CN111057516B - High-temperature curable silicone structural sealant and application thereof - Google Patents
High-temperature curable silicone structural sealant and application thereof Download PDFInfo
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J11/06—Non-macromolecular additives organic
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Abstract
The invention discloses a high-temperature curable silicone structural sealant and application thereof. According to the invention, through the matching design of the component A and the component B, the auxiliary agent with high activity and high stability is prepared from the silane coupling agent, the silane cross-linking agent and the macromolecular modified resin, and the two-component silicone structural sealant is prepared by glue mixing and sizing under the condition of wider temperature. The sealant can be used for glue mixing and sizing in the environment of a conventional temperature range, can also be used for glue mixing and sizing in the environment of high temperature, has no bubble, particle and gel phenomena before the colloid is cured, has no bubble, floating color and particle after the colloid is cured, and has excellent long-term stability in the aspects of thermal aging resistance, high and low temperature resistance, ultraviolet resistance, weather aging resistance, elastic recovery rate, displacement capacity and the like. The sealant can be used for mutual structural bonding of materials such as glass, aluminum profiles, steel, stone and the like.
Description
Technical Field
The invention belongs to the technical field of high-molecular sealants, and particularly relates to a high-temperature-curable silicone structural sealant and application thereof.
Background
With the continuous development and progress of science and technology, the application of the adhesive in various fields is also rapidly expanded. The silicone structural sealant has excellent comprehensive performances of high and low temperature resistance, ultraviolet resistance, weather aging resistance, elastic recovery rate, displacement capacity, ozone aging resistance and the like, and has the advantages of simple construction mode and light weight, so that the silicone structural sealant is more and more widely applied to the traditional application fields of buildings, electronics, traffic and the like, and is also rapidly expanded in the application of new industries such as photovoltaic installation, photovoltaic buildings and the like.
The silicone structural sealant can be divided into a single component and a double component according to different components, wherein the double component type has more applications in high-quality projects due to more stable performance and controllable reaction kinetics. However, the requirement of the application environment temperature of the conventional two-component silicone structural sealant is higher, and the conventional sealant is used under the conditions of the temperature of 10-40 ℃ and the relative humidity of 40-80 percent, so that a better bonding effect can be obtained. For example, CN1282772A, CN105255439B, CN105255439A, CN101864172A, CN105368379A, CN10320072B and the like all refer to the proposal that the test evaluation is carried out after the mixed glue sizing and curing for 14-21 days under the curing condition temperature (23 s 2) DEG C specified in GB16776 structural silicone sealant for buildings. After the standard conditions are removed, the performance of the colloid is greatly influenced, such as the phenomena of bubbles, low strength, weak bonding force with a base material, reversion and the like. CN201510133876.8 reports that a condensed type bi-component silicone sealant is placed under a sealed condition of 90 ℃ immediately after being prepared under a standard condition, eliminates the reversion phenomenon and has excellent strength and bonding property.
The environmental control of construction in the factory is easy to realize, however, in the outdoor application of the structural adhesive, a plurality of occasions which do not accord with standard conditions exist, for example, when the outdoor temperature in summer can reach more than 40 ℃, the surface of a building, particularly the surface of a steel structure roof can reach more than 65 ℃. When the two-component silicone structural sealant is mixed and applied in an environment with the temperature of more than 40 ℃, the reaction speed is high, and the problems of poor elastic recovery, weak strength, low elongation and the like are easy to occur.
Therefore, the development of a high-temperature curing type two-component silicone structural sealant can be used for glue mixing and gluing under the conventional temperature condition, can glue and glue at high temperature to obtain a colloid which has no inner foam pores and excellent performances in the aspects of thermal aging resistance, high and low temperature resistance, ultraviolet ray resistance, weather aging resistance, elastic recovery rate, displacement capacity and the like, can adapt to outdoor severe high-temperature operating environment, and is a problem to be solved by technical personnel in the industry.
Disclosure of Invention
The invention aims to make up the defects of the prior art and provides a high-temperature-curable two-component silicone structural sealant and application thereof. According to the invention, through the matching design of the component A and the component B, the two-component silicone structural sealant is prepared by mixing and sizing under the condition of a wider temperature by using the auxiliary agent with high activity and high stability prepared from the silane coupling agent, the silane crosslinking agent and the macromolecular modified resin. The sealant can be used for glue mixing and sizing in the conventional temperature range of 5-40 ℃, can also be used for glue mixing and sizing in the environment of 40-80 ℃ at high temperature, has no bubble, particle and gel phenomena before the colloid is cured, has no bubble, flooding and particle after the colloid is cured, and has excellent long-term stability in the aspects of thermal aging resistance, high and low temperature resistance, ultraviolet resistance, weather aging resistance, elastic recovery rate, displacement capacity and the like. The sealant has wide application, and can be used for structural bonding of materials such as glass, aluminum profiles, stainless steel, stone and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-temperature curable silicone structural sealant, which consists of a component A and a component B:
the component A comprises 24-50 wt% of hydroxyl-terminated polydimethylsiloxane, 5-10 wt% of modified silicone oil, 1-10 wt% of coupling agent and 39-60 wt% of first filler; the coupling agent is formed by mixing one or two of methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane according to any proportion;
the component B comprises 40-60 wt% of dimethyl silicone oil, 10-30 wt% of second filler, 5-40 wt% of auxiliary agent and 0.01-0.5 wt% of catalyst; the auxiliary agent in the component B is prepared by compounding a silane coupling agent, a silane cross-linking agent and modified resin.
According to the invention, the coupling agent is introduced into the component A, so that the active group point density in the component A is increased, the contact speed of crosslinking points in the glue mixing process of the component A and the component B is improved, and a pre-crosslinking structure is formed quickly.
Furthermore, the auxiliary agent in the component B is prepared by heating and compounding propyl trimethoxy silane, propyl triethoxy silane, 3- (2, 3-epoxypropoxy) propyl triethoxy silane, 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane and modified resin;
the propyl trimethoxy silane, the propyl triethoxy silane, the 3- (2, 3-epoxypropoxy) propyl triethoxy silane, the 3-aminopropyl trimethoxy silane, the 3-aminopropyl triethoxy silane and the modified resin respectively account for the following components in percentage by weight in total mass: 5-40 wt%, 0-10 wt%, 5-25 wt%, 3-15 wt%.
Further, the specific preparation method of the auxiliary agent in the component B comprises the following steps:
(1) adding propyl trimethoxy silane, propyl triethoxy silane, 3- (2, 3-epoxypropoxy) propyl triethoxy silane, 3-aminopropyl trimethoxy silane and 3-aminopropyl triethoxy silane into a reaction kettle, and slowly heating to 50-80 ℃ while stirring for reaction for 0.5-2 hours;
(2) slowly heating to 100-150 ℃, and adding the modified resin into the reaction kettle while stirring;
(3) and under the reflux state, continuously reacting for 2-24 hours while stirring, introducing nitrogen, naturally cooling to 25-30 ℃, discharging, and preparing to obtain the auxiliary agent.
Preferably, the modified resin is formed by mixing one or more of silane modified polyether resin, hydroxyl terminated polybutadiene resin and silane modified polyurethane resin with the viscosity of 2000-30000 cs according to any proportion.
Furthermore, the viscosity of the hydroxyl-terminated polydimethylsiloxane in the component A is 1000 cs-100000 cs.
Further, the modified silicone oil in the component A is one or more of hydroxyl modified silicone oil with the viscosity of 500 cs-10000 cs, polyether modified silicone oil, alkoxy modified silicone oil and epoxy modified silicone oil which are mixed according to any proportion.
Further, the first filler in the component A is formed by mixing one or two of active calcium carbonate with the particle size of 5 nm-25 nm and active silicon micro powder with the particle size of 2 mu m-20 mu m according to any proportion.
Preferably, the activated calcium carbonate is calcium carbonate with the surface treated by one or more of octamethylcyclotetrasiloxane, hexamethyldisilazane, dimethyldichlorosilane, rosin, fatty acid and stearic acid; the active silica micropowder is silica micropowder treated by one or more of gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane and 2- (3, 4-epoxycyclohexyl) -ethyl trimethyl silane.
Further, the second filler in the component B is formed by mixing one or two of carbon black or fumed silica with the particle size of 0.3-10 nm.
Further, the catalyst in the component B is selected from one or more of dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, dimethyltin dioctanoate, dioctanodecanoic acid, bismuth isooctanoate and organic phosphate.
The invention also provides an application of the silicone structure sealant, and the silicone structure sealant is used for mutual structural bonding among glass, aluminum profiles, stainless steel, steel or stone materials.
Further, after the silicone structural sealant is mixed in a static mixing or stirring mode, the silicone structural sealant is glued on the surface of one material to be bonded, the thickness of the material is 0.5-15 mm, and then the other material to be bonded is placed on the other surface of the structural sealant and used after maintenance.
The invention has the following technical characteristics:
1. the auxiliary agent used in the component B of the high-temperature curable silicone structural sealant is obtained by chemically compounding a silane coupling agent, a silane cross-linking agent and modified resin, has high thermal stability, and can keep better activity at high temperature.
2. The component A of the high-temperature curable silicone structural sealant disclosed by the invention is introduced with a small amount of coupling agent, so that the density of active group points in the component A can be increased, the contact speed of crosslinking points in the glue mixing process of the component A and the component B is improved, and a pre-crosslinking structure is formed quickly.
3. The formula of the component A and the component B is optimized and matched, so that the stability of the chemical reaction of the two components in a high-temperature environment is effectively improved, and a relatively stable cross-linking point structure is formed between premixes, so that a microchannel for quickly removing a large amount of bubbles is provided, and the bubble phenomenon after colloid solidification is eliminated.
4. The silicone structural sealant disclosed by the invention also has excellent long-term stability in the aspects of thermal aging resistance, high and low temperature resistance, ultraviolet ray resistance, weather aging resistance, elastic recovery rate, displacement capacity and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
In the specific embodiment of the invention, the component A is uniformly mixed at the temperature of 50-90 ℃ and the vacuum degree of 0.1-0.05 MPa, dehydrated until the water content is not higher than 1500ppm, cooled to room temperature and sealed for storage; and (3) uniformly mixing the component B at the temperature of 30-70 ℃ and dehydrating under the vacuum degree of 0.1-0.05 MPa until the water content is not higher than 800ppm, and cooling to room temperature for sealing and storing for later use.
In the specific implementation mode of the invention, the relative humidity of glue mixing, gluing and maintenance is within the range of 10-90%; before glue mixing, the component A and the component B are respectively placed for 24 hours at glue mixing and applying temperature; the curing condition is consistent with the sizing condition, and the time is 7 days.
In the concrete embodiment of the invention, each performance index of the silicone structure sealant is measured by the following method or standard:
1. pot life, surface drying time
The test method refers to the standard GB16776 Silicone structural sealant for construction.
Testing an instrument: a rubber cylinder and a timer.
And (3) testing conditions are as follows: and the curing conditions are consistent.
2. Hardness of
The test method is referred to the standard GB/T531.1 "test method for indentation hardness of vulcanized rubber or thermoplastic rubber".
Testing an instrument: film pressing machine, hardness tester.
And (3) testing conditions are as follows: temperature (23 ℃ C., 2 ℃ C.) and relative humidity (50 ℃ C., 5%) were measured.
3. Tensile strength, elongation at break and bonding area of H-shaped sample
The test method refers to the standard GB16776 Silicone structural sealant for construction.
Testing an instrument: a rubber cylinder, anodic alumina, glass and a tensile machine.
And (3) testing conditions are as follows: temperature (23 ℃ C., 2 ℃ C.) and relative humidity (50 ℃ C., 5%) were measured.
4. Elastic recovery rate
The test method refers to the standard GB/T13477 building sealing material test method.
Testing an instrument: the device comprises an isolation gasket, anodic alumina, glass and a tensile machine.
And (3) testing conditions are as follows: temperature (23 ℃ C., 2 ℃ C.) and relative humidity (50 ℃ C., 5%) were measured.
5. Tensile strength and elongation at break of dumbbell specimen
The test method refers to the standard GB/T528 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber.
Testing an instrument: a rubber cylinder, anodic alumina, glass and a tensile machine.
And (3) testing conditions are as follows: temperature (23 ℃ C., 2 ℃ C.) and relative humidity (50 ℃ C., 5%) were measured.
6. Shear strength
The test method refers to Standard GB/T7124 determination of adhesive tensile shear Strength (rigid Material to rigid Material). Testing an instrument: anodic alumina and a tensile machine.
And (3) testing conditions are as follows: temperature (23 ℃ C., 2 ℃ C.) and relative humidity (50 ℃ C., 5%) were measured.
Heat aging at 7.100 deg.C
The test method refers to the standard GB16776 Silicone structural sealant for construction.
Testing an instrument: anodic alumina and a tensile machine.
And (3) testing conditions are as follows: temperature (23 ℃ C., 2 ℃ C.) and relative humidity (50 ℃ C., 5%) were measured.
8. Capability of displacement
The test method refers to the standard GB22083 Classification and requirement of building sealant.
Testing an instrument: anodic alumina and a tensile machine.
And (3) testing conditions are as follows: temperature (23 ℃ C., 2 ℃ C.) and relative humidity (50 ℃ C., 5%) were measured.
DH high temperature high humidity aging
The test method refers to the design identification and design of crystalline silicon photovoltaic modules for ground in IEC 61215.
The test conditions are as follows: + 85 ℃ and relative humidity of 85%.
HF humid freeze aging
The test method refers to the design identification and design of crystalline silicon photovoltaic modules for ground in IEC 61215.
The test conditions are as follows: -40 ℃ to + 85 ℃ and a relative humidity of 85 +/-5%.
UV resistance to ultraviolet aging
The test method refers to the standard GB/T29848 ethylene-vinyl acetate copolymer (EVA) adhesive film for photovoltaic module packaging. The test conditions are as follows: 60 +/-5 ℃.
Example 1:
preparing a modification auxiliary agent:
(1) adding 25wt% of propyl trimethoxy silane, 10wt% of propyl triethoxy silane, 25wt% of 3- (2, 3-epoxypropoxy) propyl triethoxy silane, 25wt% of 3-aminopropyl trimethoxy silane and 12wt% of 3-aminopropyl triethoxy silane into a reaction kettle with a thermometer, a reflux condenser tube and a stirrer, and slowly heating to 55 ℃ while stirring for reaction for 2 hours;
(2) slowly heating to 150 ℃, and adding 3wt% of hydroxyl terminated liquid polybutadiene resin with the viscosity of 10000cs into the reaction kettle while stirring;
(3) and (3) under a reflux state, continuously reacting for 10 hours while stirring, introducing nitrogen, naturally cooling to 25-30 ℃, discharging, and preparing to obtain the auxiliary agent.
Preparing a component A:
30wt% of hydroxyl-terminated polydimethylsiloxane with viscosity of 20000cs, 10wt% of hydroxyl-modified silicone oil with viscosity of 8000cs, 1 wt% of methyltrimethoxysilane coupling agent, 19 wt% of activated calcium carbonate treated by octamethylcyclotetrasiloxane with particle size of 5nm and 40wt% of activated silicon micropowder treated by gamma-glycidyl ether oxypropyltrimethoxysilane with particle size of 20um are added into a kneader, the temperature of the materials is kept at 90 ℃, the vacuum degree is 0.1-0.05 MPa, the materials are kneaded and dehydrated for 60 minutes, the kneaded materials are ground by a three-roll grinder until the fineness is less than or equal to 50um measured by a scraper finesse meter and the moisture content is 1200ppm, and the component A is prepared, sealed and stored for later use.
Preparing a component B: uniformly mixing 40wt% of simethicone with the viscosity of 8000cs and 30wt% of carbon black with the particle size of 0.3nm in a planetary stirrer, heating to 40 ℃, keeping the vacuum degree at 0.1-0.05 MPa, stirring for 30-60 minutes, and cooling to below 30 ℃; under the condition of introducing nitrogen, adding 29.5 wt% of an auxiliary agent and 0.5 wt% of dibutyltin dilaurate serving as a catalyst into 3-5 batches, stirring uniformly, defoaming at a vacuum degree of 0.1-0.05 MPa for 120 minutes until the water content is 600ppm, preparing a component B, cooling to room temperature, and storing in a vacuum sealing manner for later use.
The A, B components were filled into a two-component rubber cartridge with a volume ratio of 10:1, and after mixing using a static mixing tube, sizing was performed.
A. Before mixing the component B, the mixture is placed in a constant temperature box at 80 ℃ for 24 hours. The temperature of mixing, applying glue and maintaining is all 80 ℃.
Example 2:
preparing a modification auxiliary agent:
(1) adding 30wt% of propyl trimethoxy silane, 20wt% of 3- (2, 3-epoxypropoxy) propyl triethoxy silane, 17wt% of 3-aminopropyl trimethoxy silane and 23wt% of 3-aminopropyl triethoxy silane into a reaction kettle provided with a thermometer, a reflux condenser pipe and a stirrer, and slowly heating to 60 ℃ while stirring for reaction for 1.5 hours;
(2) slowly heating to 130 ℃, and adding 10wt% of silane modified polyether resin with viscosity of 3500cs into the reaction kettle while stirring;
(3) and (3) under a reflux state, continuously reacting for 18 hours while stirring, introducing nitrogen, naturally cooling to 25-30 ℃, discharging, and preparing to obtain the auxiliary agent.
Preparing a component A:
adding 50wt% of hydroxyl-terminated polydimethylsiloxane with the viscosity of 1000cs, 5wt% of polyether modified silicone oil with the viscosity of 10000cs, 5wt% of propyl trimethoxy silane coupling agent, 30wt% of stearic acid-treated active calcium carbonate with the particle size of 25nm, 10wt% of 2- (3, 4-epoxycyclohexyl) -ethyl trimethyl silane-treated active silicon micropowder with the particle size of 2um into a kneader, keeping the material temperature at 70 ℃ and the vacuum degree at 0.1-0.05 MPa, kneading and dehydrating for 120 minutes, grinding the kneaded material by a three-roll grinder until the fineness is less than or equal to 50um measured by a scraper finesse meter and the moisture content is 1800ppm, preparing a component A, sealing and storing for later use.
Preparing a component B: uniformly mixing 49.99 wt% of dimethyl silicone oil with the viscosity of 15000cs and 10wt% of fumed silica with the particle size of 0.3nm in a planetary stirrer, heating to 50 ℃, keeping the vacuum degree of 0.1-0.05 MPa, stirring for 30-60 minutes, and cooling to below 30 ℃; under the condition of introducing nitrogen, adding 40wt% of an auxiliary agent and 0.01 wt% of dibutyltin dilaurate serving as a catalyst into 3-5 batches, stirring uniformly, defoaming at a vacuum degree of 0.1-0.05 MPa for 90 minutes until the water content is 200ppm, preparing a component B, cooling to room temperature, and storing in a vacuum seal manner for later use.
The A, B components were filled into a 9:1 by volume two-component rubber cartridge, and after mixing using a static mixing tube, sizing was performed.
A. Before mixing the component B, the mixture is placed in a constant temperature box at 40 ℃ for 24 hours. The temperature of mixing, applying glue and maintaining is all 40 ℃.
Example 3:
preparing a modification auxiliary agent:
(1) adding 36 wt% of propyl trimethoxy silane, 6wt% of propyl triethoxy silane, 5wt% of 3- (2, 3-epoxypropoxy) propyl triethoxy silane, 23wt% of 3-aminopropyl trimethoxy silane and 24wt% of 3-aminopropyl triethoxy silane into a reaction kettle with a thermometer, a reflux condenser tube and a stirrer, and slowly heating to 75 ℃ while stirring for reaction for 2 hours;
(2) slowly heating to 100 ℃, and adding 6wt% of silane modified polyurethane resin with the viscosity of 2000cs into the reaction kettle while stirring;
(3) and (3) under a reflux state, continuously reacting for 24 hours while stirring, introducing nitrogen, naturally cooling to 25-30 ℃, discharging, and preparing to obtain the auxiliary agent.
Preparing a component A:
adding 24wt% of hydroxyl-terminated polydimethylsiloxane with viscosity of 100000cs, 6wt% of alkoxy modified silicone oil with viscosity of 500cs, 5wt% of methyltriethoxysilane, 5wt% of 3-aminopropyltriethoxysilane and 60wt% of gamma-glycidyl ether oxypropyltrimethoxysilane treated active silicon micropowder with particle size of 5um into a kneader, keeping the material temperature at 50 ℃ and the vacuum degree at 0.1-0.05 MPa, kneading and dehydrating for 240 minutes, grinding the kneaded material by a three-roll grinder until the fineness is less than or equal to 50um measured by a scraper fineness gauge and the moisture content is 1500ppm, preparing the component A, sealing and storing for later use.
Preparing a component B: uniformly mixing 60wt% of dimethyl silicone oil with the viscosity of 5000cs and 34.7 wt% of carbon black with the particle size of 10nm in a planetary stirrer, heating to 60-90 ℃, keeping the vacuum degree at 0.1-0.05 MPa, stirring for 30-60 minutes, and then cooling to 80 ℃; under the condition of introducing nitrogen, adding 5wt% of an auxiliary agent and 0.3 wt% of catalyst dibutyltin dilaurate in 3-5 batches, stirring uniformly, defoaming for 30 minutes under the vacuum degree of 0.1-0.05 MPa, and keeping the moisture content at 1000ppm to prepare a component B, cooling to room temperature, and storing in a vacuum seal manner for later use.
The A, B components were filled into a two-component rubber cartridge with a volume ratio of 11:1, and after mixing using a static mixing tube, sizing was performed.
A. Before mixing the component B, the mixture is placed in a thermostat with the temperature of 5 ℃ for 24 hours. The temperature of mixing, applying glue and maintaining is 5 ℃.
Example 4:
preparing a modification auxiliary agent:
(1) adding 5wt% of propyl trimethoxy silane, 8wt% of propyl triethoxy silane, 22wt% of 3- (2, 3-epoxypropoxy) propyl triethoxy silane, 25wt% of 3-aminopropyl trimethoxy silane and 25wt% of 3-aminopropyl triethoxy silane into a reaction kettle with a thermometer, a reflux condenser and a stirrer, and slowly heating to 80 ℃ while stirring for reaction for 0.5 hour;
(2) slowly heating to 100 ℃, and adding 15wt% of silane modified polyether resin with the viscosity of 8000cs into the reaction kettle while stirring;
(3) and (3) under a reflux state, continuously reacting for 2 hours while stirring, introducing nitrogen, naturally cooling to 25-30 ℃, discharging, and preparing to obtain the auxiliary agent.
Preparing a component A:
adding 40wt% of 60000 cs-terminal hydroxyl polydimethylsiloxane, 8wt% of 2000 cs-epoxy modified silicone oil, 5wt% of 3-aminopropyltrimethoxysilane coupling agent and 53 wt% of active calcium carbonate treated by fatty acid with the particle size of 15nm into a kneader, maintaining the temperature of materials at 80 ℃ and the vacuum degree at 0.1-0.05 MPa, kneading and dehydrating for 180 minutes, grinding the kneaded materials by a three-roll grinder until the fineness of a scraper blade fineness meter is less than or equal to 50um and the moisture content is 800ppm, preparing the component A, and sealing and storing for later use.
Preparing a component B: uniformly mixing 51.9 wt% of dimethyl silicone oil with the viscosity of 10000cs and 40wt% of carbon black with the particle size of 2nm in a planetary stirrer, heating to 70 ℃, keeping the vacuum degree at 0.1-0.05 MPa, stirring for 30-60 minutes, and cooling to below 30 ℃; adding 8wt% of auxiliary agent and 0.1 wt% of catalyst dibutyltin dilaurate in 3-5 batches under the condition of introducing nitrogen, stirring uniformly, defoaming for 60 minutes under the vacuum degree of 0.1-0.05 MPa, wherein the moisture content is not 800ppm, preparing to obtain a component B, cooling to room temperature, and storing in a vacuum sealing manner for later use.
The A, B components were filled into a two-component rubber cartridge with a volume ratio of 10:1, and after mixing using a static mixing tube, sizing was performed.
A. Before mixing the component B, the mixture is placed in a constant temperature box at 23 ℃ for 24 hours. The temperature of mixing, applying glue and maintaining is 23 ℃.
Example 5:
preparing a modification auxiliary agent:
(1) adding 40wt% of propyl trimethoxy silane, 10wt% of propyl triethoxy silane, 25wt% of 3- (2, 3-epoxypropoxy) propyl triethoxy silane, 5wt% of 3-aminopropyl trimethoxy silane and 5wt% of 3-aminopropyl triethoxy silane into a reaction kettle with a thermometer, a reflux condenser tube and a stirrer, and slowly heating to 50 ℃ while stirring for reacting for 2 hours;
(2) slowly heating to 150 ℃, and adding 15wt% of silane modified polyurethane resin with the viscosity of 6000cs into the reaction kettle while stirring;
(3) and (3) under a reflux state, continuously reacting for 20 hours while stirring, introducing nitrogen, naturally cooling to 25-30 ℃, discharging, and preparing to obtain the auxiliary agent.
Preparing a component A:
adding 45 wt% of 50000 cs-terminated hydroxyl polydimethylsiloxane, 9 wt% of 4000 cs-viscosity alkoxy modified silicone oil, 3wt% of propyl trimethoxy silane, 4wt% of 3-aminopropyl trimethoxy silane coupling agent and 39 wt% of rosin-treated active calcium carbonate with the particle size of 20nm into a kneader, keeping the temperature of the material at 60 ℃ and the vacuum degree at 0.1-0.05 MPa, kneading and dehydrating for 60 minutes, grinding the kneaded material by a three-roll grinder until the tested fineness of a scraper fineness is less than or equal to 50um and the moisture content is 2000ppm, preparing the component A, and sealing and storing for later use.
Preparing a component B: uniformly mixing 45 wt% of dimethicone with the viscosity of 6000cs and 24.5 wt% of carbon black with the particle size of 5nm in a planetary stirrer, heating to 30 ℃, keeping the vacuum degree at 0.1-0.05 MPa, stirring for 30-60 minutes, and then cooling to below 30 ℃; under the condition of introducing nitrogen, adding 30wt% of an auxiliary agent and 0.5 wt% of catalyst dibutyltin dilaurate in 3-5 batches, stirring uniformly, defoaming for 100 minutes under the vacuum degree of 0.1-0.05 MPa, wherein the moisture content is 400ppm, preparing to obtain a component B, cooling to room temperature, and storing in a vacuum seal manner for later use.
The A, B components were filled into a two-component rubber cartridge with a volume ratio of 10:1, and after mixing using a static mixing tube, sizing was performed.
A. Before mixing the component B, the mixture is placed in a thermostat at 65 ℃ for 24 hours. The temperature of mixing, applying glue and maintaining is 65 ℃.
Comparative example 1:
according to the product specification, A, B components are tested according to the volume ratio of 10:1 after being glued by using an air-powered glue gun and a 32# static mixer, and relevant performances are tested. A. Before mixing the component B, the mixture is placed in a constant temperature box at 23 ℃ for 24 hours. The temperature of glue mixing, glue applying and maintenance is the same as that of the temperature environment of the comparison sample.
Comparative example 2:
according to the product specification, A, B components are tested according to the volume ratio of 10:1 after being glued by using an air-powered glue gun and a 32# static mixer, and relevant performances are tested. A. Before mixing the component B, the mixture is placed in a thermostat at 65 ℃ for 24 hours. The temperature of glue mixing, glue applying and maintenance is the same as that of the temperature environment of the comparison sample.
The performance test of the silicone sealant materials prepared in examples 1-5 and comparative examples 1-2 after curing for 7 days is shown in Table 1. Wherein, the A, B components are required to be placed in a constant temperature box for 24 hours before being mixed. The glue mixing, glue applying and maintenance are also operated in a constant temperature box at the same temperature.
The data in table 1 show that the high-temperature curable two-component silicone structural sealant disclosed by the invention can be used for mixing and gluing in the conventional temperature range of 5-40 ℃ to prepare a structural adhesive with excellent performance, and can also be used for mixing and gluing in the high-temperature environment of 40-80 ℃, so that the prepared colloid has no foam pores, no flooding and no particles, and has excellent long-term stability in the aspects of heat aging resistance, high and low temperature resistance, ultraviolet resistance, weather aging resistance, elastic recovery rate, displacement capacity and the like. The bi-component silicone structural sealant has the advantages of low material cost, simple preparation process, convenient application and operation and stable performance, and can greatly improve the application of the structural sealant in mutual structural bonding of materials such as glass, aluminum profiles, steel, stone and the like in photovoltaic modules, vehicles, building curtain walls, building roofs and photoelectric integrated buildings constructed outdoors or in workshops with large temperature change.
TABLE 1 Performance parameters of Silicone structural sealants prepared in examples 1-5 and comparative examples 1-2
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core ideas. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (8)
1. The high-temperature curable silicone structural sealant is characterized by consisting of a component A and a component B:
the component A comprises 24-50 wt% of hydroxyl-terminated polydimethylsiloxane, 5-10 wt% of modified silicone oil, 1-10 wt% of coupling agent and 39-60 wt% of first filler; the coupling agent is formed by mixing one or two of methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane according to any proportion;
the component B comprises 40-60 wt% of dimethyl silicone oil, 10-30 wt% of second filler, 5-40 wt% of auxiliary agent and 0.01-0.5 wt% of catalyst; the auxiliary agent in the component B is formed by compounding a silane coupling agent, a silane cross-linking agent and modified resin;
wherein the auxiliary agent in the component B is prepared by heating and compounding propyl trimethoxy silane, propyl triethoxy silane, 3- (2, 3-epoxypropoxy) propyl triethoxy silane, 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane and modified resin;
the propyl trimethoxy silane, the propyl triethoxy silane, the 3- (2, 3-epoxypropoxy) propyl triethoxy silane, the 3-aminopropyl trimethoxy silane, the 3-aminopropyl triethoxy silane and the modified resin respectively account for the following components in percentage by weight in total mass: 5-40 wt%, 0-10 wt%, 5-25 wt%, 3-15 wt%;
the modified resin is prepared by mixing one or more of silane modified polyether resin, hydroxyl terminated polybutadiene resin and silane modified polyurethane resin with the viscosity of 2000-30000 cs according to any proportion.
2. The high temperature curable silicone structural sealant according to claim 1,
the specific preparation method of the auxiliary agent in the component B comprises the following steps:
(1) adding propyl trimethoxy silane, propyl triethoxy silane, 3- (2, 3-epoxypropoxy) propyl triethoxy silane, 3-aminopropyl trimethoxy silane and 3-aminopropyl triethoxy silane into a reaction kettle, and slowly heating to 50-80 ℃ while stirring for reaction for 0.5-2 hours;
(2) slowly heating to 100-150 ℃, and adding the modified resin into the reaction kettle while stirring;
(3) and under the reflux state, continuously reacting for 2-24 hours while stirring, introducing nitrogen, naturally cooling to 25-30 ℃, discharging, and preparing to obtain the auxiliary agent.
3. The high-temperature curable silicone structural sealant as claimed in claim 1, wherein when the sealant is used, the component A and the component B are uniformly mixed according to the volume ratio of 9-11: 1, and then are applied to the surface of a material to be bonded for curing and curing.
4. The high-temperature curable silicone sealant as claimed in claim 1, wherein the viscosity of the hydroxyl terminated polydimethylsiloxane in the component A is 1000 cs-100000 cs; the modified silicone oil is one or more of hydroxyl modified silicone oil with the viscosity of 500 cs-10000 cs, polyether modified silicone oil, alkoxy modified silicone oil and epoxy modified silicone oil which are mixed according to any proportion.
5. The high-temperature curable silicone structural sealant as claimed in claim 1, wherein the first filler in the component A is prepared by mixing one or two of active calcium carbonate with a particle size of 5 nm-25 nm and active silica micropowder with a particle size of 2 μm-20 μm according to any proportion; the second filler in the component B is formed by mixing one or two of carbon black or fumed silica with the particle size of 0.3-10 nm.
6. The high temperature curable silicone structural sealant according to claim 5, wherein the activated calcium carbonate is calcium carbonate surface-treated with one or more of octamethylcyclotetrasiloxane, hexamethyldisilazane, dimethyldichlorosilane, rosin, fatty acid, stearic acid; the active silica micropowder is silica micropowder treated by one or more of gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane and 2- (3, 4-epoxycyclohexyl) -ethyl trimethyl silane.
7. The high-temperature curable silicone structural sealant according to claim 1, wherein the catalyst in the component B is one or more selected from the group consisting of dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, dimethyltin dioctanoate, dioctanodecanoic acid, bismuth isooctanoate, and organic phosphate.
8. Use of a high temperature curable silicone structural sealant according to any one of claims 1 to 7 for structural bonding of glass, aluminium profiles, stainless steel, steel or stone materials to one another.
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