CN111454687A - Two-component silicone adhesive and production method and application thereof - Google Patents
Two-component silicone adhesive and production method and application thereof Download PDFInfo
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- CN111454687A CN111454687A CN202010296963.6A CN202010296963A CN111454687A CN 111454687 A CN111454687 A CN 111454687A CN 202010296963 A CN202010296963 A CN 202010296963A CN 111454687 A CN111454687 A CN 111454687A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The application provides a two-component silicone adhesive and a production method and application thereof, and relates to the technical field of silicone adhesives, wherein the two-component silicone adhesive comprises an adhesive body and a hardening agent, the adhesive body comprises α, omega-dihydroxy polydimethylsiloxane and 40-80 parts by weight of nano calcium carbonate, the hardening agent comprises 100 parts by weight of a silane composite cross-linking agent, 500 parts by weight of a carbon black color paste, 60-120 parts by weight of a coupling agent, 1-10 parts by weight of a water removing agent and 0.2-5 parts by weight of an organic tin catalyst, wherein the silane composite cross-linking agent comprises a cross-linking agent and organic fatty acid, the number of carbon atoms on carbon chains of the organic fatty acid is not less than 6, under the combined action of the water removing agent in the hardening agent and the organic fatty acid, the number of carbon atoms on the carbon chains of the silane composite cross-linking agent is not less than 6, the curing reaction rate is reduced, the rate of bubbles generated in the two-component silicone adhesive body under the condition of exceeding 40 ℃ is slowed down, and.
Description
Technical Field
The invention relates to the technical field of silicone adhesive, in particular to double-component silicone adhesive and a production method and application thereof.
Background
The two-component silicone adhesive has the advantages of excellent ultraviolet aging resistance, weather aging resistance, high curing speed, deep curing, good adhesion to various base materials, strong displacement resistance and the like, and is widely used for bonding glass curtain wall structures in the building industry and the like.
At present, in the construction process, under the condition that the surface temperature of a bonded base material exceeds 40 ℃, the tensile bonding strength of the two-component silicone adhesive is rapidly reduced. Namely, the two-component silicone adhesive in the prior art cannot be applied to the bonding of the bonded substrate with the surface exceeding 40 ℃. For example, the metal color steel tile roof is easy to absorb heat, the temperature often exceeds 40 ℃, and the two-component silicone adhesive in the prior art cannot be suitable for bonding the metal color steel tile roof with the surface exceeding 40 ℃.
Disclosure of Invention
The invention provides a two-component silicone adhesive, a production method and application thereof, and aims to solve the problem that the two-component silicone adhesive cannot be applied to bonding of a bonded substrate with the surface exceeding 40 ℃.
According to a first aspect of the present invention, there is provided a two-component silicone adhesive comprising: the natural rubber and a hardening agent;
the adhesive comprises α, omega-dihydroxy polydimethylsiloxane 100 weight parts and nano calcium carbonate 40-80 weight parts;
the hardener includes: 100 parts by weight of silane composite cross-linking agent, 200 parts by weight of carbon black color paste, 60-120 parts by weight of coupling agent, 1-10 parts by weight of water removing agent and 0.2-5 parts by weight of organic tin catalyst;
the silane composite cross-linking agent comprises a cross-linking agent and organic fatty acid, wherein the number of carbon atoms on a carbon chain of the organic fatty acid is not less than 6.
Optionally, the natural rubber and the hardener are mixed according to the mass ratio of 7:1-16: 1.
Optionally, in the silane composite cross-linking agent, the mass ratio of the cross-linking agent to the organic fatty acid is 1-5: 0.5-5.
Optionally, the organic fatty acid is selected from at least one of capric acid and caprylic acid.
Optionally, the organic fatty acid is selected from: medium chain organic fatty acids and/or long chain organic fatty acids.
Optionally, the glue further comprises: 0.1 to 5 parts by weight of an ultraviolet absorber; the ultraviolet absorber is selected from: bis-1-decyloxy-2, 2, 6, 6-tetramethylpiperidin-4-ol sebacate, a polymer of succinic acid and 4-hydroxy-2, 2, 6, 6-tetramethyl-1-piperidinol, and a polymer of N, N' -bis (2, 2, 6, 6-tetramethyl-4-piperidyl) -1, 6-hexanediamine and 2, 4-dichloro-6- (1, 1, 3, 3-tetramethylbutyl) amino-1, 3, 5-triazine.
Optionally, the carbon black color paste comprises: high-structure carbon black powder obtained after acid method surface treatment or alkali method surface treatment, and an organopolysiloxane polymer; the weight ratio of the high-structure carbon black powder to the organopolysiloxane polymer is 25-40: 20-40.
Optionally, the organopolysiloxane polymer is selected from: at least one of hydroxyl-terminated polydimethylsiloxane, alkoxy-terminated polydimethylsiloxane and alkyl-terminated polydimethylsiloxane;
the viscosity of the organopolysiloxane polymer at 25 ℃ is 100-100000 cp.
Optionally, the cross-linking agent in the silane composite cross-linking agent is selected from: at least one of methyltrimethoxysilane, methyltriethoxysilane, ethyl orthosilicate and propyl orthosilicate;
the coupling agent is selected from at least one of gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, N- β -aminoethyl-gamma-aminopropyltrimethoxysilane, chloropropyltrimethoxysilane, mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane;
the water removing agent is selected from: at least one of vinyl trimethoxy silane, alkenyl trimethoxy silane, and p-toluene sulfonyl isocyanate;
the organotin catalyst is selected from: at least one of dibutyl tin dilaurate, dioctyl tin dilaurate, and dibutyl tin diacetate.
According to a second aspect of the present invention, there is provided a method for producing a two-component silicone adhesive, comprising the steps of:
preparing the adhesive, wherein the adhesive comprises α, omega-dihydroxy polydimethylsiloxane in 100 parts by weight and nano calcium carbonate in 40-80 parts by weight;
preparing a hardening agent; wherein the hardener comprises: 100 parts by weight of silane composite cross-linking agent, 200 parts by weight of carbon black color paste, 60-120 parts by weight of coupling agent, 1-10 parts by weight of water removing agent and 0.2-5 parts by weight of organic tin catalyst; the silane composite cross-linking agent comprises a cross-linking agent and organic fatty acid, wherein the number of carbon atoms on a carbon chain of the organic fatty acid is not less than 6;
mixing the natural rubber and the hardening agent according to a proportion.
According to a third aspect of the present invention there is provided the use of any one of the aforementioned two-component silicone adhesives in BIPV.
In the embodiment of the invention, after the glue and the hardening agent are mixed, the water removing agent in the hardening agent is hydrolyzed to consume water in the glue; meanwhile, organic fatty acid with 6 or more than 6 carbon atoms on the carbon chain in the silane composite cross-linking agent in the hardening agent can prevent the cross-linking agent from participating in the curing reaction too fast. Under the combined action of the water removing agent in the hardening agent and the organic fatty acid in the silane composite cross-linking agent, the curing reaction rate is reduced, the generation rate of bubbles in the two-component silicone adhesive at the temperature of over 40 ℃ is slowed down, and the tensile bonding strength of the two-component silicone adhesive at the temperature of over 40 ℃ is ensured.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments of the present invention will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without inventive exercise.
FIG. 1 shows a schematic of a bubble test method;
FIG. 2 is a photograph of the test results of the two-component silicone adhesive of example 1;
FIG. 3 is a photograph of the test results of the two-component silicone adhesive of example 2;
fig. 4 is a photograph of the test results of the two-component silicone adhesive of comparative example 1.
Description of the figure numbering:
1-glass, 2-substrate, 3-two-component silicone colloid.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The inventors of the present invention found that: in the prior art, the main reason that the tensile bonding strength of the two-component silicone adhesive is rapidly reduced under the condition that the bonding surface exceeds 40 ℃ is that the amount of bubbles in the cured two-component silicone adhesive is rapidly increased along with the increase of the temperature of the bonding surface, and the two-component silicone adhesive is not compact enough due to the bubbles, so that the tensile bonding strength is rapidly reduced. Further research shows that the bubbles can not escape from the colloid because the curing reaction is too fast in the bubble generation stage, and the bubbles are closed by the surrounding colloid which reacts and even solidifies.
The two-component silicone adhesive comprises an original adhesive and a hardening agent, wherein the content of each component is explained below, and the content is calculated by mass parts if not specifically stated, the original adhesive comprises α, omega-dihydroxy polydimethylsiloxane 100 weight parts and nano calcium carbonate 40-80 weight parts, and the hardening agent comprises silane composite cross-linking agent 100 weight parts, carbon black color paste 200-500 weight parts, coupling agent 60-120 weight parts, water removing agent 1-10 weight parts and organic tin catalyst 0.2-5 weight parts, wherein the silane composite cross-linking agent comprises cross-linking agent and organic fatty acid, and the number of carbon atoms on the carbon chain of the organic fatty acid is greater than or equal to 6.
Preferably, α, viscosity of omega-dihydroxy polydimethylsiloxane in the glue is between 10000 mPa.s and 200000 mPa.s at 25 ℃, nano calcium carbonate in the glue is preferably nano active calcium carbonate, light calcium carbonate or heavy calcium carbonate with surface treated by a treating agent, the particle size of the nano calcium carbonate is 40-80nm, and the surface treating agent is preferably at least one of fatty acid silane, a coupling agent and abietic acid.
The water removing agent and the silane composite cross-linking agent are added into the hardening agent, and after the glue is mixed with the hardening agent, the water removing agent is hydrolyzed to consume water of the glue, so that the reaction condition of the curing reaction is weakened. Moreover, other components in the silane composite cross-linking agent in the hardening agent can be fully dissolved in the organic fatty acid with the carbon atom number of more than or equal to 6 on the carbon chain, and further, the organic fatty acid with the carbon atom number of more than or equal to 6 on the carbon chain has certain constraint effect on the participation of the cross-linking agent in the curing reaction, can prevent the silane composite cross-linking agent from participating in the curing reaction too fast, and provides convenient conditions for the escape of bubbles. Under the combined action of the water removing agent in the hardening agent and the organic fatty acid with the carbon atom number of more than or equal to 6 on the carbon chain, the curing reaction rate is reduced, the generation of bubbles in the two-component silicone adhesive is inhibited under the condition of the temperature of more than 40 ℃, and the tensile bonding strength of the two-component silicone adhesive is ensured under the condition of the temperature of more than 40 ℃. Furthermore, the construction can still be carried out at the temperature of more than 40 ℃, the construction window is expanded, and experiments prove that no air bubbles are generated inside the double-component silicone colloid in the embodiment of the invention when the construction is carried out on a steel plate with the temperature of up to 70 ℃.
Meanwhile, the carbon black color paste is added into the hardening agent, and can be wound on a high polymer main chain, so that the tensile bonding strength of the two-component silicone adhesive can be improved, and the nano-scale molecular acting force on the surface of the carbon black also has a synergistic reinforcing effect on the tensile bonding strength of the two-component silicone adhesive. Therefore, the carbon black color paste can improve the tensile bonding strength of the two-component silicone adhesive.
The hardener contains 0.2-5 parts by mass of organic tin catalyst, and the content of the organic tin catalyst in the two-component silicone adhesive is low. Therefore, the activation energy of the curing reaction can be effectively reduced, the curing reaction is guaranteed to be carried out, the over-fast speed of the curing reaction is favorably slowed down, the generation of bubbles in the two-component silicone adhesive is relieved under the condition that the temperature exceeds 40 ℃, and the tensile bonding strength of the two-component silicone adhesive is guaranteed under the condition that the temperature exceeds 40 ℃. Furthermore, the construction can be still carried out at the temperature of more than 40 ℃, the construction window is expanded, and the construction progress cannot be delayed due to the temperature.
Optionally, the double-component silicone adhesive is obtained by mixing the natural adhesive and the hardening agent according to the mass ratio of 7:1-16: 1. The two-component silicone adhesive obtained by the mixing mode has better tensile bonding strength at 40 ℃ and above.
Optionally, in the silane composite cross-linking agent, the mass ratio of the cross-linking agent to the organic fatty acid is 1-5: 0.5-5, under the condition of the mass ratio, the organic fatty acid with the number of carbon atoms on the carbon chain being more than or equal to 6 can fully dissolve other components in the silane composite cross-linking agent in the hardening agent, has good constraint effect on the participation of the cross-linking agent in the curing reaction, and can effectively prevent the silane composite cross-linking agent from participating in the curing reaction.
Optionally, in the silane compound cross-linking agent, the organic fatty acid is selected from at least one of capric acid and caprylic acid, and similarly, the organic fatty acid of the above components can sufficiently dissolve other components in the silane compound cross-linking agent in the hardening agent, so that the organic fatty acid has a good binding effect on the other components in the silane compound cross-linking agent participating in the curing reaction, and can effectively prevent the silane compound cross-linking agent from participating in the curing reaction.
Optionally, in the silane compound crosslinking agent, the organic fatty acid is selected from medium-chain organic fatty acid and/or long-chain organic fatty acid. The medium-chain organic fatty acid refers to an organic fatty acid with 6-12 carbon atoms on a carbon chain. The long-chain organic fatty acid refers to an organic fatty acid with the carbon number of more than 12 on the carbon chain. The medium-chain organic fatty acid and/or the long-chain organic fatty acid have more carbon atoms on the carbon chain, can more fully dissolve other components in the silane composite cross-linking agent in the hardening agent, has good binding effect on the other components in the silane composite cross-linking agent participating in the curing reaction, and can effectively prevent the silane composite cross-linking agent from participating in the curing reaction.
Optionally, the cross-linking agent in the silane composite cross-linking agent is selected from: at least one of methyltrimethoxysilane, methyltriethoxysilane, ethyl orthosilicate and propyl orthosilicate is uniformly mixed with organic fatty acid to obtain the silane composite cross-linking agent.
Optionally, the glue can also comprise 0.1 to 5 weight parts of ultraviolet absorbent. The ultraviolet absorbent is a hindered amine light stabilizer, so that the long-term ultraviolet aging resistance of the two-component silicone adhesive can be remarkably improved, and experiments prove that the tensile elongation at break attenuation rate of the two-component silicone adhesive in the embodiment of the invention is less than 20% after water-ultraviolet 1008 hours.
The ultraviolet absorbent in the adhesive is at least one selected from the group consisting of bis-1-decyloxy-2, 2, 6, 6-tetramethylpiperidin-4-ol sebacate, a polymer of succinic acid and 4-hydroxy-2, 2, 6, 6-tetramethyl-1-piperidinol, and a polymer of N, N' -bis (2, 2, 6, 6-tetramethyl-4-piperidyl) -1, 6-hexanediamine and 2, 4-dichloro-6- (1, 1, 3, 3-tetramethylbutyl) amino-1, 3, 5-triazine. The material has stronger stability to water, light or ultraviolet rays, and further improves the long-term aging resistance of the two-component silicone adhesive.
Optionally, the carbon black color paste in the hardener comprises: high-structure carbon black powder obtained after acid method surface treatment or alkali method surface treatment, and organopolysiloxane polymer. The weight ratio of the high-structure carbon black powder to the organopolysiloxane polymer is 25-40: 20-40. The oil absorption value of the high-structure carbon black powder is more than or equal to 120ml/100 g. The carbon black color paste is obtained by mixing the high-structure carbon black powder and the organic polysiloxane polymer in vacuum. For example, the high-structure carbon black powder and the organopolysiloxane polymer are mixed in a dynamic mixing disperser under vacuum. The carbon black color paste made of the material has stronger winding capacity on a high polymer main chain, and can further improve the tensile bonding strength of the two-component silicone adhesive.
Optionally, the organopolysiloxane polymer is selected from at least one of hydroxyl-terminated polydimethylsiloxane, alkoxy-terminated polydimethylsiloxane, and alkyl-terminated polydimethylsiloxane. The carbon black color paste formed by the organic polysiloxane polymer has stronger winding capacity on a high molecular main chain, and can further improve the tensile bonding strength of the two-component silicone adhesive.
Optionally, the viscosity of the organopolysiloxane polymer at 25 ℃ is 100-100000cp, so that the bonding strength of the two-component silicone adhesive is better.
Optionally, in the hardening agent, the coupling agent is at least one selected from gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, N- β -aminoethyl-gamma-aminopropyltrimethoxysilane, chloropropyltrimethoxysilane, mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane.
Optionally, the organotin catalyst in the hardener is selected from: at least one of dibutyl tin dilaurate, dioctyl tin dilaurate, and dibutyl tin diacetate.
Optionally, the water scavenger in the hardener is selected from: at least one of vinyl trimethoxy silane, alkenyl trimethoxy silane and p-toluene sulfonyl isocyanate.
The embodiment of the invention also provides a production method of the two-component silicone adhesive. The method comprises the following steps:
and S1, preparing the adhesive, wherein the adhesive comprises α parts by weight of omega-dihydroxy polydimethylsiloxane and 40-80 parts by weight of nano calcium carbonate.
Specifically, 100 parts of α, omega-dihydroxy polydimethylsiloxane and 40-80 parts of active nano calcium carbonate are input into a double-screw extruder control system, the material feeding amount is measured electronically, the material is fed, the production is carried out by a double-screw extruder, the vacuum degree is controlled to be-0.06-0.08 MPa, the material temperature is 80-100 ℃, the rotating speed is 250-600rpm, the host machine current is 55-90A, and the adhesive is obtained after extrusion and cooling.
Step S2, preparing a hardening agent; wherein the hardener comprises: 100 parts by weight of silane composite cross-linking agent, 200 parts by weight of carbon black color paste, 60-120 parts by weight of coupling agent, 1-10 parts by weight of water removing agent and 0.2-5 parts by weight of organic tin catalyst; the silane composite cross-linking agent comprises a cross-linking agent and organic fatty acid, wherein the number of carbon atoms on a carbon chain of the organic fatty acid is not less than 6.
Specifically, 100 parts by weight of silane composite cross-linking agent, 500 parts by weight of carbon black color paste 200, 60-120 parts by weight of coupling agent, 1-10 parts by weight of water removal agent and 0.2-5 parts by weight of organic tin catalyst are added into a planetary stirrer or a high-speed dispersion stirrer, the materials are stirred in a vacuum degree of more than or equal to-0.09 MPa, the temperature of the materials is controlled by a cooling system to be less than 50 ℃, and the materials are stirred for 1-2 hours and then are sealed for storage to obtain the hardening agent. Wherein, the silane composite cross-linking agent comprises: a crosslinking agent and an organic fatty acid, wherein the number of carbon atoms on the carbon chain of the organic fatty acid is not less than 6.
Further, the step S2 may include the following sub-steps:
and the substep S21, adding the high-structure carbon black powder obtained after the surface treatment by the acid method or the alkali method and the organic polysiloxane polymer into a dynamic mixing dispersion machine, wherein the temperature is 100-120 ℃, the vacuum degree is more than or equal to-0.09 MPa, and the carbon black color paste is obtained after vacuum mixing dispersion for 0.5-2 hours and then cooling to below 45 ℃. Wherein the weight ratio of the high-structure carbon black powder to the organopolysiloxane polymer is 25-40: 20-40.
In substep S22, the crosslinking agent is selected from: at least one of methyltrimethoxysilane, methyltriethoxysilane, ethyl orthosilicate and propyl orthosilicate, placing the cross-linking agent and organic fatty acid with carbon number not less than 6 on carbon chain into a small liquid mixing stirrer, and mixing and stirring at 30-45 deg.C for 0.5 hr to obtain the silane composite cross-linking agent. The mass ratio of the cross-linking agent to the organic fatty acid is 1-5: 0.5-5.
The execution sequence of steps S1 and S2 is not particularly limited. For example, both may be performed simultaneously, or step S2 may be performed first, and then step S1 may be performed.
And step S3, mixing the natural rubber and the hardening agent according to a proportion.
Specifically, the glue and the hardener are packaged independently before mixing. And mixing the natural rubber and a hardening agent according to a ratio to obtain the double-component silicone rubber. Preferably, the mass ratio of the natural rubber and the hardening agent is 7:1-16: 1.
In the embodiment of the present invention, the ingredients, mass ratios, and the like of the present adhesive and the hardening agent in each step of the above method can refer to the related descriptions in the foregoing embodiment, and can achieve the same or similar beneficial effects, and are not repeated herein in order to avoid repetition.
The embodiment of the invention also provides application of the two-component silicone adhesive in BIPV (Building integrated photovoltaic). Specifically, the two-component silicone adhesive provided by the embodiment of the invention is used for bonding bonded materials required in BIPV. In the embodiment of the present invention, this is not particularly limited. For example, the two-component silicone adhesive provided by the embodiment of the invention is used for bonding metal color steel tiles, photovoltaic pieces and the like in the BIPV.
The invention is further illustrated by the following specific examples.
Example 1
In the double-component silicone adhesive:
the adhesive comprises α, omega-dihydroxy polydimethylsiloxane 100 weight parts, nano calcium carbonate 50 weight parts, and ultraviolet absorbent bis-1-decyloxy-2, 2, 6, 6-tetramethyl piperidine-4-alcohol sebacate 0.2 weight parts.
The hardener comprises 100 parts by weight of silane composite cross-linking agent, 300 parts by weight of carbon black color paste, 80 parts by weight of coupling agent mercaptopropyl trimethoxy silane, 2 parts by weight of water removing agent vinyl trimethoxy silane and 0.2 part by weight of organic tin catalyst dioctyl tin dilaurate; wherein, the silane composite cross-linking agent consists of 2 parts by weight of methyl triethoxysilane and 1 part by weight of octanoic acid; the carbon black color paste is prepared by mixing 30 parts by weight of high-structure carbon black and 25 parts by weight of polydimethylsiloxane terminated by hydroxyl end groups.
The adhesive and the hardener are 8: 1, in a mass ratio of 1.
Example 2
In the double-component silicone adhesive:
the adhesive comprises α, omega-dihydroxy polydimethylsiloxane, 40 parts by weight of nano calcium carbonate and 5 parts by weight of ultraviolet absorbent bis-1-decyloxy-2, 2, 6, 6-tetramethyl piperidine-4-alcohol sebacate, wherein the α, omega-dihydroxy polydimethylsiloxane is 100 parts by weight.
The hardener comprises 100 parts by weight of silane composite cross-linking agent, 300 parts by weight of carbon black color paste, 60 parts by weight of coupling agent mercaptopropyl trimethoxy silane, 2 parts by weight of water removing agent p-toluene sulfonyl isocyanate and 0.2 part by weight of organic tin catalyst dioctyl tin dilaurate; wherein the silane composite cross-linking agent consists of 2 parts by weight of methyl triethoxysilane and 1 part by weight of octanoic acid; the carbon black color paste is prepared by mixing 25 parts by weight of high-structure carbon black and 30 parts by weight of polydimethylsiloxane end-capped with terminal hydroxyl.
The adhesive and the hardener are as follows: 1, in a mass ratio of 1.
Comparative example 1
In the double-component silicone adhesive:
the adhesive comprises α, omega-dihydroxy polydimethylsiloxane, 40 parts by weight of nano calcium carbonate and 5 parts by weight of ultraviolet absorbent bis-1-decyloxy-2, 2, 6, 6-tetramethyl piperidine-4-alcohol sebacate, wherein the α, omega-dihydroxy polydimethylsiloxane is 100 parts by weight.
The hardener comprises 100 parts by weight of cross-linking agent methyl triethoxysilane, 300 parts by weight of carbon black color paste, 60 parts by weight of coupling agent mercaptopropyl trimethoxysilane and 20 parts by weight of organotin catalyst dioctyl tin dilaurate; wherein, the carbon black color paste is prepared by mixing 25 parts by weight of high-structure carbon black and 30 parts by weight of polydimethylsiloxane end-capped with hydroxyl.
The adhesive and the hardener are as follows: 1, in a mass ratio of 1.
And (3) performance testing:
the two-component silicone adhesives of example 1, example 2, and comparative example 1 were each tested using the test method shown in fig. 1. In fig. 1, 1 is glass, which may be a photovoltaic device. 2 is a base material, and 3 is a two-component silicone colloid. The substrate 2 in fig. 1 may be an aluminum plate. In FIG. 1, the glass 1 has a width of 50mm and a length of 50mm, and the two-component silicone gel has a width of 12mm and a height of 12 mm. Specifically, the two-component silicone adhesive of the above example 1, example 2, and comparative example 1 was applied to an aluminum plate at 70 ℃ to prepare H-shaped samples as shown in fig. 1, the samples were placed in an oven at 70 ℃ for 24 hours, after the samples were cooled, the tensile bond strength of the samples was measured, and the adhesive tape was cut to observe whether air bubbles were present inside the adhesive tape, wherein the tensile rate was 5 mm/min. The test results are shown in table 1 below, and fig. 2 to 4. Wherein, table 1 is: table comparing test results of the two-component silicone adhesives of example 1, example 2, comparative example 1.
Table 1: test results of the two-component silicone adhesives of example 1, example 2, comparative example 1 are shown in the table
As can be seen from table 1 and fig. 2 to 4, the two-component silicone adhesive of example 1 has a tensile bond strength of 1.3Mpa, an excellent bond strength, an elongation at break of 256.9%, a low tendency to fracture, no bubbles in the adhesive, and good adhesion properties. The two-component silicone adhesive of example 2 has a tensile bond strength of 1.2Mpa, an excellent bond strength, an elongation at break of 269.9%, is not easily broken, has no bubbles in the adhesive, and has a good adhesive property. The two-component silicone adhesive of comparative example 1 had a tensile bond strength of 0.9Mpa and an elongation at break of 239.8%, and the adhesive was easily broken, and had bubbles in the adhesive, which deteriorated the adhesive properties.
According to the two-component silicone adhesive disclosed by the embodiment of the invention, as the water removal agent and the silane composite cross-linking agent are added in the hardening agent, after the two-component silicone adhesive is mixed with the hardening agent, the water removal agent is hydrolyzed to consume water of the two-component silicone adhesive, so that the reaction condition of a curing reaction is weakened. Moreover, the organic fatty acid containing 6 or more than 6 carbon atoms in the silane composite cross-linking agent in the hardening agent has certain constraint effect on the participation of other components in the silane composite cross-linking agent in the curing reaction, and can prevent the silane composite cross-linking agent from participating in the curing reaction. Under the combined action of the water removing agent in the hardening agent and the organic fatty acid containing 6 or more than 6 carbon atoms, the curing reaction rate is reduced, the generation rate of bubbles in the two-component silicone adhesive is relieved under the condition of exceeding 40 ℃, and the tensile bonding strength of the two-component silicone adhesive is ensured under the condition of exceeding 40 ℃.
It should be noted that for simplicity of description, the method embodiments are described as a series of acts or combination of acts, but those skilled in the art will recognize that the present invention is not limited by the illustrated order of acts, as some steps may occur in other orders or concurrently depending on the embodiment of the invention. Furthermore, those skilled in the art will appreciate that the embodiments described in the specification are presently preferred and that no particular act is required to implement the invention.
While the present invention has been described with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, which are illustrative rather than restrictive, and it will be apparent to those skilled in the art that many more modifications and variations can be made without departing from the spirit of the invention and the scope of the appended claims.
Claims (11)
1. A two-component silicone adhesive, comprising: the natural rubber and a hardening agent;
the adhesive comprises α, omega-dihydroxy polydimethylsiloxane 100 weight parts and nano calcium carbonate 40-80 weight parts;
the hardener includes: 100 parts by weight of silane composite cross-linking agent, 200 parts by weight of carbon black color paste, 60-120 parts by weight of coupling agent, 1-10 parts by weight of water removing agent and 0.2-5 parts by weight of organic tin catalyst;
the silane composite cross-linking agent comprises a cross-linking agent and organic fatty acid, wherein the number of carbon atoms on a carbon chain of the organic fatty acid is not less than 6.
2. The two-component silicone adhesive according to claim 1, wherein the natural rubber and the hardener are mixed in a mass ratio of 7:1 to 16: 1.
3. The two-component silicone adhesive according to claim 1, wherein in the silane compound cross-linking agent, the mass ratio of the cross-linking agent to the organic fatty acid is 1-5: 0.5-5.
4. The two-component silicone adhesive according to claim 1 or 3, wherein the organic fatty acid is at least one selected from capric acid and caprylic acid.
5. The two-component silicone adhesive according to claim 1, wherein the organic fatty acid is selected from the group consisting of: medium chain organic fatty acids and/or long chain organic fatty acids.
6. The two-component silicone adhesive of claim 1, wherein the adhesive further comprises: 0.1 to 5 parts by weight of an ultraviolet absorber;
the ultraviolet absorber is selected from: bis-1-decyloxy-2, 2, 6, 6-tetramethylpiperidin-4-ol sebacate, a polymer of succinic acid and 4-hydroxy-2, 2, 6, 6-tetramethyl-1-piperidinol, and a polymer of N, N' -bis (2, 2, 6, 6-tetramethyl-4-piperidyl) -1, 6-hexanediamine and 2, 4-dichloro-6- (1, 1, 3, 3-tetramethylbutyl) amino-1, 3, 5-triazine.
7. The two-component silicone adhesive according to claim 1, wherein the carbon black paste comprises: high-structure carbon black powder obtained after acid method surface treatment or alkali method surface treatment, and an organopolysiloxane polymer; the weight ratio of the high-structure carbon black powder to the organopolysiloxane polymer is 25-40: 20-40.
8. The two-component silicone adhesive according to claim 7, wherein the organopolysiloxane polymer is selected from the group consisting of: at least one of hydroxyl-terminated polydimethylsiloxane, alkoxy-terminated polydimethylsiloxane and alkyl-terminated polydimethylsiloxane;
the viscosity of the organopolysiloxane polymer at 25 ℃ is 100-100000 cp.
9. The two-component silicone adhesive according to claim 1, wherein the cross-linking agent of the silane compound cross-linking agent is selected from the group consisting of: at least one of methyltrimethoxysilane, methyltriethoxysilane, ethyl orthosilicate and propyl orthosilicate;
the coupling agent is selected from at least one of gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, N- β -aminoethyl-gamma-aminopropyltrimethoxysilane, chloropropyltrimethoxysilane, mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane;
the water removing agent is selected from: at least one of vinyl trimethoxy silane, alkenyl trimethoxy silane, and p-toluene sulfonyl isocyanate;
the organotin catalyst is selected from: at least one of dibutyl tin dilaurate, dioctyl tin dilaurate, and dibutyl tin diacetate.
10. The production method of the two-component silicone adhesive is characterized by comprising the following steps:
preparing the adhesive, wherein the adhesive comprises α, omega-dihydroxy polydimethylsiloxane in 100 parts by weight and nano calcium carbonate in 40-80 parts by weight;
preparing a hardening agent; wherein the hardener comprises: 100 parts by weight of silane composite cross-linking agent, 200 parts by weight of carbon black color paste, 60-120 parts by weight of coupling agent, 1-10 parts by weight of water removing agent and 0.2-5 parts by weight of organic tin catalyst; the silane composite cross-linking agent comprises a cross-linking agent and organic fatty acid, wherein the number of carbon atoms on a carbon chain of the organic fatty acid is not less than 6;
mixing the natural rubber and the hardening agent according to a proportion.
11. Use of the two-component silicone adhesive of any one of claims 1 to 9 in BIPV.
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