High-viscosity / high-temperature-resistant organic silicon pressure-sensitive adhesive based on mussel viscosity effect and preparation method

Abstract

The invention relates to the field of organic silicon pressure-sensitive adhesives, in particular to a high-viscosity / high-temperature-resistant organic silicon pressure-sensitive adhesive based on a mussel viscosity effect and a preparation method. The problems of low adhesive force and poor high-temperature resistance of an organic silicon pressure-sensitive adhesive formed by a common technology are solved. Comprising octamethylcyclotetrasiloxane, aminopropyl siloxane, deionized water, polyphenol similar to mussel adhesion protein, an initiator, synthesized polyphenol modified aminopropyl silicone rubber, vinyl MQ resin and an organic solvent. According to the invention, the adhesion performance and high temperature resistance of the organic silicon pressure-sensitive adhesive are adjusted by adjusting the ratio of the aminopropyl siloxane monomer to the octamethylcyclotetrasiloxane monomer.

Description

Technical Field

[0001] The invention relates to the field of organosilicon pressure-sensitive adhesives, and in particular to a high-viscosity / high-temperature-resistant organosilicon pressure-sensitive adhesive based on the viscosity effect of mussels and a preparation method thereof. Background Art

[0002] At present, there are three main types of pressure-sensitive adhesives in the market: acrylic, rubber-type pressure-sensitive adhesives and silicone pressure-sensitive adhesives. Compared with the previous two, silicone pressure-sensitive adhesives are new polymer silicone materials. Silicone materials have the advantages of high and low temperature resistance, surface hydrophobicity, harmlessness to the human body, excellent electrochemistry, and chemical inertness, which makes silicone pressure-sensitive adhesives have good application prospects and have been rapidly and widely used and developed in the fields of medical and electronic industries.

[0003] At present, the basic research and development of SPSA is relatively weak, and the product adhesion is generally low, which leads to problems such as shedding and peeling in actual applications. This phenomenon is particularly obvious in high temperature and high humidity environments. In addition, the stability is insufficient in high temperature environments, and it is easy to soften and flow, which affects the service life and reliability.

[0004] Therefore, it is urgent to propose a high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive and a preparation method based on the mussel viscosity effect to solve the above-mentioned technical problems. Summary of the invention

[0005] The purpose of the present invention is to solve the problems of low adhesion and poor high temperature resistance of the silicone pressure-sensitive adhesive formed by the common technology. A brief overview of the present invention is given below to provide a basic understanding of certain aspects of the present invention. It should be understood that this overview is not an exhaustive overview of the present invention. It is not intended to determine the key or important parts of the present invention, nor is it intended to limit the scope of the present invention.

[0006] The technical solution of the present invention:

[0007] A high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive based on the mussel adhesion effect, wherein the mussel adhesion effect-enhanced silicone pressure-sensitive adhesive is composed of octamethylcyclotetrasiloxane, aminopropyl siloxane, deionized water, mussel adhesion protein-like polyphenols, an initiator, a synthetic polyphenol-modified aminopropyl silicone rubber, a vinyl MQ resin, and an organic solvent;

[0008] The mass fraction of octamethylcyclotetrasiloxane is 17.8-41.5 parts, the mass fraction of aminopropyl siloxane is 10.8-32.4 parts, the mass fraction of deionized water is 1.6-5.2 parts, the mass fraction of mussel adhesion protein-like polyphenol is 3.4-6.8 parts, the mass fraction of initiator is 0.02-0.08 parts, the mass fraction of synthetic polyphenol-modified aminopropyl silicone rubber is 20-40 parts, the mass fraction of vinyl MQ resin is 10-30 parts, and the mass fraction of organic solvent is 30 parts.

[0009] Preferably, the aminopropylsiloxane is one or more of γ-aminopropyldiethoxysilane, N-(β-aminoethyl-γ-aminopropyl)methyldimethoxysilane, aminoethylaminoisobutylmethyldimethoxysilane, and 3-aminopropyldimethoxymethylsilane.

[0010] Preferably, the polyphenol of the mussel adhesion protein-like material is one or more of 3,4,5-trihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3-(3,4-dihydroxyphenyl)-DL-alanine and 2,4,6-trihydroxybenzoic acid.

[0011] A method for preparing a high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive based on the mussel viscosity effect comprises the following steps:

[0012] Step 1: Add aminopropylsiloxane into a reaction vessel, add deionized water to hydrolyze at room temperature, stir evenly, and introduce nitrogen;

[0013] Step 2: Heat the reaction vessel to 60°C and distill under reduced pressure for 1 to 2 hours while stirring evenly;

[0014] Step 3: Add octamethylcyclotetrasiloxane and alkali into a reaction vessel, stir evenly, and introduce nitrogen for purging;

[0015] Step 4: Heat the reaction vessel and stir evenly. After 1 to 1.5 hours of polymerization reaction, purge with nitrogen and continue the reaction for 1 to 3 hours.

[0016] Step 5: Heat the reaction vessel to 160°C, react for 0.5h, and then cool to 70°C;

[0017] Step 6: dissolving the polyphenol in anhydrous ethanol, pouring the solution into the reaction container after the reaction container cools down, stirring evenly and introducing nitrogen, reacting for 1 to 1.5 hours, cooling to room temperature after the reaction is completed, and preparing polyphenol-modified aminopropyl silicone rubber;

[0018] Step 7: placing the polyphenol-modified aminopropyl silicone rubber and the vinyl MQ resin in a reaction container, adding an organic solvent to dissolve them, heating the reaction container, stirring evenly and introducing nitrogen, and reacting for 1 to 2 hours to obtain an organic silicone pressure-sensitive adhesive;

[0019] Step 8: Coat the silicone pressure-sensitive adhesive on the PI and PE films, place in a vacuum oven at 180°C, take out and age at room temperature for 24 hours to prepare a high-viscosity / high-temperature resistant silicone pressure-sensitive adhesive.

[0020] Preferably, the hydrolysis time in step 1 is 0.5-1.0 h, the purging time in step 3 is 5 min, the temperature of the reaction container in step 4 is raised to 110-120° C., and the temperature of the reaction container in step 7 is raised to 60° C.

[0021] Preferably, in step eight, the vacuum oven temperature is 180° C., the curing time is 5 to 15 minutes, and the aging time is 24 hours.

[0022] The present invention has the following beneficial effects:

[0023] The present invention adjusts the adhesion performance and high temperature resistance of the organic silicon pressure-sensitive adhesive by adjusting the ratio of the aminopropylsiloxane monomer and the octamethylcyclotetrasiloxane monomer.

[0024] The present invention adjusts the adhesion performance and high temperature resistance of the silicone pressure-sensitive adhesive by adjusting the types of aminopropyl monomers and mussel adhesion protein-like polyphenol monomers;

[0025] The invention adjusts the adhesion performance and high temperature resistance of the organic silicon pressure-sensitive adhesive by adjusting the ratio of silicone rubber and silicone resin. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is described below by specific embodiments. However, it should be understood that these descriptions are only exemplary and are not intended to limit the scope of the present invention. In addition, in the following description, the description of well-known structures and technologies is omitted to avoid unnecessary confusion of the concept of the present invention.

[0027] Specific implementation method 1: The high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive based on the mussel adhesion effect of this implementation method, the mussel adhesion effect enhanced silicone pressure-sensitive adhesive is composed of octamethylcyclotetrasiloxane, aminopropyl siloxane, deionized water, mussel adhesion protein-like polyphenols, initiator, synthetic polyphenol-modified aminopropyl silicone rubber, vinyl MQ resin, and organic solvent;

[0028] The mass fraction of octamethylcyclotetrasiloxane is 17.8-41.5 parts, the mass fraction of aminopropyl siloxane is 10.8-32.4 parts, the mass fraction of deionized water is 1.6-5.2 parts, the mass fraction of mussel adhesion protein-like polyphenol is 3.4-6.8 parts, the mass fraction of initiator is 0.02-0.08 parts, the mass fraction of synthetic polyphenol-modified aminopropyl silicone rubber is 20-40 parts, the mass fraction of vinyl MQ resin is 10-30 parts, and the mass fraction of organic solvent is 30 parts.

[0029] Specific embodiment 2: In this embodiment of the high-viscosity / high-temperature resistant silicone pressure-sensitive adhesive based on the mussel viscosity effect, the aminopropyl siloxane is one or more of Y-aminopropyldiethoxysilane, N-(β-aminoethyl-Y-aminopropyl)methyldimethoxysilane, aminoethylaminoisobutylmethyldimethoxysilane, and 3-aminopropyldimethoxymethylsilane.

[0030] Specific implementation method three: In this implementation method, the high-viscosity / high-temperature resistant silicone pressure-sensitive adhesive based on the mussel viscosity effect, the polyphenol of the mussel adhesion protein is one or more of 3,4,5-trihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3-(3,4-dihydroxyphenyl)-DL-alanine, and 2,4,6-trihydroxybenzoic acid.

[0031] Specific embodiment 4: The preparation method of the high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive based on the mussel viscosity effect of this embodiment comprises the following steps:

[0032] Step 1: placing aminopropylsiloxane in a reaction vessel, and adding deionized water for hydrolysis at room temperature for 0.5 to 1.0 h, while stirring evenly and introducing nitrogen;

[0033] Step 2: Heat the reaction vessel to 60°C and distill under reduced pressure for 1 to 2 hours while stirring evenly.

[0034] Step 3: Add octamethylcyclotetrasiloxane and alkali into a reaction vessel, stir evenly, and purge with nitrogen for 5 minutes to remove oxygen in the system;

[0035] Step 4: Heat the reaction vessel to 110-120°C, condense and reflux, and stir evenly. After 1-1.5 hours of polymerization reaction, purge with nitrogen to remove water produced during the polymerization process to increase the degree of polymerization. Continue the reaction for 1-3 hours. The molecular weight can be controlled by the polymerization time.

[0036] Step 5: Heat the reaction vessel to 160°C to decompose the alkali glue for 0.5h, then cool it down to 70°C;

[0037] Step 6: dissolving the polyphenol in anhydrous ethanol, pouring the mixture into the reaction container after the reaction container is cooled to the target temperature, stirring evenly and introducing nitrogen, reacting for 1 to 1.5 hours, removing the organic solvent, cooling to room temperature, and discharging the polyphenol-modified aminopropyl silicone rubber;

[0038] Step 7: Place the polyphenol-modified aminopropyl silicone rubber and vinyl MQ resin in a reaction container, add an organic solvent to dissolve, heat to 60° C., stir evenly and introduce nitrogen, react for 1 to 2 hours to obtain an organic silicone pressure-sensitive adhesive;

[0039] Step 8: Coat the silicone pressure-sensitive adhesive on the PI and PE films, cure in a vacuum oven at 180°C for 5-15 minutes, take out and age at room temperature for 24 hours to prepare a high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive.

[0040] The stirring rate of steps 1 to 8 is 100 r / min, the organic solvent of the polyphenol-modified aminopropyl silicone rubber is anhydrous ethanol, and the organic solvent for miscible silicone rubber and silicone resin is toluene.

[0041] Embodiment 1

[0042] This embodiment discloses a method for preparing a high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive based on the mussel viscosity effect, comprising the following steps:

[0043] Step 1: Weigh 10.8 g of N-(β-aminoethyl-Y-aminopropyl)methyldimethoxysilane into a reaction container, and add 1.6 g of deionized water to hydrolyze at room temperature for 0.5 h, while stirring evenly and passing nitrogen.

[0044] Step 2: Heat the reaction vessel to 60°C and distill under reduced pressure for 1 hour while stirring evenly to remove excess water in the system.

[0045] Step 3: Weigh 17.8 g of octamethylcyclotetrasiloxane and 0.02 g of alkali glue and place them in a reaction container, stir evenly, and purge with nitrogen for 5 minutes to remove oxygen in the system.

[0046] Step 4: Heat the reaction vessel to 110°C, condense and reflux, and stir evenly. After the polymerization reaction for 1 hour, introduce nitrogen to purge to remove the water produced during the polymerization process to increase the degree of polymerization, and continue the reaction for 1 hour.

[0047] Step 5: Heat the reaction vessel to 160°C to decompose the alkali glue for 0.5h, then cool it down to 70°C.

[0048] Step 6: Dissolve 3.4 g of 3,4,5-trihydroxybenzoic acid in 30 g of anhydrous ethanol, and pour it into the reaction container after the reaction container cools down to the target temperature. Stir evenly and introduce nitrogen. React for 1 hour, remove the organic solvent, cool to room temperature, and obtain polyphenol-modified aminopropyl silicone rubber, named L-GASR.

[0049] Step 7: Weigh 40 g of the prepared L-GASR and 10 g of vinyl MQ resin into a reaction container, add 30 g of toluene to mix, heat to 60° C., stir evenly and introduce nitrogen, react for 1 hour to obtain a silicone pressure-sensitive adhesive.

[0050] Step 8: The silicone pressure-sensitive adhesive is coated on the PI and PE films, cured in a vacuum oven at 180°C for 5 minutes, and then taken out and aged at room temperature for 24 hours to prepare a high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive.

[0051] Example 2

[0052] This embodiment discloses a method for preparing a high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive based on the mussel viscosity effect, comprising the following steps:

[0053] Step 1: Weigh 21.6 g of N-(β-aminoethyl-Y-aminopropyl)methyldimethoxysilane into a reaction container, and add 3.4 g of deionized water for hydrolysis at room temperature for 1 h, while stirring evenly and introducing nitrogen;

[0054] Step 2: Heat the reaction vessel to 60°C and distill under reduced pressure for 1.5 hours while stirring evenly to remove excess water in the system;

[0055] Step 3: Weigh 29.7 g of octamethylcyclotetrasiloxane and 0.05 g of alkali glue into a reaction container, stir evenly, and purge with nitrogen for 5 minutes to remove oxygen in the system;

[0056] Step 4: The reaction vessel was heated to 115°C, condensed and refluxed, and stirred evenly. After the polymerization reaction for 1.5 hours, nitrogen was purged to remove the water produced during the polymerization process to increase the degree of polymerization, and the reaction was continued for 2 hours;

[0057] Step 5: Heat the reaction vessel to 160°C to decompose the alkali glue for 0.5h, then cool it down to 70°C;

[0058] Step 6: Dissolve 5.1 g of 3,4,5-trihydroxybenzoic acid in 30 g of anhydrous ethanol, and pour the mixture into the reaction container after the reaction container is cooled to the target temperature. Stir evenly and introduce nitrogen. React for 1 h, remove the organic solvent, cool to room temperature, and obtain polyphenol-modified aminopropyl silicone rubber, named GASR.

[0059] Step 7: Weigh 30g of the prepared GASR and 20g of vinyl MQ resin into a reaction container, add 30g of toluene to mix, heat to 60°C, stir evenly, pass nitrogen, and react for 1.5h to obtain a silicone pressure-sensitive adhesive;

[0060] Step 8: Coat the silicone pressure-sensitive adhesive on the PI and PE films, cure them in a vacuum oven at 180°C for 10 minutes, take them out and age them at room temperature for 24 hours to prepare a high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive.

[0061] Example 3

[0062] This embodiment discloses a method for preparing a high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive based on the mussel viscosity effect, comprising the following steps:

[0063] Step 1: Weigh 32.4 g of N-(β-aminoethyl-Y-aminopropyl)methyldimethoxysilane into a reaction container, and add 5.2 g of deionized water for hydrolysis at room temperature for 1 h, while stirring evenly and introducing nitrogen;

[0064] Step 2: Heat the reaction vessel to 60°C and distill under reduced pressure for 2 hours while stirring evenly to remove excess water in the system;

[0065] Step 3: Weigh 41.5 g of octamethylcyclotetrasiloxane and 0.08 g of alkali glue into a reaction container, stir evenly, and purge with nitrogen for 5 minutes to remove oxygen in the system;

[0066] Step 4: The reaction vessel was heated to 120°C, condensed and refluxed, and stirred evenly. After the polymerization reaction for 1.5 hours, nitrogen was purged to remove the water produced during the polymerization process to increase the degree of polymerization, and the reaction was continued for 3 hours;

[0067] Step 5: Heat the reaction vessel to 160°C to decompose the alkali glue for 0.5h, then cool it down to 70°C;

[0068] Step 6: Dissolve 6.8 g of 3,4,5-trihydroxybenzoic acid in 30 g of anhydrous ethanol, and pour the mixture into the reaction container after the reaction container is cooled to the target temperature. Stir evenly and introduce nitrogen. React for 1.5 h, remove the organic solvent, cool to room temperature, and obtain polyphenol-modified aminopropyl silicone rubber, named H-GASR.

[0069] Step 7: Weigh 20 g of the prepared H-GASR and 30 g of vinyl MQ resin into a reaction container, add 30 g of toluene to mix, heat to 60° C., stir evenly and introduce nitrogen, react for 2 h to obtain a silicone pressure-sensitive adhesive;

[0070] Step 8: Coat the silicone pressure-sensitive adhesive on the PI and PE films, cure them in a vacuum oven at 180°C for 15 minutes, take them out and age them at room temperature for 24 hours to prepare a high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive.

[0071] Example 4

[0072] This embodiment discloses a method for preparing a high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive based on the mussel viscosity effect, comprising the following steps:

[0073] Step 1: Weigh 22.1 g of aminoethylaminoisobutylmethyldimethoxysilane into a reaction container, add deionized water and hydrolyze at room temperature for 1 h, while stirring evenly and introducing nitrogen;

[0074] Step 2: Heat the reaction vessel to 60°C and distill under reduced pressure for 1.5 hours while stirring evenly to remove excess water in the system;

[0075] Step 3: Weigh 29.7 g of octamethylcyclotetrasiloxane and 0.05 g of alkali glue into a reaction container, stir evenly, and purge with nitrogen for 5 minutes to remove oxygen in the system;

[0076] Step 4: The reaction vessel was heated to 115°C, condensed and refluxed, and stirred evenly. After the polymerization reaction for 1.5 hours, nitrogen was purged to remove the water produced during the polymerization process to increase the degree of polymerization, and the reaction was continued for 2 hours;

[0077] Step 5: Heat the reaction vessel to 160°C to decompose the alkali glue for 0.5h, then cool it down to 70°C;

[0078] Step 6: Dissolve 5.1 g of 2,4,6-trihydroxybenzoic acid in 30 g of anhydrous ethanol, and pour the mixture into the reaction container after the temperature of the reaction container drops to the target temperature. Stir evenly and introduce nitrogen. React for 1 h, remove the organic solvent, cool to room temperature, and obtain polyphenol-modified aminopropyl silicone rubber, named TASR.

[0079] Step 7: Weigh 30g of TASR and 20g of vinyl MQ resin into a reaction container, add 30g of toluene to mix, heat to 60°C, stir evenly and introduce nitrogen, react for 1.5h to obtain a silicone pressure-sensitive adhesive;

[0080] Step 8: Coat the silicone pressure-sensitive adhesive on the PI and PE films, cure them in a vacuum oven at 180°C for 10 minutes, take them out and age them at room temperature for 24 hours to prepare a high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive.

[0081] Example 5

[0082] This embodiment discloses a method for preparing a high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive based on the mussel viscosity effect, comprising the following steps:

[0083] Step 1: Weigh 19.1 g of Y-aminopropyldiethoxysilane into a reaction container, add deionized water and hydrolyze at room temperature for 1 h, while stirring evenly and introducing nitrogen;

[0084] Step 2: Heat the reaction vessel to 60°C and distill under reduced pressure for 1.5 hours while stirring evenly to remove excess water in the system;

[0085] Step 3: Weigh 29.7 g of octamethylcyclotetrasiloxane and 0.05 g of alkali glue into a reaction container, stir evenly, and purge with nitrogen for 5 minutes to remove oxygen in the system;

[0086] Step 4: The reaction vessel was heated to 115°C, condensed and refluxed, and stirred evenly. After the polymerization reaction for 1.5 hours, nitrogen was purged to remove the water produced during the polymerization process to increase the degree of polymerization, and the reaction was continued for 2 hours;

[0087] Step 5: Heat the reaction vessel to 160°C to decompose the alkali glue for 0.5h, then cool it down to 70°C;

[0088] Step 6: Dissolve 5.9 g of 3-(3,4-dihydroxyphenyl)-DL-alanine in 30 g of anhydrous ethanol, pour into the reaction container after the reaction container is cooled to the target temperature, stir evenly and introduce nitrogen, react for 1 hour, remove the organic solvent, cool to room temperature, and obtain polyphenol-modified aminopropyl silicone rubber, named DLSR;

[0089] Step 7: Weigh 30 g of DLSR and 20 g of vinyl MQ resin into a reaction container, add 30 g of toluene to mix, heat to 60° C., stir evenly and introduce nitrogen, react for 1.5 h to obtain a silicone pressure-sensitive adhesive;

[0090] Step 8: Coat the silicone pressure-sensitive adhesive on the PI and PE films, cure them in a vacuum oven at 180°C for 10 minutes, take them out and age them at room temperature for 24 hours to prepare a high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive.

[0091] Example 6

[0092] This embodiment discloses a method for preparing a high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive based on the mussel viscosity effect, comprising the following steps:

[0093] Step 1: Weigh 16.3 g of 3-aminopropyldimethoxymethylsilane into a reaction container, add deionized water and hydrolyze at room temperature for 1 h, while stirring evenly and introducing nitrogen;

[0094] Step 2: Heat the reaction vessel to 60°C and distill under reduced pressure for 1.5 hours while stirring evenly to remove excess water in the system;

[0095] Step 3: Weigh 29.7 g of octamethylcyclotetrasiloxane and 0.05 g of alkali glue into a reaction container, stir evenly, and purge with nitrogen for 5 minutes to remove oxygen in the system;

[0096] Step 4: The reaction vessel was heated to 115°C, condensed and refluxed, and stirred evenly. After the polymerization reaction for 1.5 hours, nitrogen was purged to remove the water produced during the polymerization process to increase the degree of polymerization, and the reaction was continued for 2 hours;

[0097] Step 5: Heat the reaction vessel to 160°C to decompose the alkali glue for 0.5h, then cool it down to 70°C;

[0098] Step 6: Dissolve 4.6 g of 3,4-dihydroxybenzoic acid in 30 g of anhydrous ethanol, and pour the mixture into the reaction container after the reaction container is cooled to the target temperature. Stir evenly and introduce nitrogen. React for 1 h, remove the organic solvent, cool to room temperature, and obtain polyphenol-modified aminopropyl silicone rubber, named DASR.

[0099] Step 7: Weigh 30g of DASR and 20g of vinyl MQ resin into a reaction container, add 30g of toluene to mix, heat to 60°C, stir evenly and introduce nitrogen, react for 1.5h to obtain a silicone pressure-sensitive adhesive;

[0100] Step 8: Coat the silicone pressure-sensitive adhesive on the PI and PE films, cure them in a vacuum oven at 180°C for 10 minutes, take them out and age them at room temperature for 24 hours to prepare a high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive.

[0101] Comparative Example 1

[0102] This comparative example preparation method comprises the following steps:

[0103] Step 1: Weigh 19.1 g of Y-aminopropyldiethoxysilane into a reaction vessel, add 3.4 g of deionized water and hydrolyze at room temperature for 1 h, while stirring evenly and introducing nitrogen;

[0104] Step 2: Heat the reaction vessel to 60°C and distill under reduced pressure for 1.5 hours while stirring evenly to remove excess water in the system;

[0105] Step 3: Weigh 29.7 g of octamethylcyclotetrasiloxane and 0.05 g of alkali glue into a reaction container, stir evenly, and purge with nitrogen for 5 minutes to remove oxygen in the system;

[0106] Step 4: The reaction vessel was heated to 115°C, condensed and refluxed, and stirred evenly. After the polymerization reaction for 1.5 hours, nitrogen was purged to remove the water produced during the polymerization process to increase the degree of polymerization, and the reaction was continued for 2 hours;

[0107] Step 5: The reaction vessel is heated to 160°C to decompose the alkali rubber for 0.5 h, and then cooled to room temperature to obtain aminopropyl silicone rubber;

[0108] Step 6: Weigh 30g of aminopropyl silicone rubber and 20g of vinyl MQ resin into a reaction container, add 30g of toluene to mix, heat to 60°C, stir evenly, pass nitrogen, react for 1.5h, and obtain a silicone pressure-sensitive adhesive;

[0109] Step 7: Coat the silicone pressure-sensitive adhesive on the PI and PE films, cure them in a vacuum oven at 180°C for 10 minutes, and then take them out and mature them at room temperature for 24 hours.

[0110] Comparative Example 2

[0111] This comparative example preparation method comprises the following steps:

[0112] Step 1: Weigh 21.6 g of N-(β-aminoethyl-Y-aminopropyl)methyldimethoxysilane into a reaction container, and add 3.4 g of deionized water for hydrolysis at room temperature for 1 h, while stirring evenly and introducing nitrogen;

[0113] Step 2: Heat the reaction vessel to 60°C and distill under reduced pressure for 1.5 hours while stirring evenly to remove excess water in the system;

[0114] Step 3: Weigh 29.7 g of octamethylcyclotetrasiloxane and 0.05 g of alkali glue into a reaction container, stir evenly, and purge with nitrogen for 5 minutes to remove oxygen in the system;

[0115] Step 4: The reaction vessel was heated to 115°C, condensed and refluxed, and stirred evenly. After the polymerization reaction for 1.5 hours, nitrogen was purged to remove the water produced during the polymerization process to increase the degree of polymerization, and the reaction was continued for 2 hours;

[0116] Step 5: The reaction vessel is heated to 160°C to decompose the alkali rubber for 0.5 h, and then cooled to room temperature to obtain aminopropyl silicone rubber;

[0117] Step 6: Weigh 30g of aminopropyl silicone rubber and 20g of vinyl MQ resin into a reaction container, add 30g of toluene to mix, heat to 60°C, stir evenly and introduce nitrogen, react for 1.5h, and obtain a silicone pressure-sensitive adhesive;

[0118] Step 7: Coat the silicone pressure-sensitive adhesive on the PI and PE films, cure them in a vacuum oven at 180°C for 10 minutes, and then take them out and age them at room temperature for 24 hours;

[0119] Comparative Example 3

[0120] This comparative example preparation method comprises the following steps:

[0121] Step 1: Weigh 16.3 g of 3-aminopropyldimethoxymethylsilane into a reaction container, add 3.4 g of deionized water and hydrolyze at room temperature for 1 h, while stirring evenly and introducing nitrogen;

[0122] Step 2: Heat the reaction vessel to 60°C and distill under reduced pressure for 1.5 hours while stirring evenly to remove excess water in the system;

[0123] Step 3: Weigh 29.7 g of octamethylcyclotetrasiloxane and 0.05 g of alkali glue into a reaction container, stir evenly, and purge with nitrogen for 5 minutes to remove oxygen in the system;

[0124] Step 4: The reaction vessel was heated to 115°C, condensed and refluxed, and stirred evenly. After the polymerization reaction for 1.5 hours, nitrogen was purged to remove the water produced during the polymerization process to increase the degree of polymerization, and the reaction was continued for 2 hours;

[0125] Step 5: The reaction vessel is heated to 160°C to decompose the alkali rubber for 0.5 h, and then cooled to room temperature to obtain aminopropyl silicone rubber;

[0126] Step 6: Weigh 30g of aminopropyl silicone rubber and 20g of vinyl MQ resin into a reaction container, add 30g of toluene to mix, heat to 60°C, stir evenly and introduce nitrogen, react for 1.5h, and obtain a silicone pressure-sensitive adhesive;

[0127] Step 7: Coat the silicone pressure-sensitive adhesive on the PI and PE films, cure them in a vacuum oven at 180°C for 10 minutes, and then take them out and mature them at room temperature for 24 hours.

[0128] The molecular weight test, 180° peel strength test, 80°C high temperature adhesion test, ring initial adhesion test, and thermal weight loss test were performed on Examples 1 to 5 and Comparative Examples 1 to 3. The test data are shown in the following table:

[0129]

[0130]

[0131] 1. Gel Permeation Chromatography (GPC)

[0132] At 30 °C, tetrahydrofuran was used as the eluent at a flow rate of 1.0 ml min -1 The number average relative molecular mass of polyphenol-modified aminopropyl silicone rubber was determined by gel permeation chromatography, and the relative molecular mass was calculated based on the calibration curve calibrated by standard polystyrene.

[0133] 2. 180° peeling force

[0134] According to the standard GB / T2792-2014, the samples were subjected to a 180° peel force test. The coated samples were subjected to a 180° peel test using an electronic peel tester. The strips were cut into 25mm*200mm strips. These strips were removed from the release liner and applied to a standard test plate. The strips were rolled 3 times with a 2.5kg roller and then pulled out from the standard test plate at a speed of 300mm / min at 180°.

[0135] 3. High temperature adhesion

[0136] The sample is coated between two substrates, and after cooling and curing, it is fixed in the oven "Oven Type Adhesive Tape Retention Tester KJ-6012A" and attached with a known weight. After hanging for a period of time at a certain temperature, the ability of the adhesive tape to resist pulling off is characterized by the displacement of the sample sticking or the time for the sample to completely detach.

[0137] 4. Ring initial bonding

[0138] According to the standard GB / T2792-2014, the test temperature is 23℃±2℃, the humidity is 50%RH±5%RH, and the test specimen should be placed for at least 4 hours before testing. Cut five specimens with a width of 25mm and a length of at least 175mm for testing. Remove the tape backing before testing, with the adhesive surface facing outward, and hold the two ends of the tape to form a ring. The end of the ring is 10mm clamped into the upper fixture of the tensile machine, and the ring hangs vertically. Clamp the glass plate into the lower fixture, with its radial direction perpendicular to the radial direction of the tape. Make the ring contact with the glass plate at a speed of 300mm / min. When in contact, immediately reverse and separate at a speed of 300mm / min. The important point is to make the reverse separation lag time as short as possible, and record the maximum force value of separating the ring and the glass plate.

[0139] From the results in the above table, it can be seen that the adhesion performance and high temperature resistance of the prepared mussel adhesion effect enhanced silicone pressure-sensitive adhesive are effectively improved, and the performance of Example 2 is the best, the 180° peeling force can reach 17.38N / 25mm, the high temperature of 80°C can be maintained for 84h without falling off, the ring initial adhesion can reach 18.67N, the thermal weight loss 5% temperature is 502.3°C, and the adhesion performance and high temperature resistance are excellent. The present invention provides a new modification process for the modification of silicone pressure-sensitive adhesive, and the prepared mussel adhesion effect enhanced silicone pressure-sensitive adhesive has adhesion performance and high temperature resistance that meet the use requirements of bonding and has excellent use performance.

[0140] It should be noted that in the above embodiments, as long as the technical solutions are not contradictory, they can be arranged and combined, and those skilled in the art can exhaust all possibilities based on the mathematical knowledge of arrangement and combination. Therefore, the present invention will no longer describe the technical solutions after arrangement and combination one by one, but it should be understood that the technical solutions after arrangement and combination have been disclosed by the present invention.

[0141] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. High viscosity / high temperature resistant silicone pressure sensitive adhesive based on mussel viscosity effect, characterized by: The mussel adhesion effect enhanced silicone pressure-sensitive adhesive is composed of octamethylcyclotetrasiloxane, aminopropylsiloxane, deionized water, mussel adhesion protein-like polyphenol, initiator, synthetic polyphenol-modified aminopropyl silicone rubber, vinyl MQ resin, and organic solvent; The mass fraction of octamethylcyclotetrasiloxane is 17.8-41.5 parts, the mass fraction of aminopropyl siloxane is 10.8-32.4 parts, the mass fraction of deionized water is 1.6-5.2 parts, the mass fraction of mussel adhesion protein-like polyphenol is 3.4-6.8 parts, the mass fraction of initiator is 0.02-0.08 parts, the mass fraction of synthetic polyphenol-modified aminopropyl silicone rubber is 20-40 parts, the mass fraction of vinyl MQ resin is 10-30 parts, and the mass fraction of organic solvent is 30 parts.

2. The high viscosity / high temperature resistant silicone pressure-sensitive adhesive based on mussel viscosity effect according to claim 1, characterized in that: The aminopropylsiloxane is one or more of γ-aminopropyldiethoxysilane, N-(β-aminoethyl-γ-aminopropyl)methyldimethoxysilane, aminoethylaminoisobutylmethyldimethoxysilane, and 3-aminopropyldimethoxymethylsilane.

3. The high viscosity / high temperature resistant silicone pressure sensitive adhesive based on mussel viscosity effect according to claim 1, characterized in that: The polyphenols of the mussel adhesive protein-like substance are one or more of 3,4,5-trihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3-(3,4-dihydroxyphenyl)-DL-alanine and 2,4,6-trihydroxybenzoic acid.

4. The method for preparing a high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive based on the mussel viscosity effect according to claim 1, characterized in that: The steps include: Step 1: Add aminopropylsiloxane into a reaction vessel, add deionized water to hydrolyze at room temperature, stir evenly, and introduce nitrogen; Step 2: Heat the reaction vessel to 60°C and distill under reduced pressure for 1 to 2 hours while stirring evenly; Step 3: Add octamethylcyclotetrasiloxane and alkali into a reaction vessel, stir evenly, and introduce nitrogen for purging; Step 4: Heat the reaction vessel and stir evenly. After 1 to 1.5 hours of polymerization reaction, purge with nitrogen and continue the reaction for 1 to 3 hours. Step 5: Raise the temperature of the reaction vessel to 160°C, react for 0.5h, and then cool down to 70°C; Step 6: dissolving the polyphenol in anhydrous ethanol, pouring the solution into the reaction container after the reaction container cools down, stirring evenly and introducing nitrogen, reacting for 1 to 1.5 hours, cooling to room temperature after the reaction is completed, and preparing polyphenol-modified aminopropyl silicone rubber; Step 7: placing the polyphenol-modified aminopropyl silicone rubber and the vinyl MQ resin in a reaction container, adding an organic solvent to dissolve them, heating the reaction container, stirring evenly and introducing nitrogen, and reacting for 1 to 2 hours to obtain an organic silicone pressure-sensitive adhesive; Step 8: Coat the silicone pressure-sensitive adhesive on the PI and PE films, place them in a vacuum oven for curing, and then take them out and mature them at room temperature to prepare a high-viscosity / high-temperature resistant silicone pressure-sensitive adhesive.

5. The method for preparing a high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive based on the mussel viscosity effect according to claim 4, characterized in that: The hydrolysis time in step 1 is 0.5-1.0 h, the purging time in step 3 is 5 min, the temperature of the reaction container in step 4 is raised to 110-120° C., and the temperature of the reaction container in step 7 is raised to 60° C.

6. The method for preparing a high-viscosity / high-temperature-resistant silicone pressure-sensitive adhesive based on the mussel viscosity effect according to claim 4, characterized in that: In step eight, the vacuum oven temperature is 180° C., the curing time is 5 to 15 minutes, and the aging time is 24 hours.

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