heat to 55°C and continue stirring and reacting for 3 hours, then add dibenzoyl peroxide and continue stirring and reacting for 3 hours, and after the reaction is completed, cool the reaction product to room temperature to obtain a high-performance pressure-sensitive adhesive based on modified methyl MQ resin.

[0048] Comparative Example 1:

[0049] This comparative example is a method for preparing a high-performance pressure-sensitive adhesive based on modified methyl MQ resin, comprising the following steps:

[0050] Step S1: 10 parts of silicone rubber, 13 parts of toluene and 0.15 parts of dibenzoyl peroxide are weighed in parts by weight for later use; the silicone rubber is 110-5S methyl vinyl silicone rubber;

[0051] Step S2: Add silicone rubber and toluene into a three-necked flask equipped with a stirrer, a thermometer and an air duct, introduce nitrogen protection, stir and react for 30 minutes at a temperature of 30°C and a stirring rate of 400 r / min, then raise the temperature to 55°C and continue to stir and react for 3 hours, then add dibenzoyl peroxide and continue to stir and react for 3 hours, and after the reaction is completed, cool the reaction product to room temperature to obtain a high-performance pressure-sensitive adhesive based on modified methyl MQ resin.

[0052] Comparative Example 2:

[0053] This comparative example is a method for preparing a high-performance pressure-sensitive adhesive based on modified methyl MQ resin, comprising the following steps:

[0054] Step S1: 6.5 g of hexamethyldisiloxane, 4.8 g of tetramethyldivinyldisiloxane, 12 mL of deionized water, 21 mL of anhydrous ethanol and 1.5 mL of a 30% hydrochloric acid solution were added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a constant pressure dropping funnel, and nitrogen was introduced for protection. The mixture was stirred for reaction at a temperature of 30° C. and a stirring rate of 400 r / min for 30 min, and then 11 g of tetraethoxysilane was added dropwise while stirring, and the dropping rate was controlled to be 2 drops / s. After the dropwise addition was completed, the mixture was heated to 45° C. and continued to stir for reaction for 3 h. After the reaction was completed, the reaction product was cooled to room temperature, and then extracted with toluene 3 times. The extracts were combined and rotary evaporated to remove the solvent, and then placed in a vacuum drying oven and dried at a temperature of 55° C. for 3 h to obtain a modified methyl MQ resin;

[0055] Step S2: 10 parts of silicone rubber, 5.2 parts of modified methyl MQ resin, 13 parts of toluene and 0.15 parts of dibenzoyl peroxide are weighed in parts by weight for later use; the silicone rubber is 110-5S methyl vinyl silicone rubber;

[0056] Step S3: Add silicone rubber, modified methyl MQ resin and toluene into a three-necked flask equipped with a stirrer, a thermometer and an air duct, introduce nitrogen protection, stir and react for 30 minutes at a temperature of 30°C and a stirring rate of 400 r / min, then heat to 55°C and continue stirring and reacting for 3 hours, then add dibenzoyl peroxide and continue stirring and reacting for 3 hours, and after the reaction is completed, cool the reaction product to room temperature to obtain a high-performance pressure-sensitive adhesive based on modified methyl MQ resin.

[0057] Comparative Example 3:

[0058] This comparative example is a method for preparing a high-performance pressure-sensitive adhesive based on modified methyl MQ resin, comprising the following steps:

[0059] Step S1: 10 mmol 2,6-dimethylbromobenzene, 30 mmol sodium hydroxide, 35 mL 2-methyl-2-propanol and 35 mL deionized water were added to a three-necked flask equipped with a stirrer, a thermometer and an air guide tube, and nitrogen was introduced for protection. The mixture was stirred for reaction at a temperature of 30° C. and a stirring rate of 400 r / min for 30 min. Then, 15 g potassium permanganate was added and the mixture was heated to 75° C. and the stirring reaction was continued for 15 h. Then, 10 g sodium sulfite was added and the stirring reaction was continued for 1.5 h. Then, the mixture was filtered while hot, and the filtrate was cooled to below 5° C., and then the pH value was adjusted to 2 with a hydrochloric acid solution having a mass fraction of 30%, and then vacuum filtered. The filter cake was placed in a vacuum drying oven and dried at a temperature of 55° C. for 3 h to obtain an intermediate 3.

[0060] Step S2: 10 mmol of intermediate 3, 20 mmol of 2-mercaptoethanol, 0.04 g of p-toluenesulfonic acid and 80 mL of cyclohexane were added to a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at a temperature of 30° C. and a stirring rate of 400 r / min for 30 min, and then the temperature was raised to 95° C. and the stirring reaction was continued for 7 h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation to obtain a resin modifier;

[0061] Step S3: 6.5 g of hexamethyldisiloxane, 4.8 g of tetramethyldivinyldisiloxane, 12 mL of deionized water, 21 mL of anhydrous ethanol and 1.5 mL of a 30% hydrochloric acid solution were added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a constant pressure dropping funnel, and nitrogen was introduced for protection. The mixture was stirred for reaction for 30 min at a temperature of 30 ° C and a stirring rate of 400 r / min. Then, 11 g of tetraethoxysilane was added dropwise while stirring, and the dropping rate was controlled to be 2 drops / s. After the addition was completed, the mixture was heated to 45 ° C and continued to stir for 3 h. Then, 1.9 g of a resin modifier was added and continued to stir for 3 h. After the reaction was completed, the reaction product was cooled to room temperature, and then extracted with toluene 3 times. The extracts were combined and rotary evaporated to remove the solvent, and then placed in a vacuum drying oven and dried at a temperature of 55 ° C for 3 h to obtain a modified methyl MQ resin;

[0062] Step S4: 10 parts of silicone rubber, 5.2 parts of modified methyl MQ resin, 13 parts of toluene and 0.15 parts of dibenzoyl peroxide are weighed in parts by weight for later use; the silicone rubber is 110-5S methyl vinyl silicone rubber;

[0063] Step S5: Add silicone rubber, modified methyl MQ resin and toluene into a three-necked flask equipped with a stirrer, a thermometer and an air duct, introduce nitrogen protection, stir and react for 30 minutes at a temperature of 30°C and a stirring rate of 400r / min, then raise the temperature to 55°C and continue to stir and react for 3 hours, then add dibenzoyl peroxide and continue to stir and react for 3 hours, and after the reaction is completed, cool the reaction product to room temperature to obtain a high-performance pressure-sensitive adhesive based on modified methyl MQ resin.

[0064] The high-performance pressure-sensitive adhesive based on modified methyl MQ resin of Examples 1-3 and Comparative Examples 1-3 was coated on a PET film with a thickness of 50 μm, and then placed in a vacuum drying oven, dried at a temperature of 130° C. for 5 minutes, and cured to form a pressure-sensitive adhesive tape with a dry adhesive thickness of 30 μm;

[0065] The pressure-sensitive adhesive tape is attached to a stainless steel plate, and the 180° peel strength is tested at room temperature according to the GB / T 2792-1998 method to obtain a first peel strength;

[0066] The pressure-sensitive adhesive tape was placed in a vacuum drying oven and baked at 200°C for 30 minutes, then taken out and cooled to room temperature, and then the 180° peel strength was tested according to the GB / T 2792-1998 method to obtain the second peel strength;

[0067] The pressure-sensitive tape was soaked in boiling water for 1 hour, then taken out and placed in a vacuum drying oven, dried at 50°C for 2 hours, then taken out and cooled to room temperature, and then tested for 180° peel strength according to the GB / T 2792-1998 method to obtain the third peel strength.

[0068] The test results are shown in the following table:

[0069] .

[0070] Referring to the data in the above table, based on the comparison between Examples 1-3 and Comparative Examples 1-3, it can be known that the high-performance pressure-sensitive adhesive based on the modified methyl MQ resin of the present application has excellent peel strength and still has high performance in high temperature environment and water environment.

[0071] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0072] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined in this application, they shall all fall within the protection scope of the present invention.

Claims

1. A high-performance pressure-sensitive adhesive based on modified methyl MQ resin, characterized in that: It comprises the following components in parts by weight: 10 parts of silicone rubber, 0.8-5.2 parts of modified methyl MQ resin, 9-13 parts of toluene and 0.05-0.15 parts of dibenzoyl peroxide; Wherein, the modified methyl MQ resin is prepared by the following steps: Step a1: Add 2,6-dimethylbromobenzene, perfluorohexylethanol, anhydrous potassium carbonate and anhydrous acetone into a three-necked flask equipped with a stirrer, a thermometer and an air guide tube, introduce nitrogen protection, stir and react for 20-30 minutes at a temperature of 25-30° C. and a stirring rate of 300-400 r / min, then heat to 95-100° C. and continue stirring and reacting for 3-4 hours. After the reaction is completed, the reaction product is cooled to room temperature, then vacuum filtered, and the filtrate is rotary evaporated to remove the solvent to obtain intermediate 1; Step a2: Add intermediate 1, sodium hydroxide, 2-methyl-2-propanol and deionized water to a three-necked flask equipped with a stirrer, a thermometer and an air guide tube, introduce nitrogen protection, stir and react for 20-30 minutes at a temperature of 25-30° C. and a stirring rate of 300-400 r / min, then add potassium permanganate and continue to stir and react for 10-15 hours under the condition of heating to 70-75° C., then add sodium sulfite and continue to stir and react for 1-1.5 hours, then filter while hot, cool the filtrate to below 5° C., then adjust the pH to 1-2 with hydrochloric acid solution, then vacuum filter, place the filter cake in a vacuum drying oven, and dry it at a temperature of 50-55° C. for 2-3 hours to obtain intermediate 2; Step a3: Add intermediate 2, 2-mercaptoethanol, p-toluenesulfonic acid and cyclohexane to a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, introduce nitrogen protection, stir and react for 20-30 minutes at a temperature of 25-30° C. and a stirring rate of 300-400 r / min, then heat to 90-95° C. and continue stirring and reacting for 6-7 hours. After the reaction is completed, the reaction product is cooled to room temperature, and then the solvent is removed by rotary evaporation to obtain a resin modifier; Step a4: add hexamethyldisiloxane, tetramethyldivinyldisiloxane, deionized water, anhydrous ethanol and hydrochloric acid solution to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a constant pressure dropping funnel, introduce nitrogen protection, stir and react for 20-30 minutes at a temperature of 25-30°C and a stirring rate of 300-400r / min, then add tetraethoxysilane dropwise while stirring, and control the dropping rate to 1-2 drops / s. After the dropwise addition is completed, continue to stir and react for 2-3 hours at a temperature of 40-45°C, then add a resin modifier and continue to stir and react for 2-3 hours. After the reaction is completed, cool the reaction product to room temperature, then extract it with toluene 2-3 times, combine the extracts and rotary evaporate them to remove the solvent, then place them in a vacuum drying oven, and dry them at a temperature of 50-55°C for 2-3 hours to obtain a modified methyl MQ resin.

2. The high-performance pressure-sensitive adhesive based on modified methyl MQ resin according to claim 1, characterized in that: The usage ratio of the 2,6-dimethylbromobenzene, perfluorohexylethanol, anhydrous potassium carbonate and anhydrous acetone in step a1 is 10 mmol: 10 mmol: 15-20 mmol: 70-80 mL.

3. The high-performance pressure-sensitive adhesive based on modified methyl MQ resin according to claim 1, characterized in that: The usage ratio of the intermediate 1, sodium hydroxide, 2-methyl-2-propanol, deionized water, potassium permanganate and sodium sulfite in step a2 is 10 mmol: 25-30 mmol: 30-35 mL: 30-35 mL: 10-15 g: 6-10 g.

4. The high-performance pressure-sensitive adhesive based on modified methyl MQ resin according to claim 1, characterized in that: The mass fraction of the hydrochloric acid solution in step a2 is 25-30%.

5. The high performance pressure sensitive adhesive based on modified methyl MQ resin according to claim 1, characterized in that: The usage ratio of the intermediate 2, 2-mercaptoethanol, p-toluenesulfonic acid and cyclohexane in step a3 is 10 mmol: 20 mmol: 0.02-0.04 g: 70-80 mL.

6. The high-performance pressure-sensitive adhesive based on modified methyl MQ resin according to claim 1, characterized in that: The dosage ratio of the hexamethyldisiloxane, tetramethyldivinyldisiloxane, deionized water, anhydrous ethanol, hydrochloric acid solution, tetraethoxysilane and resin modifier in step a4 is 3.5-6.5g:1.2-4.8g:8-12mL:15-21mL:0.5-1.5mL:7-11g:0.3-1.9g.

7. The high-performance pressure-sensitive adhesive based on modified methyl MQ resin according to claim 1, characterized in that: The mass fraction of the hydrochloric acid solution in step a4 is 25-30%.

8. A method for preparing a high-performance pressure-sensitive adhesive based on modified methyl MQ resin, characterized in that: The following steps are involved: Step 1: Weigh 10 parts of silicone rubber, 0.8-5.2 parts of modified methyl MQ resin, 9-13 parts of toluene and 0.05-0.15 parts of dibenzoyl peroxide according to weight, and set aside; Step 2: Add silicone rubber, modified methyl MQ resin and toluene to a three-necked flask equipped with a stirrer, a thermometer and an air duct, introduce nitrogen protection, stir and react for 20-30 minutes at a temperature of 25-30°C and a stirring rate of 300-400r / min, then heat to 50-55°C and continue stirring and reacting for 2-3 hours, then add dibenzoyl peroxide and continue stirring and reacting for 2-3 hours, and after the reaction is completed, cool the reaction product to room temperature to obtain a high-performance pressure-sensitive adhesive based on modified methyl MQ resin.

9. The method for preparing a high-performance pressure-sensitive adhesive based on modified methyl MQ resin according to claim 8, characterized in that: The silicone rubber is methyl vinyl silicone rubber with model number 110-5S.