Silane coupling agent and its use in the preparation of two-component moisture hardening silicone resin compositions

Abstract

The application discloses a silane coupling agent and application thereof in a two-component moisture hardening silicone resin composition, and belongs to the technical field of high polymer materials. The silane coupling agent provided by the application can effectively reduce the touch dry time of the silicone resin composition, improve the curing depth, effectively improve the water immersion and water purple bonding property of the silicone resin composition, and improve the initial adhesion of the silicone resin composition to substrates such as plastics and light aluminum; and the storage stability of the obtained silicone resin composition is excellent. Meanwhile, the silane coupling agent and the two-component moisture hardening silicone resin composition provided by the application have a wide source of raw materials, a simple preparation process, and are beneficial to actual large-scale production.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of high polymer materials, and particularly relates to a silane coupling agent and application thereof in preparing a two-component moisture hardening silicone resin composition. BACKGROUND

[0002] The moisture hardening silicone resin composition has excellent resistance to ultraviolet light, weathering and high temperature and humidity, and its durability under harsh conditions is particularly outstanding compared with other types of sealant. Among them, the silicone structural adhesive has high strength, can withstand large load, is resistant to aging and fatigue, and has a wide application in bonding between different materials such as glass, metal and ceramic, and is simple and time-saving in construction without damaging the original structure. However, the silicone structural adhesive also has some disadvantages, among which the slow curing speed, low initial adhesion, poor water immersion and water violet adhesion to aluminum, and low storage period are the biggest problems.

[0003] The curing speed includes two aspects, one is the dry, and the other is the curing depth, while the initial adhesion generally refers to the initial surface adhesion between materials. In general, after the construction of the two-component silicone structural adhesive is completed, the initial adhesion is weak after 4-24h of curing. In addition, the two-component moisture hardening silicone resin composition has poor water immersion and water violet adhesion to aluminum substrate, and due to the difference in activity of the components in the curing agent, the storage period is relatively low, and the dry and breaking time changes rapidly. SUMMARY

[0004] The present application aims to overcome the shortcomings of the prior art and provide a silane coupling agent applied in a two-component moisture hardening silicone resin composition, which has high initial adhesion and fast curing speed, and the obtained two-component moisture hardening silicone resin composition has excellent adhesion after water immersion and water violet treatment, and high storage stability.

[0005] To achieve the above-mentioned purpose, in the first aspect of the present application, the present application provides a silane coupling agent, the structural formula of which is shown as formula I:

[0006]

[0007] wherein R is selected from methyl or ethyl, n is 1, 2 or 3, and m = 0 or 1.

[0008] The silane coupling agent provided by the present application applied in a two-component moisture hardening silicone resin composition can effectively improve the dry time of the two-component moisture hardening silicone resin composition, accelerate the curing speed and depth, and also can well improve the water immersion and water violet adhesion of the two-component moisture hardening silicone resin composition, and also can effectively improve the initial adhesion of the two-component moisture hardening silicone resin.

[0009] Specifically, in the first aspect, the silane coupling agent provided by the application contains a phenolic hydroxyl group in the molecular structure, which can assist in catalyzing condensation reaction, effectively shorten the drying time, and improve the curing depth of the subsequent silicone resin composition; in the second aspect, the silane coupling agent can convert the traditional primary amine group into a secondary amine group through reaction, reduce the basicity of the amino silane, and at the same time, the molecular structure also has a long hydrophobic long-chain group, which can effectively improve the water immersion and water purple adhesion of the subsequent silicone resin composition; in the third aspect, the polar phenolic hydroxyl group and the phenyl skeleton in the molecular structure of the silane coupling agent provided by the application can improve the wettability and activity of the silicone resin composition system and the contact surface prepared subsequently, and the heat resistance of the silicone resin composition system itself, improve the compatibility with plastic base materials (such as PET and PVC), improve the initial adhesion, and through the surface interaction of the polar phenolic hydroxyl group and the phenyl skeleton with the PET, PVC and aluminum foil base materials, the initial adhesion of the obtained silicone resin composition to the aluminum foil base materials is improved.

[0010] Preferably, when m is 0, the substituent on the corresponding nitrogen is hydrogen.

[0011] In the second aspect of the application, the application provides a preparation method of the silane coupling agent, which comprises the following steps:

[0012] The amino silane compound shown in formula II, the formaldehyde aqueous solution and the catalyst are added into an organic alcohol solution and first stirred, then the phenolic substance shown in formula III is added for reflux reaction, after the reaction is completed, concentration is performed, then saturated sodium carbonate aqueous solution is added for second stirring, after the second stirring is completed, extraction, washing, separation, and concentration are performed, and the silane coupling agent is obtained.

[0013]

[0014] wherein R is selected from methyl or ethyl, and n is 1, 2 or 3.

[0015] The raw materials used in the preparation method provided by the application have a wide source, the preparation method adopts one-pot process, the operation is simple, the process is simple and convenient, the production process is green and environmentally friendly, and it is conducive to the actual process scale production.

[0016] As a preferred embodiment of the preparation method of the application, the amino silane compound shown in formula II includes at least one of aminoethyl aminopropyl trimethoxysilane, aminoethyl aminopropyl triethoxysilane, and aminopropyl methyl dimethoxysilane.

[0017] As a preferred embodiment of the preparation method of the application, the catalyst includes at least one of hydrochloric acid, sulfuric acid and trifluoroacetic acid.

[0018] As a preferred embodiment of the preparation method of the application, the organic alcohol includes at least one of methanol and ethanol.

[0019] As a preferred embodiment of the preparation method of the present application, the phenolic substance shown in formula III includes cardanol.

[0020] As a preferred embodiment of the preparation method of the present application, the mass percentage of formaldehyde in the aqueous formaldehyde solution is 35-40%.

[0021] The present application researches and finds that when the above-mentioned type of substance is further selected as the raw material of the reaction, the comprehensive performance of the obtained silicone resin composition is better when the obtained silane coupling agent is applied to the preparation of the subsequent two-component moisture curing silicone resin composition.

[0022] As a preferred embodiment of the preparation method of the present application, the molar ratio of the amino silane compound, formaldehyde, and phenolic substance is 1:(1-3):(1-3).

[0023] Exemplarily, the molar ratio of the amino silane compound, formaldehyde, and phenolic substance can be any point value or any two-point range value between 1:(1-3):(1-3), such as 1:1:1, 1:1:2, 1:1:3, 1:2:1, 1:2:3, 1:3:1, 1:3:2, 1:3:3, etc.

[0024] Preferably, the molar ratio of the amino silane compound, formaldehyde, and phenolic substance is 1:(1.8-2):(1.8-2).

[0025] As a preferred embodiment of the preparation method of the present application, the mass percentage of the organic alcohol solution is 5-70% based on the total mass of the amino silane compound, the aqueous formaldehyde solution, the phenolic substance, and the catalyst.

[0026] Exemplarily, the mass percentage of the organic alcohol solution can be any point value or any two-point range value between 5-70% based on the total mass of the amino silane compound, the aqueous formaldehyde solution, the phenolic substance, and the catalyst, such as 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, etc.

[0027] Preferably, the mass percentage of the organic alcohol solution is 50-65% based on the total mass of the amino silane compound, the aqueous formaldehyde solution, the phenolic substance, and the catalyst.

[0028] As a preferred embodiment of the preparation method of the present application, the mass percentage of the catalyst is 1-3% based on the mass of the amino silane compound.

[0029] Exemplarily, the mass percentage of the catalyst can be any point value or any two-point range value between 1-3% based on the mass of the amino silane compound, such as 1%, 2%, 3%, etc.

[0030] As a preferred embodiment of the preparation method of the application, the first stirring time is 20-40 min.

[0031] As a preferred embodiment of the preparation method of the application, the reflux reaction time is 6-10 h.

[0032] As a preferred embodiment of the preparation method of the application, the second stirring time is 20-40 min.

[0033] The application researches and finds that when the molar or mass ratio of the raw materials during the reaction is further selected within the above range, and the parameters during the reaction are within the above range, the obtained silane coupling agent has better effect.

[0034] In the third aspect of the application, the application provides application of the silane coupling agent in preparation of a two-component moisture curing silicone resin composition.

[0035] The silane coupling agent provided by the application can be effectively applied in the two-component moisture curing silicone resin composition, helping to improve the curing speed and initial adhesion of the silicone resin composition, and improving the storage stability of the silicone resin composition.

[0036] In the fourth aspect of the application, the application provides a two-component moisture curing silicone resin composition, which comprises an A component and a B component, and the mass ratio of the A component and the B component is (12-18):1.

[0037] The A component comprises the following raw materials in parts by mass: 100 parts of polysiloxane, 8-30 parts of a first plasticizer, and 80-135 parts of a first inorganic filler.

[0038] The B component comprises the following raw materials in parts by mass: 100 parts of a second plasticizer, 6-35 parts of a crosslinking agent, 4-20 parts of the silane coupling agent of the application, 0.5-55 parts of a second inorganic filler, and 0.05-0.7 parts of a catalyst.

[0039] The application researches and finds that the two-component moisture curing silicone resin composition provided by the application has good synergistic effect between the components by selecting the A component and the B component within the appropriate mass ratio range and adding the silane coupling agent of the application in the B component, can effectively improve the curing speed of the silicone resin composition, reduce the dry-to-touch time, has good water immersion and water purple adhesion, has high initial adhesion, and has excellent storage stability.

[0040] As a preferred embodiment of the two-component moisture curing silicone resin composition of the present application, the mass ratio of the A component and the B component is (13-15) : 1.

[0041] As a preferred embodiment of the two-component moisture curing silicone resin composition of the present application, the A component comprises the following raw materials in parts by mass: polysiloxane 100 parts, first plasticizer 10-25 parts, first inorganic filler 110-130 parts.

[0042] As a preferred embodiment of the two-component moisture curing silicone resin composition of the present application, the B component comprises the following raw materials in parts by mass: second plasticizer 100 parts, crosslinking agent 20-30 parts, silane coupling agent of the present application 5-8 parts, second inorganic filler 5-40 parts, catalyst 0.5-0.6 parts.

[0043] The present application has found that the mass ratio of the A component and the B component in the two-component moisture curing silicone resin composition, and the number of components in the A component and the B component, will affect the comprehensive performance of the silicone resin. When the mass ratio of the A component and the B component in the two-component moisture curing silicone resin composition, and the number of components in the A component and the B component are further selected within the above ranges, the obtained silicone resin composition has shorter dry time, higher tack, and more excellent water immersion and water violet adhesion.

[0044] As a preferred embodiment of the two-component moisture curing silicone resin composition of the present application, the viscosity of the polysiloxane at 25℃ is 5-50 Pa.s.

[0045] It should be noted that the viscosity of the polysiloxane at 25℃ is obtained by Brookfield viscometer test.

[0046] Preferably, the viscosity of the polysiloxane at 25℃ is 5-15 Pa.s.

[0047] The present application has found that the viscosity of the polysiloxane at 25℃ will affect the compatibility between the polysiloxane and other components and the flowability of the system. When the viscosity of the polysiloxane at 25℃ is further selected within the above range, especially 5-15 Pa.s, the comprehensive performance of the obtained product is more excellent.

[0048] As a preferred embodiment of the two-component moisture curing silicone resin composition of the present application, the viscosity of the first plasticizer and the second plasticizer at 25℃ is independently 0.1-12.5 Pa.s.

[0049] It should be noted that the viscosity of the first plasticizer and the second plasticizer at 25℃ is obtained by Brookfield viscometer test.

[0050] Preferably, the viscosity of the first plasticizer and the second plasticizer at 25°C is 0.1-5 Pa·s.

[0051] The present invention has found that the viscosity of the first and second plasticizers at 25°C also affects their compatibility with other components and the flowability of the system. When the viscosity of the first and second plasticizers at 25°C is further selected to be within the above range, especially 0.1-5 Pa·s, the overall performance of the obtained product is better.

[0052] In a preferred embodiment of the two-component moisture-curing silicone resin composition of the present invention, the average particle size of the first inorganic filler and the second inorganic filler is independently 40-100 nm.

[0053] It should be noted that the average particle size of the first inorganic filler and the second inorganic filler was obtained by measuring the particle size using a particle size analyzer.

[0054] As a preferred embodiment of the two-component moisture-curing silicone resin composition of the present invention, the polysiloxane includes at least one of α,ω-dihydroxy polydimethylsiloxane and methyldimethoxy-terminated polydimethylsiloxane.

[0055] In a preferred embodiment of the two-component moisture-curing silicone resin composition of the present invention, the first plasticizer and the second plasticizer are each independently selected from at least one of dimethyl silicone oil, MDT silicone oil, and hydroxyl silicone oil.

[0056] As a preferred embodiment of the two-component moisture-curing silicone resin composition of the present invention, the first inorganic filler includes surface-treated calcium carbonate, and the surface treatment agent used for the surface treatment includes at least one of rosin acid, fatty acid, and stearic acid.

[0057] As a preferred embodiment of the two-component moisture-curing silicone resin composition of the present invention, the second inorganic filler includes at least one of carbon black, surface-treated calcium carbonate, and fumed silica, and the surface treatment agent used for the surface treatment includes at least one of rosin acid, fatty acid, and stearic acid.

[0058] As a preferred embodiment of the two-component moisture-curing silicone resin composition of the present invention, the crosslinking agent includes at least one of methyltrimethoxysilane, vinyltrimethoxysilane, propyltrimethoxysilane, methyl orthosilicate, ethyl orthosilicate, and No. 3 waterproofing agent.

[0059] In a preferred embodiment of the two-component moisture-curing silicone resin composition of the present invention, the catalyst includes at least one of dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate, dimethyltin dineodecanate, and dibutyltin diacetylacetonate.

[0060] The present invention has found that when the components are further selected as substances of the above type, the overall performance of the obtained product is even better.

[0061] In a fifth aspect, the present invention provides a method for preparing the two-component moisture-curing silicone resin composition, the method comprising the following steps:

[0062] (1) Preparation of component A: Mix and knead the raw materials of component A to obtain component A;

[0063] (2) Preparation of component B: The second plasticizer and the second inorganic filler are mixed and stirred and then cooled. Then, the crosslinking agent, the silane coupling agent described in this invention and the catalyst are added and mixed in an inert gas environment to obtain component B.

[0064] In a preferred embodiment of the preparation method of the present invention, in step (1), the mixing and kneading temperature is 90-110℃, the vacuum degree is (-0.088)-(-0.092)MPa, and the time is 110-130min.

[0065] In a preferred embodiment of the preparation method of the present invention, in step (2), the mixing and stirring temperature is 90-110℃, the vacuum degree is (-0.088)-(-0.092)MPa, and the time is 1.5-2.5h.

[0066] In a preferred embodiment of the preparation method of the present invention, the temperature after cooling in step (2) is 28-32°C.

[0067] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0068] The silane coupling agent provided by this invention, when applied to a two-component moisture-curing silicone resin composition, can effectively reduce the finger-drying time of the silicone resin composition, increase the curing depth, and effectively improve the water immersion and water-based adhesion of the silicone resin composition, as well as the initial tack to substrates such as plastics and aluminum. Furthermore, the resulting silicone resin composition exhibits excellent storage stability. In addition, the silane coupling agent and the two-component moisture-curing silicone resin composition provided by this invention have widely available raw materials and a simple preparation process, which is beneficial for large-scale practical production. Detailed Implementation

[0069] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0070] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in the art; and unless otherwise specified, the components used in the examples and comparative examples are the same.

[0071] Polysiloxane 1: α,ω-dihydroxypolydimethylsiloxane, viscosity at 25℃ is 10 Pa·s, Jiangxi Lanxing Xinghuo Organosilicon Co., Ltd. 107V10000;

[0072] Polysiloxane 2: α,ω-dihydroxypolydimethylsiloxane, viscosity at 25℃ is 50 Pa·s, Jiangxi Lanxing Xinghuo Organosilicon Co., Ltd. 107V50000;

[0073] Polysiloxane 3: Methyldimethoxy-terminated polydimethylsiloxane, viscosity at 25°C is 10 Pa·s, Jiangsu Kexing New Materials Co., Ltd. J-100;

[0074] Plasticizer 1: Dimethyl silicone oil, viscosity at 25°C 0.35 Pa·s, Jiangxi Lanxing Xinghuo Organosilicon Co., Ltd., Starsil TM PDMS 47V350;

[0075] Plasticizer 2: Dimethyl silicone oil, viscosity at 25°C 12.5 Pa·s, Jiangxi Lanxing Xinghuo Organosilicon Co., Ltd., Starsil TM PDMS 47V12500;

[0076] Inorganic filler 1: Calcium carbonate with stearic acid surface treatment, with an average particle size of 70 nm, Guangxi Huana New Materials Co., Ltd., CCS-25i;

[0077] Inorganic filler 2: Calcium carbonate with stearic acid surface treatment, with an average particle size of 100nm, Guangxi Huana New Materials Co., Ltd., CCS-18;

[0078] Inorganic filler 3: Carbon black, Cabot M470 carbon black;

[0079] Crosslinking agent: Methyltrimethoxysilane, commercially available;

[0080] Catalyst: Dibutyltin dilaurate, commercially available.

[0081] Example 1

[0082] This invention provides a silane coupling agent ZJ-1 (structural formula shown in Formula IV), and the preparation method of the silane coupling agent ZJ-1 includes the following steps:

[0083]

[0084] (1) In a four-necked flask equipped with a thermometer, dropping funnel, mechanical stirrer and condenser, 16.2 g of 37% formaldehyde aqueous solution, 22.2 g of aminoethylaminopropyltrimethoxysilane and 60 g of ethanol were added in sequence. Stirring was started and 0.5 g of hydrochloric acid was added. The mixture was stirred at room temperature for 30 min. Then 60.4 g of m-[(Z)-8-pentadecanenyl]phenol was added and the mixture was heated to reflux for 8 h.

[0085] The molar ratio of aminosilane compounds, formaldehyde, and phenolic substances is 1:2:2.

[0086] The total mass percentage of the organic alcohol solution, based on the total mass of aminosilane compounds, formaldehyde aqueous solution, phenolic substances, and catalyst, is 60.4%.

[0087] The mass percentage of the catalyst is 2% based on the mass of aminosilane compounds.

[0088] (2) After the reflux reaction is completed, the solvent is removed by rotary evaporation, 20 mL of saturated sodium bicarbonate aqueous solution is added and stirred for 30 min, then 100 mL of dichloromethane is added for extraction, and then washed with saturated brine until neutral, dried with anhydrous sodium sulfate, filtered, and the solvent is removed by rotary evaporation to obtain silane coupling agent ZJ-1.

[0089] The 1H NMR spectrum of silane coupling agent ZJ-1 is as follows: δ 0.6 (2H), 0.95 (6H), 1.29-1.4 (32H), 1.6 (4H), 2.0 (8H), 2.5-2.6 (12H), 3.55-3.6 (13H), 5.4 (4H), 6.45-6.9 (6H).

[0090] Example 2

[0091] This invention provides a silane coupling agent ZJ-2 (structural formula shown in Formula V), and the preparation method of the silane coupling agent ZJ-2 includes the following steps:

[0092]

[0093] (1) In a four-necked flask equipped with a thermometer, dropping funnel, mechanical stirrer and condenser, 16.2 g of 37% formaldehyde aqueous solution, 26.4 g of aminoethylaminopropyltriethoxysilane and 60 g of ethanol were added in sequence. Stirring was started and 0.5 g of hydrochloric acid was added. The mixture was stirred at room temperature for 30 min. Then 60.4 g of m-[(Z)-8-pentadecanenyl]phenol was added and the mixture was heated to reflux for 8 h.

[0094] The molar ratio of aminosilane compounds, formaldehyde, and phenolic substances is 1:2:2.

[0095] The organic alcohol solution comprises 58.0% by mass, based on the total mass of aminosilane compounds, formaldehyde aqueous solution, phenolic substances and catalyst.

[0096] The catalyst has a mass percentage of 1.9% based on the mass of aminosilane compounds.

[0097] (2) After the reflux reaction is completed, the solvent is removed by rotary evaporation, 20 mL of saturated sodium bicarbonate aqueous solution is added and stirred for 30 min, then 100 mL of dichloromethane is added for extraction, and then washed with saturated brine until neutral, dried with anhydrous sodium sulfate, filtered, and the solvent is removed by rotary evaporation to obtain silane coupling agent ZJ-2.

[0098] The 1H NMR spectrum of silane coupling agent ZJ-2 is as follows: δ 0.6 (2H), 0.95 (15H), 1.29-1.4 (32H), 1.6 (4H), 2.0 (8H), 2.5-2.6 (12H), 3.55-3.6 (10H), 5.4 (4H), 6.45-6.9 (6H).

[0099] Example 3

[0100] This invention provides a silane coupling agent ZJ-3 (a mixture of structures as shown in Formula IV and Formula VI), and the preparation method of the silane coupling agent ZJ-3 includes the following steps:

[0101]

[0102] (1) In a four-necked flask equipped with a thermometer, dropping funnel, mechanical stirrer and condenser, 14.6 g of 37% formaldehyde aqueous solution, 22.2 g of aminoethylaminopropyltrimethoxysilane and 60 g of ethanol were added in sequence. Stirring was started and 0.5 g of hydrochloric acid was added. The mixture was stirred at room temperature for 30 min. Then 54.4 g of m-[(Z)-8-pentadecanenyl]phenol was added and the mixture was heated to reflux for 8 h.

[0103] The molar ratio of aminosilane compounds, formaldehyde, and phenolic substances is 1:1.8:1.8.

[0104] The total mass percentage of the organic alcohol solution, based on the total mass of aminosilane compounds, formaldehyde aqueous solution, phenolic substances, and catalyst, is 65.4%.

[0105] The catalyst has a mass percentage of 1.9% based on the mass of aminosilane compounds.

[0106] (2) After the reflux reaction is completed, the solvent is removed by rotary evaporation, 20 mL of saturated sodium bicarbonate aqueous solution is added and stirred for 30 min, then 100 mL of dichloromethane is added for extraction, and then washed with saturated brine until neutral, dried with anhydrous sodium sulfate, filtered, and the solvent is removed by rotary evaporation to obtain silane coupling agent ZJ-3.

[0107] Application Examples 1-5

[0108] This invention provides a two-component moisture-curing silicone resin. The mass fractions of the components of the two-component moisture-curing silicone resin and the mass fractions of component A and component B during use are shown in Table 1.

[0109] Table 1

[0110]

[0111]

[0112] The preparation method of the two-component moisture-curing silicone resin provided in Application Example 1 includes the following steps:

[0113] (1) Add polysiloxane 1, plasticizer 1 and inorganic filler 1 to a kneader, keep the material temperature at 100℃ and the vacuum degree at -0.09MPa, knead, dehydrate and mix for 120min, and filter the material after kneading to obtain component A.

[0114] (2) In a planetary reactor, plasticizer 2 and inorganic filler 3 are mixed evenly, heated to 120°C, stirred for 2 hours under vacuum of -0.09MPa, cooled to about 30°C, and crosslinking agent, ZJ-1 and catalyst are added in sequence under nitrogen atmosphere and stirred evenly to obtain component B; the preparation method of the two-component moisture-curing silicone resin provided in Application Examples 2-5 is consistent with that in Application Example 1.

[0115] Application Example 6

[0116] The present invention provides a two-component moisture-curing silicone resin, the only difference between the two-component moisture-curing silicone resin and the application example 1 is that polysiloxane 2 is used instead of polysiloxane 1.

[0117] Application Example 7

[0118] The present invention provides a two-component moisture-curing silicone resin, the only difference between the two-component moisture-curing silicone resin and the application example 1 is that polysiloxane 3 is used instead of polysiloxane 1.

[0119] Application Example 8

[0120] The present invention provides a two-component moisture-curing silicone resin, the only difference between the two-component moisture-curing silicone resin and the application example 1 is that inorganic filler 2 is used instead of inorganic filler 1.

[0121] Application Example 9

[0122] The present invention provides a two-component moisture-curing silicone resin, the only difference between the two-component moisture-curing silicone resin and Application Example 1 is that ZJ-2 is used instead of ZJ-1.

[0123] Application Example 10

[0124] This invention provides a two-component moisture-curing silicone resin, the only difference between the two-component moisture-curing silicone resin and Application Example 1 is that ZJ-3 is used instead of ZJ-1.

[0125] Comparative Application Example 1

[0126] The present invention provides a two-component moisture-curing silicone resin in a comparative application example. The only difference between the two-component moisture-curing silicone resin and application example 1 is that aminoethylaminopropyltrimethoxysilane is used instead of ZJ-1.

[0127] Comparative Application Example 2

[0128] The present invention provides a two-component moisture-curing silicone resin in a comparative application example. The only difference between the two-component moisture-curing silicone resin and application example 1 is that aminopropyltrimethoxysilane is used instead of ZJ-1.

[0129] Comparative Application Example 3

[0130] The present invention provides a two-component moisture-curing silicone resin in a comparative application example. The only difference between the two-component moisture-curing silicone resin and application example 1 is that the mass ratio of component A to component B is 8:1.

[0131] Comparative Application Example 4

[0132] The present invention provides a two-component moisture-curing silicone resin in a comparative application example. The only difference between the two-component moisture-curing silicone resin and application example 1 is that the mass ratio of component A to component B is 21:1.

[0133] Example of effect

[0134] This invention investigates the performance of the two-component moisture-curing silicone resins prepared in Application Examples 1-10 and Comparative Application Examples 1-4. Components A and B were mixed uniformly according to the stated weight ratio and degassed before application. The pot life and finger-drying time were tested. H-type adhesive specimens (using an aluminum-glass substrate) were prepared according to the method provided in Chapter 7 of GB / T13477.8-2002 and cured for 7 days at a temperature of (23±2)℃ and a relative humidity of (50±5)%. The pot life, tensile bond strength at 23℃, after immersion in water, and after water-UV irradiation, as well as the area of ​​failure and aging retention rate (bond strength retention rate = tensile bond strength after aging / tensile bond strength at 23℃ * 100%) were tested according to the requirements of GB / T 16776-2005. A 1mm thick adhesive sample was prepared according to GB / T13477.5-2002, and the finger-drying time of the thin-layer curing was tested using Method B.

[0135] The results are shown in Table 2;

[0136] Table 2

[0137]

[0138]

[0139] As can be seen from Table 2, when the technical solution provided by this invention is adopted, the obtained product has excellent curing speed, bonding strength, water immersion, and water-purple stability. Specifically, the short-term pot life of the obtained product is between 25-36 minutes, and the 6-month pot life is between 35-50 minutes, that is, the pot life meets the requirements of GB / T16776-2005. The finger drying time is between 0.8h and 1.5h, which meets the application requirements. Under standard conditions, the bonding strength is above 1.30MPa, the bonding failure area is below 4%, the failure area after water immersion is below 10%, the bonding strength retention rate after water immersion is above 80%, the failure area after water-purple treatment is below 10%, and the bonding strength retention rate after water-purple treatment is above 75%.

[0140] As can be seen from Application Example 1 and Comparative Application Examples 1-2, when the silane coupling agent provided by the present invention is not used, the water immersion resistance and water violet treatment ability of the obtained product are significantly reduced; as can be seen from Application Example 1 and Comparative Application Examples 3-4, when the mass ratio of component A to component B is not within the range of the present invention, the overall performance of the obtained product also shows a significant downward trend.

[0141] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present invention and not to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A silane coupling agent characterized by, The silane coupling agent has a structural formula as shown in Formula Ia or Formula Ib. Formula Ia, Formula Ib, R is selected from methyl or ethyl, and n is 1, 2 or 3.

2. The method for preparing a silane coupling agent according to claim 1, wherein The preparation method comprises the following steps: The amino silane compound shown in Formula II, the formaldehyde aqueous solution and the catalyst are added into an organic alcohol solution and stirred for the first time, then the phenolic substance shown in Formula III is added for reflux reaction, after the reaction is completed, concentration is performed, then saturated sodium carbonate aqueous solution is added for the second stirring, after the second stirring is completed, extraction, washing, separation, concentration are performed, and the silane coupling agent is obtained; Formula II, Formula III, R is selected from methyl or ethyl, and n is 1, 2 or 3.

3. The preparation method according to claim 2, characterized in that, At least one of the following: a. The amino silane compound shown in Formula II comprises at least one of aminoethylaminopropyltrimethoxysilane and aminoethylaminopropyltriethoxysilane; b. The catalyst comprises at least one of hydrochloric acid, sulfuric acid and trifluoroacetic acid; c. The organic alcohol comprises at least one of methanol and ethanol; d. The phenolic substance shown in Formula III comprises cardanol; e. In the formaldehyde aqueous solution, the mass percentage of formaldehyde is 35-40%.

4. The production method according to claim 2, characterized by, The molar ratio of the amino silane compound, the formaldehyde and the phenolic substance is 1: (1-3): (1-3); And / or, the mass percentage of the organic alcohol solution is 5-70% based on the total mass of the amino silane compound, the formaldehyde aqueous solution, the phenolic substance and the catalyst; And / or, the mass percentage of the catalyst is 1-3% based on the mass of the amino silane compound; And / or, the time of the first stirring is 20-40 min; And / or, the time of the reflux reaction is 6-10 h; And / or, the time of the second stirring is 20-40 min.

5. The silane coupling agent according to claim 1 is applied to the preparation of a two-component moisture-curing silicone resin composition.

6. A two-component moisture hardening silicone resin composition, characterized by, The two-component moisture-curing silicone resin composition comprises an A component and a B component, and the mass ratio of the A component and the B component is (12-18): 1; The A component comprises the following raw materials in mass parts: 100 parts of polysiloxane, 8-30 parts of a first plasticizer and 80-135 parts of a first inorganic filler; The B component comprises the following raw materials in mass parts: 100 parts of a second plasticizer, 6-35 parts of a crosslinking agent, 4-20 parts of the silane coupling agent according to claim 1, 0.5-55 parts of a second inorganic filler and 0.05-0.7 parts of a catalyst.

7. The two-part moisture curing silicone resin composition according to claim 6, characterized in that, The mass ratio of the A component and the B component is (13-15): 1; And / or, the A component comprises the following raw materials in mass parts: 100 parts of polysiloxane, 10-25 parts of a first plasticizer and 110-130 parts of a first inorganic filler; And / or, the B component comprises the following raw materials in mass parts: 100 parts of a second plasticizer, 20-30 parts of a crosslinking agent, 5-8 parts of the silane coupling agent according to claim 1, 5-40 parts of a second inorganic filler and 0.5-0.6 parts of a catalyst.

8. The two-part moisture curing silicone resin composition according to claim 6, characterized in that, The viscosity of the polysiloxane at 25°C is 5-50 Pa.s; And / or, the viscosity of the first plasticizer and the second plasticizer at 25°C is independently 0.1-12.5 Pa.s; And / or, the average particle size of the first inorganic filler and the second inorganic filler is independently 40-100nm.

9. The two-part moisture curing silicone resin composition according to claim 6, characterized in that, The polysiloxane comprises at least one of α,ω-dihydroxy polydimethylsiloxane, methyl dimethoxy terminated polydimethylsiloxane; And / or, the first plasticizer and the second plasticizer are independently selected from at least one of dimethyl silicone oil, MDT silicone oil, hydroxyl silicone oil; And / or, the first inorganic filler comprises surface-treated calcium carbonate, and the surface treatment agent used in the surface treatment comprises at least one of rosin acid, fatty acid, stearic acid; And / or, the second inorganic filler comprises at least one of carbon black, surface-treated calcium carbonate, fumed silica, and the surface treatment agent used in the surface treatment comprises at least one of rosin acid, fatty acid, stearic acid; And / or, the crosslinking agent comprises at least one of methyl trimethoxysilane, vinyl trimethoxysilane, propyl trimethoxysilane, methyl orthosilicate, ethyl orthosilicate, and No. 3 waterproof agent; And / or, the catalyst comprises at least one of dibutyl tin diacetate, dibutyl tin dilaurate, dioctyl tin dilaurate, stannous octoate, dimethyl tin dineodecanoate, and dibutyl tin acetylacetone.

10. The method of making a two-part moisture curing silicone composition according to any one of claims 6 to 9, characterized in that, The preparation method comprises the following steps: (1) Preparation of component A: mix and knead the raw materials of component A to obtain component A; (2) Preparation of component B: mix and stir the second plasticizer and the second inorganic filler, then cool, and subsequently mix the crosslinking agent, the silane coupling agent as claimed in claim 1, and the catalyst in an inert gas environment to obtain component B.

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