A high-temperature-resistant boron and imide-containing tackifier for silicone rubber and a preparation method and application thereof

Abstract

The application provides a high-temperature-resistant boron and imide-containing tackifier for silicone rubber and a preparation method and application thereof. The preparation method of the boron and imide-containing tackifier comprises the following steps: mixing an imide compound, a borate compound and optionally added or not added solvent, and performing an ester exchange reaction to prepare the boron and imide-containing tackifier. The boron and imide-containing tackifier can be used in an addition type silicone rubber, a condensation type silicone rubber and a high-temperature vulcanized silicone rubber system. The boron and imide-containing tackifier can greatly improve the bonding performance of the silicone rubber to a polyimide base material at room temperature and high temperature without using a traditional primer, and expand the application field of the silicone rubber and the polyimide. The preparation method of the boron and imide-containing tackifier is novel, efficient, high in product purity, easy to control structure and simple in operation method, and is suitable for industrial production.

Description

TECHNICAL FIELD

[0001] The present application relates to a high-temperature-resistant boron and imide-containing adhesion promoter for silicone rubber and a preparation method and application thereof, and belongs to the technical field of silicone rubber adhesion and sealing materials and preparation thereof. BACKGROUND

[0002] Silicone rubber has excellent high and low temperature resistance, weather resistance, ozone resistance, and physiological inertness, and particularly its high temperature resistance, so that it has been widely used in the fields of aerospace, etc. Polyimide also has excellent high temperature resistance, but the adhesion performance of the adhesion and sealing agent for silicone rubber to polyimide (film, sheet, etc.) is not high, and the adhesion strength is even worse under high temperature environment.

[0003] Therefore, it is urgent to provide a series of high-temperature-resistant adhesion promoters for silicone rubber, which can improve the adhesion performance of silicone rubber to polyimide base material at room temperature and high temperature, and expand the application of silicone rubber and polyimide under high temperature environment. SUMMARY

[0004] In order to improve the deficiencies in the prior art, the present application provides a high-temperature-resistant boron and imide-containing adhesion promoter for silicone rubber and a preparation method and application thereof. The boron and imide-containing adhesion promoter can be used in addition type silicone rubber, condensation type silicone rubber and high temperature vulcanized silicone rubber system. The boron and imide-containing adhesion promoter can greatly improve the adhesion performance of silicone rubber to polyimide base material at room temperature and high temperature without using traditional primer, and expand the application field of silicone rubber and polyimide. The preparation method of the boron and imide-containing adhesion promoter is novel, efficient, high in product purity, easy to control structure and simple in operation method, and is suitable for industrial production.

[0005] The purpose of the present application is achieved by the following technical solutions:

[0006] A preparation method of a boron and imide-containing adhesion promoter, comprising the following steps:

[0007] The imide compound, the borate compound and the optional solvent are mixed to perform ester exchange reaction, so as to prepare the boron and imide-containing adhesion promoter.

[0008] According to the embodiment of the present application, the imide compound and the borate compound are mixed to perform ester exchange reaction, or the imide compound, the borate compound and the solvent are mixed to perform ester exchange reaction.

[0009] According to an embodiment of the present application, the molar ratio of the imide compound to the solvent is 1:0-100 (unit: mol:mol), and specifically, it can be 1:0, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90 or 1:100. Among them, when the molar ratio of the imide compound to the solvent is 1:0, it means that the reaction system does not contain solvent.

[0010] According to an embodiment of the present application, the molar ratio of the imide compound to the borate compound is 1:0.5-5 (unit: mol:mol), and specifically, it can be 1:0.5, 1:0.6, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5 or 1:5. By adjusting the molar ratio of the imide compound and the borate compound, the adhesion of the boron-containing and imide-containing adhesion agent to the polyimide substrate material can be adjusted.

[0011] According to an embodiment of the present application, the mixing method can be direct mixing or dropwise mixing.

[0012] According to an embodiment of the present application, the temperature of the transesterification reaction is 20-150°C, and specifically, it can be 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C or 150°C.

[0013] According to an embodiment of the present application, the time of the transesterification reaction is 3-24h, for example, 3h, 4h, 5h, 6h, 8h, 10h, 12h, 15h, 18h, 20h or 24h.

[0014] According to an embodiment of the present application, the transesterification reaction is a three-stage reaction, including a first-stage reaction, a second-stage reaction, and a third-stage reaction, wherein the temperature of the first-stage reaction is 20-100°C, specifically 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, or 100°C, and the time of the first-stage reaction is 1-6h, specifically 1h, 2h, 3h, 4h, 5h, or 6h; the temperature of the second-stage reaction is 60-120°C, specifically 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, or 120°C, and the time of the second-stage reaction is 1-12h, specifically 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, or 12h; the temperature of the third-stage reaction is 100-150°C, specifically 100°C, 110°C, 120°C, 130°C, 140°C, or 150°C, and the time of the third-stage reaction is 1-10h, specifically 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, or 10h.

[0015] According to an embodiment of the present application, the temperature of the third-stage reaction is higher than that of the second-stage reaction, and the temperature of the second-stage reaction is higher than that of the first-stage reaction.

[0016] According to an embodiment of the present application, in order to promote the transesterification reaction in a positive direction, the temperature of the reaction system is increased to 60-120°C (at this time, the second-stage reaction is entered), and the reaction is continued for 1-12h until no distillate is distilled out of the water trap; after no distillate is distilled out, the temperature of the reaction system is further increased to 100-150°C (at this time, the third-stage reaction is entered), and the reaction is continued for 1-10h until no distillate is distilled out of the water trap.

[0017] According to an embodiment of the present application, the reaction is carried out under an inert atmosphere, specifically a nitrogen atmosphere, a helium atmosphere, or an argon atmosphere.

[0018] According to an embodiment of the present application, the solvent includes at least one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, and dichloromethane.

[0019] According to an embodiment of the present application, the borate compound includes at least one of trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, tri-tert-butyl borate, tris(trimethylsilyl) borate, and triphenyl borate.

[0020] According to an embodiment of the present application, the imide compound is a compound containing an imide structure and a hydroxyl group, specifically an imide compound containing a hydroxyl group (i.e., an alcohol compound containing an imide structure).

[0021] According to an embodiment of the present application, the imide compound can be a solid or a liquid.

[0022] According to an embodiment of the present application, the imide compound is a reactant of a dianhydride compound and an amino alcohol compound; preferably, the dianhydride compound and the amino alcohol compound are reactants at 0-200°C.

[0023] The present application also provides a boron- and imide-containing adhesion promoter prepared by the above preparation method.

[0024] The present application also provides a boron- and imide-containing adhesion promoter, raw materials for preparing the boron- and imide-containing adhesion promoter comprising the following components:

[0025] (a) an imide compound;

[0026] (b) a borate compound;

[0027] (c) optionally added or not added solvent.

[0028] According to an embodiment of the present application, the raw materials for preparing the boron- and imide-containing adhesion promoter comprise the following components in parts by weight of each component:

[0029] (a) an imide compound: 1 part;

[0030] (b) a borate compound: 0.5-5 parts;

[0031] (c) optionally added or not added solvent: 0-100 parts.

[0032] According to an embodiment of the present application, the raw materials for preparing the imide compound comprise the following components:

[0033] (1) a dianhydride compound;

[0034] (2) an amino alcohol compound;

[0035] (3) optionally added or not added solvent.

[0036] According to an embodiment of the present application, the raw materials for preparing the imide compound comprise the following components in parts by weight of each component:

[0037] (1) a dianhydride compound: 1 part;

[0038] (2) an amino alcohol compound: 0.5-5 parts;

[0039] (3) optionally added or not added solvent: 0-50 parts.

[0040] According to an embodiment of the present application, the boron- and imide-containing adhesion promoter is a small molecule adhesion promoter.

[0041] According to an embodiment of the present application, the molecular weight of the boron and imide containing adhesion promoter is 500-1000 g / mol, for example 500, 550, 600, 650, 700, 750, 800, 850, 900, 950 or 1000 g / mol.

[0042] According to an embodiment of the present application, the boron and imide containing adhesion promoter is a high temperature resistant boron and imide containing adhesion promoter.

[0043] According to an embodiment of the present application, the boron and imide containing adhesion promoter is a high temperature resistant boron and imide containing adhesion promoter for silicone rubber.

[0044] According to an embodiment of the present application, the temperature resistant range of the boron and imide containing adhesion promoter is 20-450 °C.

[0045] The present application also provides a use of the above-mentioned boron and imide containing adhesion promoter in silicone rubber.

[0046] According to an embodiment of the present application, the silicone rubber comprises at least one of addition type silicone rubber, condensation type silicone rubber and high temperature vulcanized silicone rubber.

[0047] According to an embodiment of the present application, the addition type silicone rubber is any one of the addition type silicone rubbers known in the art. The condensation type silicone rubber is any one of the condensation type silicone rubbers known in the art. The high temperature vulcanized silicone rubber is any one of the high temperature vulcanized silicone rubbers known in the art.

[0048] According to an embodiment of the present application, the use of the boron and imide containing adhesion promoter can greatly improve the room temperature bonding strength and high temperature bonding strength of silicone rubber to polyimide base material, and the silicone rubber can be directly used as a bonding sealant without the need of additional primer.

[0049] The present application also provides a bonding sealant comprising the above-mentioned boron and imide containing adhesion promoter.

[0050] According to an embodiment of the present application, the mass of the boron and imide containing adhesion promoter accounts for 0.1-2% of the total mass of the bonding sealant, for example 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8% or 2%.

[0051] According to an embodiment of the present application, the bonding sealant further comprises silicone rubber.

[0052] According to an embodiment of the present application, the silicone rubber comprises at least one of addition type silicone rubber, condensation type silicone rubber and high temperature vulcanized silicone rubber.

[0053] The beneficial effects of the present application are as follows:

[0054] 1) The preparation method of the boron and imide containing adhesion promoter is novel, simple, efficient and easy to operate, and is suitable for industrial production.

[0055] 2) The boron and imide containing adhesion promoter is used in a silicone rubber component, which can greatly improve the bonding performance of silicone rubber to a polyimide base material after room temperature and high temperature aging, thereby expanding the application range of silicone rubber and polyimide materials. DETAILED DESCRIPTION

[0056] As described above, the imide compound of the present application can also be prepared by the following method:

[0057] 1) The dianhydride compound, amino alcohol compound and optional solvent are mixed and reacted to prepare the imide compound.

[0058] According to an embodiment of the present application, in step 1), the dianhydride compound and the amino alcohol compound are mixed; or the dianhydride compound, the amino alcohol compound and the solvent are mixed.

[0059] According to an embodiment of the present application, in step 1), the molar ratio of the dianhydride compound to the amino alcohol compound is 1:0.5-5 (unit mol:mol), and specifically can be 1:0.5, 1:0.6, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5 or 1:5.

[0060] According to an embodiment of the present application, in step 1), the molar ratio of the dianhydride compound to the solvent is 1:0-50 (unit mol:mol), and specifically can be 1:0, 1:1, 1:2, 1:5, 1:8, 1:10, 1:12, 1:15, 1:18, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45 or 1:50. When the molar ratio of the dianhydride compound to the solvent is 1:0, it means that no solvent is contained.

[0061] According to an embodiment of the present application, in step 1), the temperature of the reaction is 0-200℃, and specifically can be 0℃, 10℃, 20℃, 30℃, 40℃, 50℃, 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃ or 200℃.

[0062] According to an embodiment of the present application, in step 1), the reaction time is 0.5-5 hours, and can be 0.5 hour, 1 hour, 2 hours, 3 hours, 4 hours or 5 hours.

[0063] According to an embodiment of the present application, in step 1), the reaction is carried out under an inert atmosphere, and can be under a nitrogen atmosphere, a helium atmosphere or an argon atmosphere.

[0064] According to an embodiment of the present application, in step 1), the dianhydride compound includes at least one of cyclobutane tetra carboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride and 4,4'-oxydiphthalic dianhydride.

[0065] According to an embodiment of the present application, in step 1), the amino alcohol compound includes at least one of 6-amino-1-hexanol, 5-amino-1-pentanol, 2-amino-1-hexanol, 1-amino-1-cyclopentanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-aminocyclohexanol, 5-amino-2,2-dimethylpentanol, 4-aminobenzyl alcohol, 2-aminobenzyl alcohol, 3-aminobenzyl alcohol and ethanolamine.

[0066] According to an embodiment of the present application, in step 1), the solvent includes at least one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene and dichloromethane.

[0067] According to an embodiment of the present application, the method further includes the following steps:

[0068] 2) washing and rotary evaporation of the reaction product of step 1).

[0069] According to an embodiment of the present application, the washing is, for example, adding distilled water or a hydrochloric acid solution (the concentration of the hydrochloric acid solution is 0.01M-1M) to the obtained product, stirring sufficiently and filtering, and repeating three times to remove unreacted reactants.

[0070] According to an embodiment of the present application, the rotary evaporation is, for example, warming and rotary evaporation of the product after washing to remove the solvent. The pressure of the rotary evaporation is ≤0.08MPa, and the temperature of the rotary evaporation is 20-150°C. Exemplarily, the step of the rotary evaporation is removing the solvent in the mixed system after the reaction under a pressure of 0.0001-0.08MPa and a temperature of 20-150°C.

[0071] The preparation method of the present application will be further described in detail below in connection with specific examples. It should be understood that the following examples are only illustrative and explanatory of the present application and should not be construed as limiting the scope of protection of the present application. Any technology realized based on the above description of the present application is encompassed within the scope of protection intended by the present application.

[0072] The experimental methods used in the following examples are conventional methods unless otherwise specified; the reagents, materials, etc. used in the following examples are commercially available unless otherwise specified.

[0073] The test standard for the T-type peeling strength of the polyimide film sample of the following examples and comparative examples is GB / T2791-1995.

[0074] Example 1, Preparation of a Silicon Rubber Adhesion Promoter Containing Boron and Imide and Its Application

[0075] (1) Preparation of a Silicon Rubber Adhesion Promoter Containing Boron and Imide

[0076] In a single-neck flask, 50 g of pyromellitic dianhydride, 25 g of 3-amino-1-propanol, and 100 g of N,N-dimethylformamide were added, a spherical condenser was installed, and cooling water was turned on. The reaction was carried out at a temperature of 150°C for 6 h. The obtained solution was washed with 0.1 M hydrochloric acid solution three times to remove unreacted reactants. The obtained solution was distilled under reduced pressure at a pressure of 0.01 MPa and a temperature of 100°C to remove the solvent. 50 g of the obtained product and 40 g of trimethyl borate were added to a three-neck flask equipped with a water separator, mixed uniformly, heated to 50°C, and after 2 h, the temperature was increased to 75°C, and steam appeared in the water separator. The reaction was continued for 7 h until no steam appeared in the water separator. The temperature was increased to 110°C, and steam appeared in the water separator after about 1 h. When no steam appeared, the reaction was stopped, and a silicon rubber adhesion promoter containing boron and imide was obtained.

[0077] (2) Application of the Silicon Rubber Adhesion Promoter Containing Boron and Imide in Addition Type Silicon Rubber

[0078] 0.5 g of the silicon rubber adhesion promoter containing boron and imide prepared in this example was uniformly mixed with 50 g of vinyl-terminated silicone oil with a viscosity of 30 Pa·s, 2.5 g of hydrogen-containing silicone oil with a hydrogen content of 0.085%, 10 g of silica, and 0.05 g of Karstedt platinum catalyst to obtain an addition type silicon rubber adhesive sealant, which was coated on a polyimide film and cured at 100°C for 1 h to obtain a polyimide film peeling sample.

[0079] (3) Application of the Silicon Rubber Adhesion Promoter Containing Boron and Imide in Condensation Type Silicon Rubber

[0080] The 0.5 g of the boron and imide containing silicone rubber tackifier prepared in this example was mixed with 50 g of hydroxyl silicone oil with a viscosity of 20 Pa-s, 10 g of ethyl silicate, 10 g of silica and 0.5 g of dibutyltin dilaurate to obtain a condensation type silicone rubber adhesive sealant, which was coated on a polyimide film and cured at 80 °C for 2 days to obtain a polyimide film peel test sample.

[0081] (4) Application of the boron and imide containing silicone rubber tackifier in a high temperature vulcanized silicone rubber system

[0082] The 0.5 g of the boron and imide containing silicone rubber tackifier prepared in this example was mixed with 50 g of high temperature vulcanized silicone rubber with a vinyl content of 0.15%, 10 g of silica and 0.5 g of bisdipentyl to obtain a high temperature vulcanized silicone rubber adhesive sealant, which was coated on a polyimide film and cured at 170 °C and a pressure of 5 MPa for 30 min to obtain a polyimide film peel test sample.

[0083] (5) The three groups of polyimide film peel test samples prepared were placed in an aging oven, heated to 300 °C and kept for 1 h at a heating rate of 1 °C / min.

[0084] Example 2, Preparation of the boron and imide containing silicone rubber tackifier and its application

[0085] (1) Preparation of the boron and imide containing silicone rubber tackifier

[0086] In a single-neck flask, 50 g of pyromellitic dianhydride, 25 g of 3-amino-1-propanol and 100 g of N,N-dimethylformamide were added, a spherical condenser was installed and cooling water was turned on, and the reaction was carried out at a temperature of 150 °C for 6 h. The obtained solution was washed with 0.1 M hydrochloric acid solution three times to remove the unreacted reactants. The obtained solution was distilled under reduced pressure at a pressure of 0.01 MPa and a temperature of 100 °C to remove the solvent. 50 g of the obtained product and 50 g of triethyl borate were added to a three-neck flask equipped with a water separator, mixed uniformly, heated to 60 °C, after 2 h, the temperature was increased to 90 °C, and steam appeared in the water separator, the reaction was continued for 7 h until no steam appeared in the water separator, the temperature was increased to 110 °C, and steam appeared in the water separator, about 1 h later, when no steam appeared, the reaction was stopped to obtain the boron and imide containing silicone rubber tackifier.

[0087] (2) Application of the boron and imide containing silicone rubber tackifier in an addition type silicone rubber

[0088] The 0.5 g of the boron and imide containing silicone rubber tackifier prepared in this example was mixed with 50 g of vinyl terminated silicone oil with a viscosity of 30 Pa-s, 2.5 g of hydrogen containing silicone oil with a hydrogen content of 0.085%, 10 g of silica and 0.05 g of Karstedt platinum catalyst to obtain an addition type silicone rubber adhesive sealant, which was coated on a polyimide film and cured at 100°C for 1 h to obtain a polyimide film peel test sample.

[0089] (3) Application of the boron and imide containing silicone rubber tackifier in condensation type silicone rubber

[0090] The 0.5 g of the boron and imide containing silicone rubber tackifier prepared in this example was mixed with 50 g of hydroxyl silicone oil with a viscosity of 20 Pa-s, 10 g of ethyl orthosilicate, 10 g of silica and 0.5 g of dibutyltin dilaurate to obtain a condensation type silicone rubber adhesive sealant, which was coated on a polyimide film and cured at 80°C for 2 days to obtain a polyimide film peel test sample.

[0091] (4) Application of the boron and imide containing silicone rubber tackifier in high temperature vulcanized silicone rubber system

[0092] The 0.5 g of the boron and imide containing silicone rubber tackifier prepared in this example was mixed with 50 g of high temperature vulcanized silicone rubber with a vinyl content of 0.15%, 10 g of silica and 0.5 g of bis-dipent to obtain a high temperature vulcanized silicone rubber adhesive sealant, which was coated on a polyimide film and cured at 170°C and a pressure of 5 MPa for 30 min to obtain a polyimide film peel test sample.

[0093] (5) The three groups of polyimide film peel test samples prepared were placed in an aging oven, heated to 300°C and kept for 1 h at a heating rate of 1°C / min.

[0094] Example 3, Preparation of the boron and imide containing silicone rubber tackifier and its application

[0095] (1) Preparation of the boron and imide containing silicone rubber tackifier

[0096] In a single-neck flask, 50 g of cyclobutane tetracarboxylic dianhydride and 33 g of 6-amino-1-hexanol were added and reacted at 150°C for 6 hours. The obtained liquid product was added to 100 g of dichloromethane, and then washed with 0.1 M hydrochloric acid solution three times to remove unreacted reactants. The obtained solution was distilled under reduced pressure at 100°C and 0.01 MPa to remove the solvent. 50 g of the obtained product and 40 g of trimethyl borate were added to a three-neck flask equipped with a water separator, mixed well, heated to 60°C, and reacted for 2 hours. Then, the temperature was increased to 90°C, and the water separator started to produce steam. The reaction was continued for 7 hours until no steam was produced in the water separator. Then, the temperature was increased to 110°C, and the water separator started to produce steam again. After about 1 hour, no steam was produced, and the reaction was stopped. A silicone rubber adhesion promoter containing boron and imide was obtained.

[0097] (2) Application of the silicone rubber adhesion promoter containing boron and imide in addition-type silicone rubber

[0098] 0.5 g of the silicone rubber adhesion promoter containing boron and imide prepared in this example was mixed with 50 g of vinyl-terminated silicone oil with a viscosity of 30 Pa·s, 2.5 g of hydrogen-containing silicone oil with a hydrogen content of 0.085%, 10 g of silica, and 0.05 g of Karstedt platinum catalyst to obtain an addition-type silicone rubber adhesive sealant. The sealant was coated on a polyimide film and cured at 100°C for 1 hour to obtain a polyimide film peel test sample.

[0099] (3) Application of the silicone rubber adhesion promoter containing boron and imide in condensation-type silicone rubber

[0100] 0.5 g of the silicone rubber adhesion promoter containing boron and imide prepared in this example was mixed with 50 g of hydroxy silicone oil with a viscosity of 20 Pa·s, 10 g of ethyl orthosilicate, 10 g of silica, and 0.5 g of dibutyltin dilaurate to obtain a condensation-type silicone rubber adhesive sealant. The sealant was coated on a polyimide film and cured at 80°C for 2 days to obtain a polyimide film peel test sample.

[0101] (4) Application of the silicone rubber adhesion promoter containing boron and imide in high-temperature vulcanized silicone rubber system

[0102] 0.5 g of the silicone rubber adhesion promoter containing boron and imide prepared in this example was mixed with 50 g of high-temperature vulcanized silicone rubber with a vinyl content of 0.15%, 10 g of silica, and 0.5 g of bis-dipent to obtain a high-temperature vulcanized silicone rubber adhesive sealant. The sealant was coated on a polyimide film and cured at 170°C and 5 MPa for 30 minutes to obtain a polyimide film peel test sample.

[0103] (5) The three groups of polyimide film peel test samples prepared were placed in an aging oven and heated to 300°C at a rate of 1°C / min and held for 1 hour.

[0104] Comparative Example 1

[0105] 50 g of end-vinyl silicone oil having a viscosity of 30 Pa-s, 2.5 g of hydrogen- containing silicone oil having a hydrogen content of 0.085%, 10 g of silica, and 0.05 g of Karstedt platinum catalyst were mixed uniformly to obtain an addition-type silicone rubber adhesive sealant, which was coated on a polyimide film and cured at 100°C for 1 h to obtain a polyimide film peeling test sample.

[0106] The prepared polyimide film peeling test sample was heated to 300°C at a rate of 1°C / min in an aging oven and left for 1 h.

[0107] Comparative Example 2

[0108] 50 g of hydroxy silicone oil having a viscosity of 20 Pa-s, 10 g of ethyl orthosilicate, 10 g of silica, and 0.5 g of dibutyltin dilaurate were mixed uniformly to obtain a condensation-type silicone rubber adhesive sealant, which was coated on a polyimide film and cured at 80°C for 2 days to obtain a polyimide film peeling test sample.

[0109] The prepared polyimide film peeling test sample was heated to 300°C at a rate of 1°C / min in an aging oven and left for 1 h.

[0110] Comparative Example 3

[0111] 50 g of high-temperature vulcanized silicone rubber having a vinyl content of 0.15%, 10 g of silica, and 0.5 g of bis-dipentyl were mixed uniformly to obtain a high-temperature vulcanized silicone rubber adhesive sealant, which was coated on a polyimide film and cured at 170°C at a pressure of 5 MPa for 30 min to obtain a polyimide film peeling test sample.

[0112] The prepared polyimide film peeling test sample was heated to 300°C at a rate of 1°C / min in an aging oven and left for 1 h.

[0113] Table 1: Test results of addition-type silicone rubber adhesive sealant

[0114]

[0115] Table 2: Test results of condensation-type silicone rubber adhesive sealant

[0116]

[0117]

[0118] Table 3: Test results of high-temperature vulcanized silicone rubber adhesive sealant

[0119]

[0120] The above describes the embodiments of the present application. However, the present application is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement, and the like made within the spirit and principle of the present application should be included in the scope of protection of the present application.

Claims

1. A method for preparing a boron- and imide-containing tackifier, the preparation method comprising the following steps: The boron- and imide-containing thickener is prepared by mixing an imide compound, a boron ester compound, and a solvent (optionally added or not added) and carrying out an ester exchange reaction. The imide compound is a compound containing an imide structure and a hydroxyl group, and the imide compound is a reactant of a dianhydride compound and an amino alcohol compound.

2. The preparation method according to claim 1, wherein, The molar ratio of the imide compound to the solvent is 1:0 to 100; and / or, the molar ratio of the imide compound to the borate ester compound is 1:0.5 to 5.

3. The preparation method according to claim 1, wherein, The transesterification reaction is carried out at a temperature of 20~150℃ for 3~24h.

4. The preparation method according to claim 3, wherein, The transesterification reaction is a three-stage reaction, including a first stage reaction, a second stage reaction and a third stage reaction. The temperature of the first stage reaction is 20~100℃ and the time is 1~6h; the temperature of the second stage reaction is 60~120℃ and the time is 1~12h; the temperature of the third stage reaction is 100~150℃ and the time is 1~10h.

5. The preparation method according to claim 4, wherein, The temperature of the third stage reaction is higher than that of the second stage reaction; the temperature of the second stage reaction is higher than that of the first stage reaction.

6. The preparation method according to claim 1, wherein, The solvent includes at least one selected from N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, and dichloromethane; And / or, the borate ester compounds include at least one of trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, tri-tert-butyl borate, tri(trimethylsilyl) borate, and triphenyl borate.

7. The preparation method according to claim 1, wherein, The imide compounds are reactants of dianhydride compounds and amino alcohol compounds at 0~200℃.

8. The preparation method according to claim 1, wherein, The imide compounds were prepared by the following method: 1) The dianhydride compound, the amino alcohol compound, and a solvent (optionally added or not added) are mixed and reacted to prepare the imide compound.

9. The preparation method according to claim 8, wherein, In step 1), the molar ratio of the dianhydride compound to the amino alcohol compound is 1:0.5~5; and / or, the molar ratio of the dianhydride compound to the solvent is 1:0~50.

10. The preparation method according to claim 8, wherein, In step 1), the reaction temperature is 0~200℃ and the reaction time is 0.5~5h.

11. The preparation method according to claim 8, wherein, In step 1), the dianhydride compounds include at least one of cyclobutanetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, ethylenediaminetetraacetic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, pyromellitic dianhydride, and 4,4'-oxobisphthalic anhydride.

12. The preparation method according to claim 8, wherein, In step 1), the amino alcohol compound includes at least one of 6-amino-1-hexanol, 5-amino-1-pentanol, 2-amino-1-hexanol, 1-amino-1-cyclopentanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-aminocyclohexanol, 5-amino-2,2-dimethylpentanol, 4-aminobenzyl alcohol, 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, and ethanolamine.

13. The preparation method according to claim 8, wherein, In step 1), the solvent includes at least one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, and dichloromethane.

14. A boron- and imide-containing thickener prepared by the preparation method according to any one of claims 1-13.

15. A boron- and imide-containing tackifier, wherein the raw materials for preparing the boron- and imide-containing tackifier comprise the following components: (a) Imide compounds; said imide compounds are compounds containing an imide structure and a hydroxyl group; (b) Boron ester compounds; (c) Solvents may be added or not added at will; The raw materials for preparing the imide compounds include the following components: (1) Dianhydride compounds; (2) Amino alcohols; (3) Solvents may be added or not added at will.

16. The boron- and imide-containing thickener according to claim 15, wherein, The raw materials for preparing the boron- and imide-containing tackifier include the following components in parts by weight: (a) Imidamine compounds: 1 part; (b) Boron ester compounds: 0.5 to 5 parts; (c) Solvents to be added or not added: 0 to 100 parts.

17. The boron- and imide-containing thickener according to claim 15, wherein, The raw materials for preparing the imide compounds include the following components in parts by weight: (1) Dianhydride compounds: 1 part; (2) Amino alcohols: 0.5-5 parts; (3) Solvents to be added or not added: 0 to 50 parts.

18. The boron- and imide-containing tackifier according to claim 15, wherein, The boron- and imide-containing thickener has a molecular weight of 500-1000 g / mol.

19. The use of a boron- and imide-containing tackifier as described in any one of claims 15-18 in silicone rubber.

20. The application according to claim 19, wherein, The silicone rubber includes at least one of addition-type silicone rubber, condensation-type silicone rubber, and high-temperature vulcanized silicone rubber.

21. An adhesive sealant comprising the boron- and imide-containing tackifier as described in any one of claims 15-18.

22. The adhesive sealant according to claim 21, wherein, The adhesive sealant also includes silicone rubber, which includes at least one of addition-type silicone rubber, condensation-type silicone rubber, and high-temperature vulcanized silicone rubber.

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