CN109609083B - Bi-component silicone structural adhesive for solar photo-thermal power generation and preparation method thereof - Google Patents
Bi-component silicone structural adhesive for solar photo-thermal power generation and preparation method thereof Download PDFInfo
- Publication number
- CN109609083B CN109609083B CN201811584133.2A CN201811584133A CN109609083B CN 109609083 B CN109609083 B CN 109609083B CN 201811584133 A CN201811584133 A CN 201811584133A CN 109609083 B CN109609083 B CN 109609083B
- Authority
- CN
- China
- Prior art keywords
- parts
- component
- gamma
- omega
- structural adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- C09J11/08—Macromolecular additives
-
- 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
-
- 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
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Sealing Material Composition (AREA)
Abstract
The invention discloses a bi-component silicone structural adhesive for solar photo-thermal power generation, which comprises a component A and a component B, wherein the component A comprises: 10-40 parts of class 1 alpha, omega-dihydroxy polydimethylsiloxane; 60-100 parts of 2-type alpha, omega-dihydroxy polydimethylsiloxane; 5-35 parts of a plasticizer; 80-150 parts of class 1 filler; 0.5-10 parts of a class 2 filler; the component B comprises: 20-35 parts of carbon black; 25-40 parts of a plasticizer; 10-80 parts of a class 1 crosslinking agent; 25-80 parts of a 2 nd cross-linking agent; 2.5-20 parts of a coupling agent; 0.1-2 parts of a catalyst. The invention also discloses a preparation method of the bi-component silicone structural adhesive for solar photo-thermal power generation. The silicone sealant can be used for structural bonding outdoors, and is particularly suitable for structural bonding and fixing between a reflector for solar photo-thermal power generation and a support.
Description
Technical Field
The invention relates to a silicone adhesive and a preparation method thereof, in particular to a bi-component silicone structural adhesive for solar photo-thermal power generation and a preparation method thereof, and belongs to the technical field of organic silicon structural adhesives.
Background
According to different solar power generation modes, the solar photovoltaic power generation and the solar photothermal power generation can be divided. The solar photo-thermal power generation is a solar energy utilization technology which utilizes a light-gathering solar heat collector to gather solar radiation energy, then utilizes the energy to heat a certain working medium to hundreds of degrees centigrade, and drives a generator to generate power by the working medium. The solar-thermal power generation technology is born from the 50 th generation to the present, and the global solar-thermal power generation market is mainly concentrated in the countries such as spain, usa and the like. The solar photo-thermal power generation industry is gradually developed in China only from the last few years, the solar photo-thermal power generation technology belongs to the emerging industry in China, and a plurality of technologies are in experimental verification stages.
The reflector for solar photo-thermal power generation is one of the most important factors influencing the power generation efficiency of the reflector, and the connection between the reflector and the mirror surface support is a key factor influencing the structural reliability and durability of the reflecting equipment. At present, the connection mode between the reflector and the bracket mainly comprises 2 types: 1) the ceramic gasket is bonded on the protective paint on the outermost layer of the mirror surface by using an adhesive, and then the ceramic gasket is mechanically connected with the bracket or the reflector is directly bonded with the bracket by using the adhesive; 2) and (4) fixing by using rivets. The method for fixing the reflector by using the adhesive belongs to a flexible connection mode, and has the advantages of simple assembly process, economy, feasibility, no damage to the reflector surface and the like compared with a mechanical connection mode. The organic silicon structural adhesive for solar photo-thermal power generation is mainly used for structural connection or bonding fixation between a solar reflector and a support, and whether the reflector is firmly fixed on the support is a key index for evaluating the organic silicon structural adhesive. The reflector can not only receive outdoor severe environments such as high temperature, rainwater and strong ultraviolet rays, but also ensure that the reflector which is fixedly bonded can withstand the test of strong wind of a certain level. Therefore, the organic silicon structural adhesive for solar photo-thermal power generation needs to have excellent tensile bonding strength and good tensile bonding strength after double 85 aging treatment.
As the solar photo-thermal power generation industry belongs to the new industry in China, the organic silicon structural adhesive matched with the solar photo-thermal power generation industry is relatively less. Domestic reports on the organosilicon sealant for solar power generation mainly focus on the sealant for solar photovoltaic modules, and the most applied organosilicon sealant is a single-component ketoxime removal type organosilicon sealant at present. The performance of the organic silicon sealant colloid for the photovoltaic module is mainly required to have good mechanical strength, the colloid after double 85 aging has good strength and excellent yellowing resistance, reports on the good tensile bonding strength after double 85 aging are less, and corresponding technical indexes are mainly implemented by referring to GB/T29595. For example, patent with application publication number CN 105505297a discloses a pure good single component dealcoholized solar photovoltaic module sealant with yellowing resistance and a preparation method thereof, which adopts a tackifier prepared by reacting an epoxy siloxane coupling agent and an amino hydrocarbon siloxane coupling agent to obtain the sealant with excellent yellowing resistance after aging of double 85, does not research the tensile bonding strength after aging of double 85, and compared with a double component product, the single component dealcoholized RTV has a slow deep curing speed and is mainly used for waterproof sealing of a photovoltaic module frame. The method is not suitable for continuous assembly production of the photo-thermal power generation reflector from the use point of view, and is not suitable for structural bonding directly exposed outdoors from the performance point of view. The patent with the application publication number of CN101768421A discloses a bi-component silicone sealant for a solar photovoltaic module and a preparation method thereof, wherein the yellowing resistance of a sizing material after double 85 aging is mainly researched, and the tensile adhesion after the double 85 aging treatment for 1008 hours is not researched. The patent with the application publication number of CN102936483A discloses a sealant for a single-component organic silicon solar photovoltaic module and a preparation method thereof, wherein the prepared single-component sealant has excellent yellowing resistance after being aged for 1000h at 150 ℃, and the tensile bonding strength after being aged for 1000h of double 85 is not mentioned. The organic silicon sealant for the photovoltaic module has higher similarity with the organic silicon structural adhesive for the solar photo-thermal power generation fixed reflector in the use environment, and needs to be exposed outdoors for long time for use. The organic silicon sealant for the photovoltaic module mainly plays a role in sealing and waterproof protection of a solar cell panel, the organic silicon structural adhesive for the solar photo-thermal power generation for installing and fixing the reflector mainly plays a role in structural bonding and fixing, and the requirements on the tensile bonding strength and the tensile bonding strength after double 85 aging are higher than those of the organic silicon sealant for the photovoltaic module. Therefore, the prior organosilicon sealant for the solar photovoltaic component can not meet the requirement of the structural adhesive for fixing the photo-thermal power generation reflector.
The development of domestic organic silicon structural adhesive mainly focuses on structural adhesive for buildings, and compared with the direct exposure of structural adhesive colloid for photo-thermal power generation in outdoor use environment, the use environment of the structural adhesive is relatively mild. The building organosilicon structural adhesive is mainly used for preparing hollow glass for glass curtain walls and structural bonding between the hollow glass and an auxiliary frame, and after the hollow glass is hung on the curtain wall, the outermost layer is subjected to waterproof sealing treatment by using organosilicon weather-resistant sealant. Therefore, the building organic silicon structural adhesive is required to have excellent bonding strength and higher elongation, the double 85 aging performance is not required, and related products are mainly executed according to the GB/T16776 standard. For example, patent application publication No. CN105255439A discloses a high-elongation two-component silicone structural adhesive and a preparation method thereof, which is suitable for structural adhesive sealing of high-rise glass building curtain walls and has high elongation, but tensile adhesive strength and adhesive failure area after double 85 aging treatment are not mentioned in the patent.
At present, the domestic silicone sealant for solar photovoltaic modules and the silicone structural adhesive for building curtain walls cannot meet the requirements of the structural adhesive for photo-thermal power generation due to the difference of the use environment and the technical requirements. The silicone structural adhesive for solar photo-thermal power generation is mainly used for structural bonding between a photo-thermal power generation reflector and a support, and has higher requirements compared with an organic silicon sealing adhesive for a photovoltaic module and an organic silicon structural adhesive for a building because the adhesive is directly exposed outdoors for structural connection. Therefore, the silicone structural adhesive for solar photo-thermal power generation requires tensile bonding strength equivalent to that of a building organic silicon structural adhesive, and has good tensile bonding strength after double 85 aging treatment 1008h and double 85 aging treatment which are the same as those of the organic silicon sealant for the photovoltaic module. The room temperature vulcanized silicone rubber has a reversion phenomenon that the crosslinking density of the sealing material is reduced under a high-temperature and high-humidity environment, and the bonding performance is shown in that the bonding strength of the sealing material to a base material is greatly reduced after double 85 aging. Therefore, it is necessary to develop a silicone structural adhesive (for mounting and fixing the reflector) with good tensile bonding strength after aging of the double 85 for solar photothermal power.
Disclosure of Invention
The invention aims to solve the technical difficulty that the tensile adhesion of double-component dealcoholized room temperature vulcanized silicone rubber is reduced after the wet-heat aging treatment, and provides dealcoholized double-component silicone structural adhesive for solar photo-thermal power generation, which has high tensile adhesion strength, good tensile adhesion strength to base materials after the double-85 aging treatment, good adhesion damage area to the base materials 0 and good adhesion to base materials such as reflectors, aluminum profiles, ceramic wafers and the like, and a preparation method thereof, so as to meet the special requirements and application requirements of fixed reflectors of solar photo-thermal power generation systems on the structural adhesive.
The invention is realized by the following steps:
a bi-component silicone structural adhesive for solar photo-thermal power generation comprises a component A and a component B, wherein the component A and the component B respectively comprise the following components in parts by weight:
the component A comprises:
and B component:
the further scheme is as follows:
the viscosity of the 1 st alpha, omega-dihydroxy polydimethylsiloxane is 100 to 3000 mPas, preferably 500 to 1500 mPas.
The viscosity of the 2 nd alpha, omega-dihydroxy polydimethylsiloxane is 10000-80000 mPas or the viscosity of the alpha, omega-dihydroxy polydimethylsiloxane compounded by different viscosities is 10000-80000 mPas.
The further scheme is as follows:
A. the plasticizer in the component B is selected from one or more compound compounds of vinyl-terminated polydimethylsiloxane, methyl polydimethylsiloxane and alpha, omega-dihydroxy polydimethylsiloxane, and the viscosity range of the plasticizer is preferably 100-1000 mPa & s.
The further scheme is as follows:
the 1 st filler is one or a mixture of several substances of nano active calcium carbonate, heavy calcium carbonate and silica powder, wherein the crystal form of the nano active calcium carbonate is a cubic structure, and the PH is less than 10 by adopting a GB/T19281 method.
The further scheme is as follows:
the 2 nd filler is at least one of fumed silica and precipitated silica.
The further scheme is as follows:
the carbon black is a common pigment carbon black.
The further scheme is as follows:
the crosslinking agent of the 1 st class has the following structural characteristics:
wherein R1 and R2 are one of methyl OR ethyl and siloxane group Si-OR1、Si-OR2The sum of the number of the compounds is 6, and X is an alkyl group with the carbon atom number more than or equal to 2.
The further scheme is as follows:
the 2 nd cross-linking agent is selected from one or a mixture of ethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate, polyethyl orthosilicate, methyltriethoxysilane, polymethyltriethoxysilane, methyltrimethoxysilane and its partially hydrolyzed oligomer, dimethyldimethoxysilane, phenyltrimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane and tetracosyltrimethoxysilane.
The further scheme is as follows:
the coupling agent is a mixture of an amino-hydrocarbyl silane coupling agent and gamma-glycidyl ether oxypropyl trimethoxy silane in a mass ratio of 0.5-5: 1, wherein the amino-hydrocarbyl silane coupling agent can be one or a combination of gamma-aminopropyl triethoxy silane, gamma-aminopropyl trimethoxy silane, N-beta (aminoethyl) -gamma-aminopropyl triethoxy silane, 3-aminopropyl methyl dimethoxy silane, N-N-butyl-3-aminopropyl triethoxy silane and gamma-ureido propyl trimethoxy silane.
The further scheme is as follows:
the mixing method of the coupling agent is as follows:
heating the metered amino-containing alkyl silane coupling agent to 80-90 ℃ under the protection of nitrogen, slowly dripping gamma-glycidoxypropyltrimethoxysilane into the amino-containing alkyl silane coupling agent, wherein the dripping speed is based on the principle that the reaction temperature is not more than 90 ℃.
The further scheme is as follows:
the catalyst is one or more selected from dibutyl tin dilaurate, dimethyl tin diacetate, dibutyl tin diacetate, dimethyl tin dineodecanoate and stannous octoate.
The invention also aims to provide a preparation method of the bi-component silicone structural adhesive for solar photo-thermal power generation, which comprises the following steps:
(1) preparation of component A
Dispersing and mixing 10-40 parts by mass of 1 type alpha, omega-dihydroxy polydimethylsiloxane, 60-100 parts by mass of 2 type alpha, omega-dihydroxy polydimethylsiloxane, 5-35 parts by mass of plasticizer, 80-150 parts by mass of 1 type filler and 0.5-10 parts by mass of 2 type filler uniformly under a vacuum condition to obtain a component A;
(2) preparation of component B
Dispersing and uniformly mixing 20-35 parts by mass of carbon black, 25-40 parts by mass of a plasticizer, 10-80 parts by mass of a 1 st cross-linking agent, 25-80 parts by mass of a 2 nd cross-linking agent, 2.5-20 parts by mass of a coupling agent, 0.1-2 parts by mass of a catalyst and the like under a vacuum condition to obtain a component B;
(3) a, B mixing the components
A. The component B is prepared according to the following steps of A: and B is used after being uniformly mixed according to the mass ratio of 10-15: 1.
The invention has at least the following beneficial effects:
1) the component A is prepared from a low-viscosity base polymer (alpha, omega-dihydroxy polydimethylsiloxane) with a high proportion, the number of functional groups (Si-OH content) capable of participating in a crosslinking reaction is more than that of the common component A, and the component A prepared by basic polymerization matched in the way is beneficial to improving the crosslinking density of a cured rubber material, so that the stretching and bonding performance of the organic silicon structural adhesive for solar photo-thermal power generation after humidity, heat and aging resistance is improved.
2) The invention adopts active nano active calcium carbonate with a cubic crystal structure and a pH value less than 10, and matches with a certain proportion of heavy calcium carbonate (the pH value is almost neutral) as a semi-reinforcing filler and matches with white carbon black for reinforcement, the method adopts the active nano active calcium carbonate with a lower pH value and simultaneously reduces the using amount of the active nano active calcium carbonate, so that the pH value of a sizing material system is biased to be neutral, thereby obviously reducing the de-crosslinking reaction of a crosslinking point in a high-temperature high-humidity environment, and further improving the humidity-resistant and aging-resistant performance of the cured sizing material. After the calcium carbonate semi-reinforcing system is matched with white carbon black for reinforcement, the tensile bonding strength of a sizing material to a base material can be greatly improved, and the prepared bi-component silicone structural adhesive for solar photo-thermal power generation is not less than 0.9MPa after being aged for 1008 hours twice by 85 hours.
3) The invention utilizes the reactivity of epoxy group in gamma-glycidoxypropyltrimethoxysilane, adds the epoxy group into aminosiloxane with a preset proportion by a starvation feeding method, and takes a composite coupling agent which is obtained by processing primary amine in the aminosiloxane to react and then changing the primary amine into secondary amine or tertiary amine as a tackifier under certain reaction conditions. The method greatly reduces the number of active H atoms of the residual amino alkyl in the vulcanized silicone structural adhesive, thereby improving the humidity and heat aging resistance of the silicone structural adhesive.
4) The invention adopts siloxane with high functional group number in a certain proportion as a cross-linking agent, and the cross-linking agent is matched with proper reinforcing powder, coupling agent and other cross-linking agent, thereby having the following advantages: firstly, the crosslinking agent has more functional groups which can participate in crosslinking reaction, and the base material prepared by the invention has good adhesion to various base materials after being cured, and has good adhesion to base materials such as solar reflectors, ceramic gaskets, aluminum profiles, stainless steel and the like; secondly, the higher number of the reactive functional groups can greatly improve the crosslinking density of the vulcanized rubber material, thereby improving the tensile adhesion of the structural rubber after wet heat aging resistance.
5) The dealcoholized double-component room temperature vulcanized silicone rubber is used as the silicone structural adhesive for solar photo-thermal power generation, has low smell and good deep curing performance, can adjust the curing speed, is suitable for industrial operation, has good tensile bonding strength after being subjected to damp-heat aging resistance treatment, and can meet the requirement of outdoor structural bonding.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
Preparation of component A
The component A is prepared by uniformly dispersing and mixing 20 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 700 mPas, 80 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 20000 mPas, 20 parts of polydimethylsiloxane with the viscosity of 500 mPas, 30 parts of nano active calcium carbonate, 50 parts of ground calcium carbonate and 5 parts of fumed silica under vacuum conditions.
Preparation of component B
30 parts of pigment carbon black, 40 parts of polydimethylsiloxane with the viscosity of 500 mPas, 20 parts of the 1 st cross-linking agent, 40 parts of ethyl orthosilicate, 10 parts of coupling agent and 2 parts of dibutyl tin dilaurate are dispersed and mixed uniformly under a vacuum condition to obtain the component B.
Wherein the 1 st cross-linking agent adopts a cross-linking agent with the structure that X is ethyl, R1 and R2 are methyl, and the molecular structure of the cross-linking agent is
Wherein the coupling agent is: the gamma-aminopropyl triethoxysilane and the gamma-glycidoxypropyl trimethoxysilane are metered according to the mass ratio of 1:1, and the gamma-glycidoxypropyl trimethoxysilane is slowly dropped into the gamma-aminopropyl triethoxysilane at the temperature of 85 ℃ to prepare a mixture.
A. Mixing the component B
A, B components are uniformly mixed according to the mass ratio of 14:1 to prepare a sample for testing
Example 2
Preparation of component A
Dispersing and mixing 10 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 700 mPas, 100 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 20000 mPas, 20 parts of polydimethylsiloxane with the viscosity of 500 mPas, 100 parts of nano active calcium carbonate, 50 parts of ground calcium carbonate and 2 parts of fumed silica uniformly under vacuum conditions to obtain the component A.
Preparation of component B
30 parts of pigment carbon black, 40 parts of polydimethylsiloxane with the viscosity of 500 mPas, 15 parts of the 1 st cross-linking agent, 40 parts of ethyl orthosilicate, 10 parts of coupling agent and 2 parts of dibutyl tin dilaurate are dispersed and mixed uniformly under a vacuum condition to obtain the component B.
Wherein the 1 st cross-linking agent adopts a cross-linking agent with X being octyl and R1 and R2 being methyl structures, and the molecular structure of the cross-linking agent is
Wherein the coupling agent is: the gamma-aminopropyl triethoxysilane and the gamma-glycidoxypropyl trimethoxysilane are metered according to the mass ratio of 1:1, and the gamma-glycidoxypropyl trimethoxysilane is slowly dropped into the gamma-aminopropyl triethoxysilane at the temperature of 85 ℃ to prepare a mixture.
A. Mixing the component B
A, B components are uniformly mixed according to the mass ratio of 14:1 to prepare a sample for testing
Example 3
Preparation of component A
The component A is prepared by uniformly dispersing and mixing 40 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 700 mPas, 60 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 20000 mPas, 10 parts of polydimethylsiloxane with the viscosity of 500 mPas, 60 parts of nano active calcium carbonate, 60 parts of ground calcium carbonate and 5 parts of fumed silica under vacuum conditions.
Preparation of component B
30 parts of pigment carbon black, 40 parts of polydimethylsiloxane with the viscosity of 500 mPas, 20 parts of the 1 st cross-linking agent, 40 parts of ethyl orthosilicate, 10 parts of coupling agent and 2 parts of dibutyl tin dilaurate are dispersed and mixed uniformly under a vacuum condition to obtain the component B.
Wherein the 1 st cross-linking agent adopts a cross-linking agent with the molecular structure of X being ethyl and R1 and R2 being ethyl
Wherein the coupling agent is: the weight ratio of the N-beta- (aminoethyl) -gamma-aminopropyl trimethoxyl silane to the gamma-glycidoxypropyl trimethoxyl silane is 1:1, and the mixture is prepared by slowly dripping the gamma-glycidoxypropyl trimethoxyl silane into the N-beta- (aminoethyl) -gamma-aminopropyl trimethoxyl silane at 90 ℃.
A. Mixing the component B
A, B components are uniformly mixed according to the mass ratio of 15:1 to prepare a sample for testing
Example 4
Preparation of component A
Dispersing and mixing 10 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 700 mPas, 80 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 20000 mPas, 20 parts of polydimethylsiloxane with the viscosity of 500 mPas, 60 parts of nano active calcium carbonate, 50 parts of heavy calcium carbonate and 3 parts of fumed silica uniformly under vacuum conditions to obtain the component A.
Preparation of component B
30 parts of pigment carbon black, 40 parts of polydimethylsiloxane with the viscosity of 500 mPas, 20 parts of the 1 st cross-linking agent, 40 parts of ethyl orthosilicate, 10 parts of coupling agent and 2 parts of dibutyl tin dilaurate are dispersed and mixed uniformly under a vacuum condition to obtain the component B.
Wherein the 1 st cross-linking agent adopts a cross-linking agent with the structure that X is ethyl, R1 and R2 are methyl, and the molecular structure of the cross-linking agent is
Wherein the coupling agent is: gamma-aminopropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane are metered in a mass ratio of 0.5:1, and the gamma-glycidoxypropyltrimethoxysilane is slowly added dropwise to the gamma-aminopropyltriethoxysilane at 85 ℃.
A. Mixing the component B
A, B components are uniformly mixed according to the mass ratio of 14:1 to prepare a sample for testing
Example 5
Preparation of component A
The component A is prepared by uniformly dispersing and mixing 20 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 700 mPas, 70 parts of alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 20000 mPas, 20 parts of polydimethylsiloxane with the viscosity of 500 mPas, 60 parts of nano active calcium carbonate, 50 parts of ground calcium carbonate and 3 parts of fumed silica under vacuum conditions.
Preparation of component B
30 parts of pigment carbon black, 40 parts of polydimethylsiloxane with the viscosity of 500 mPas, 15 parts of the 1 st cross-linking agent, 45 parts of ethyl orthosilicate, 15 parts of coupling agent and 2 parts of dibutyl tin dilaurate are dispersed and mixed uniformly under a vacuum condition to obtain the component B.
Wherein the 1 st cross-linking agent adopts a cross-linking agent with the structure that X is ethyl, R1 and R2 are methyl, and the molecular structure of the cross-linking agent is
Wherein the coupling agent is: the mixture of N-beta- (aminoethyl) -gamma-aminopropyl trimethoxyl silane and gamma-glycidoxypropyl trimethoxyl silane in the weight ratio of 5 to 1 is prepared through dropping gamma-glycidoxypropyl trimethoxyl silane slowly into N-beta- (aminoethyl) -gamma-aminopropyl trimethoxyl silane at 85 deg.c.
A. Mixing the component B
A, B components are uniformly mixed according to the mass ratio of 13:1 to prepare a sample for testing
Test results
Remarking: the test substrate is a reflecting mirror paint surface for solar photo-thermal power generation, the comparative example 1 is a certain commercially available bi-component silicone structural adhesive for a building, and the comparative example 2 is a certain commercially available single-component silicone sealant for a photovoltaic module; in the comparison test, due to different application fields of glue samples, the architectural double-component structural glue in the comparative example 1 is poor in adhesion to the reflector and 100% debonds after double 85 aging, the photovoltaic module single-component silicone sealant in the comparative example 2 has certain adhesion to the reflector for solar photo-thermal power generation, and 100% debonds after double 85 aging.
Description of the drawings: preparation, maintenance and aging test of samples
Preparing and maintaining a sample: mixing the component A and the component B according to the mass ratio of 10: 1-15: 1 to prepare a rubber material, preparing an H-shaped adhesive test piece (using a solar reflector paint surface as a test base material) according to a method provided by the seventh chapter of GB/T13477.8-2002, and vulcanizing and curing for 28 days in an environment with the temperature of 23 +/-2 ℃ and the relative humidity of 50 +/-5%.
Aging treatment mode of the sample: and (3) aging the prepared H-shaped module for 1008H at the temperature of 85 ℃ and the humidity of 85 ℃.
And (3) sample testing: and (3) performing a tensile bonding test on the H-shaped module which is cured or aged by the double 85 ageing treatment according to GB/T16776 (silicone structural sealant for buildings).
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (4)
1. The bi-component silicone structural adhesive for solar photo-thermal power generation comprises a component A and a component B, and is characterized in that: the component A and the component B respectively comprise the following components in parts by weight:
the component A comprises:
10-40 parts of 1-type alpha, omega-dihydroxy polydimethylsiloxane
60-100 parts of 2-type alpha, omega-dihydroxy polydimethylsiloxane
5-35 parts of plasticizer
80-150 parts of class 1 filler
0.5-10 parts of class 2 filler
The 1 st filler is nano active calcium carbonate, or the 1 st filler is the nano active calcium carbonate and heavy calcium carbonate which are matched for use; wherein the crystal form of the nano activated calcium carbonate is a cubic structure, and the pH value is less than 10 by adopting a GB/T19281 method; the 2 nd filler is at least one of fumed silica and precipitated silica;
the viscosity of the 1 st alpha, omega-dihydroxy polydimethylsiloxane is 100-3000 mPa ∙ s;
the viscosity of the 2-class alpha, omega-dihydroxy polydimethylsiloxane is 10000-80000 mPa ∙ s or the viscosity of the alpha, omega-dihydroxy polydimethylsiloxane compounded by different viscosities is 10000-80000 mPa ∙ s;
and B component:
20 to 35 parts of carbon black
25-40 parts of plasticizer
10-80 parts of class 1 crosslinking agent
25-80 parts of class 2 crosslinking agent
2.5-20 parts of coupling agent
0.1-2 parts of catalyst
The crosslinking agent of the 1 st class has the following structural characteristics:
wherein R1 and R2 are one of methyl OR ethyl, the sum of the numbers of siloxane groups Si-OR1 and Si-OR2 is 6, and X is an alkane with the carbon atom number more than OR equal to 2;
the 2 nd cross-linking agent is selected from one or a mixture of ethyl orthosilicate, propyl orthosilicate, isopropyl orthosilicate, poly ethyl orthosilicate, methyl triethoxysilane, polymethyl triethoxysilane, methyl trimethoxysilane and partial hydrolysis oligomer thereof, dimethyl dimethoxysilane, phenyl trimethoxysilane, propyl triethoxysilane, octyl trimethoxysilane, dodecyl trimethoxysilane, hexadecyl trimethoxysilane and tetracosyl trimethoxysilane;
the coupling agent is a mixture of an amino-hydrocarbyl silane coupling agent and gamma-glycidyl ether oxypropyl trimethoxy silane in a mass ratio of 0.5-5: 1, wherein the amino-hydrocarbyl silane coupling agent is one or a combination of gamma-aminopropyl triethoxy silane, gamma-aminopropyl trimethoxy silane, N-beta- (aminoethyl) -gamma-aminopropyl triethoxy silane, 3-aminopropyl methyl dimethoxy silane, N-N-butyl-3-aminopropyl triethoxy silane and gamma-ureido propyl trimethoxy silane.
2. The bi-component silicone structural adhesive for solar photothermal power of claim 1, wherein:
A. the plasticizer in the component B is selected from one or more compounds of vinyl-terminated polydimethylsiloxane, methyl polydimethylsiloxane and alpha, omega-dihydroxy polydimethylsiloxane, and the viscosity range of the plasticizer is 100-1000 mPa ∙ s.
3. The bi-component silicone structural adhesive for solar photothermal power of claim 1, wherein:
the carbon black is common pigment carbon black; the catalyst is one or more selected from dibutyl tin dilaurate, dimethyl tin diacetate, dibutyl tin diacetate, dimethyl tin dineodecanoate and stannous octoate.
4. The bi-component silicone structural adhesive for solar photothermal power of claim 1, wherein:
the mixing method of the coupling agent comprises the following steps:
heating the weighed aminoalkyl silane coupling agent to 80-90 ℃ under the protection of nitrogen, slowly dripping gamma-glycidoxypropyltrimethoxysilane into the aminoalkyl silane coupling agent, wherein the dripping speed is based on the principle that the reaction temperature is not more than 90 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811584133.2A CN109609083B (en) | 2018-12-24 | 2018-12-24 | Bi-component silicone structural adhesive for solar photo-thermal power generation and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811584133.2A CN109609083B (en) | 2018-12-24 | 2018-12-24 | Bi-component silicone structural adhesive for solar photo-thermal power generation and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109609083A CN109609083A (en) | 2019-04-12 |
| CN109609083B true CN109609083B (en) | 2021-04-02 |
Family
ID=66010538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811584133.2A Active CN109609083B (en) | 2018-12-24 | 2018-12-24 | Bi-component silicone structural adhesive for solar photo-thermal power generation and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109609083B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511596A (en) * | 2019-09-09 | 2019-11-29 | 青州宇信钙业股份有限公司 | A kind of silicone sealant high elongation rate composite Nano filler and preparation method thereof |
| CN112646542A (en) * | 2020-12-24 | 2021-04-13 | 上海回天新材料有限公司 | Solar photovoltaic module bi-component structural adhesive and preparation method thereof |
| CN112724925B (en) * | 2020-12-29 | 2022-08-02 | 广州市白云化工实业有限公司 | Two-component organic silicon packaging adhesive and preparation method and application thereof |
| CN113337122B (en) * | 2021-06-28 | 2023-10-13 | 湖南航天三丰科工有限公司 | Dealcoholized room-temperature cured silicone rubber with ultra-long storage period and preparation method thereof |
| CN114133912B (en) * | 2021-11-26 | 2023-11-24 | 广州市白云化工实业有限公司 | Bi-component silicone structural adhesive with strong initial adhesion |
| CN115141600B (en) * | 2022-08-19 | 2023-08-29 | 新疆西部合盛硅业有限公司 | Neutral oil-resistant silicone sealant and preparation method thereof |
| CN115505367B (en) * | 2022-09-15 | 2023-03-17 | 成都高新区今天硅材料有限公司 | High-strength organic silicon adhesive and preparation method thereof |
| CN115449337B (en) * | 2022-10-19 | 2023-08-01 | 杭州之江新材料有限公司 | Cleaning agent corrosion-resistant silicone structural adhesive and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2202276A1 (en) * | 2008-12-23 | 2010-06-30 | Sika Technology AG | Silicon compound with accelerated integration |
| CN102304345A (en) * | 2011-08-25 | 2012-01-04 | 文仁光 | Composition of double-component organosilicon photovoltaic component sealant, and preparation method thereof |
| CN102382615A (en) * | 2010-09-03 | 2012-03-21 | 广州市白云化工实业有限公司 | Organosilicon sealant for solar photovoltaic modules and preparation method for organosilicon sealant |
| CN102504755A (en) * | 2011-12-02 | 2012-06-20 | 北京天山新材料技术股份有限公司 | Epoxy resin modified two-component silicone rubber adhesive |
| CN104845377A (en) * | 2015-06-02 | 2015-08-19 | 北京天山新材料技术有限公司 | Double-component room temperature curing silicone rubber and preparation method thereof |
| CN107267112A (en) * | 2017-05-19 | 2017-10-20 | 天永诚高分子材料（常州）有限公司 | A kind of photovoltaic single-component silicon structure sealant and preparation method thereof |
-
2018
- 2018-12-24 CN CN201811584133.2A patent/CN109609083B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2202276A1 (en) * | 2008-12-23 | 2010-06-30 | Sika Technology AG | Silicon compound with accelerated integration |
| CN102382615A (en) * | 2010-09-03 | 2012-03-21 | 广州市白云化工实业有限公司 | Organosilicon sealant for solar photovoltaic modules and preparation method for organosilicon sealant |
| CN102304345A (en) * | 2011-08-25 | 2012-01-04 | 文仁光 | Composition of double-component organosilicon photovoltaic component sealant, and preparation method thereof |
| CN102504755A (en) * | 2011-12-02 | 2012-06-20 | 北京天山新材料技术股份有限公司 | Epoxy resin modified two-component silicone rubber adhesive |
| CN104845377A (en) * | 2015-06-02 | 2015-08-19 | 北京天山新材料技术有限公司 | Double-component room temperature curing silicone rubber and preparation method thereof |
| CN107267112A (en) * | 2017-05-19 | 2017-10-20 | 天永诚高分子材料（常州）有限公司 | A kind of photovoltaic single-component silicon structure sealant and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 脱醇型有机硅密封胶在太阳能光伏行业的应用;郁泽林等;《有机硅材料》;20170420;第31卷(第S1期);132-136 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109609083A (en) | 2019-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109609083B (en) | Bi-component silicone structural adhesive for solar photo-thermal power generation and preparation method thereof | |
| CN107880797B (en) | Special moisture-heat-resistant high-strength silicone structural adhesive for photovoltaic module | |
| CN109135660B (en) | Dealcoholized bi-component sealant and preparation method thereof | |
| CN106590501B (en) | Single-component epoxy modified organosilicon sealant and preparation method thereof | |
| CN109280533B (en) | Single-component dealcoholized transparent silicone sealant and preparation method and application thereof | |
| CN101353563A (en) | Single-component silicone fluid sealant for solar energy cell assembly and manufacturing method thereof | |
| CN108822790B (en) | Single-component dealcoholized low-modulus silicone weather-resistant sealant and preparation method thereof | |
| CN108546543B (en) | Organosilicon sealant and preparation method and application thereof | |
| CN108059945B (en) | Organosilicon sealant for photovoltaic dual-glass assembly and preparation method thereof | |
| CN102504755B (en) | Epoxy resin modified two-component silicone rubber adhesive | |
| CN113337245B (en) | Dealcoholized photovoltaic module sealant and preparation method thereof | |
| CN114262600B (en) | Low-water-vapor-permeability silicone sealant | |
| CN110272713B (en) | Silicone sealant and preparation method and application thereof | |
| CN107523259B (en) | Preparation of alpha-570 coupling agent modified organosilicon sealant | |
| CN109181623B (en) | Silicone sealant for fast curing photovoltaic module and preparation method thereof | |
| CN107057625B (en) | Building sealant for housing industrialization and preparation method thereof | |
| CN108047968B (en) | Low-modulus high-volume-resistivity silicone structural adhesive | |
| CN114874744A (en) | Mildew-proof beauty glue for interior decoration and preparation method thereof | |
| CN109666448A (en) | A kind of photovoltaic module dealcoholized type sealant and preparation method thereof | |
| CN115746565B (en) | Room temperature vulcanized silicone rubber and preparation method and application thereof | |
| CN109796926B (en) | Moisture-heat-resistant silicone structural adhesive for photovoltaic module | |
| CN103740322A (en) | Inflaming retarding type solar photovoltaic module sealant | |
| CN107868469B (en) | Water-resistant ultraviolet-bonding dealcoholized double-component room temperature vulcanized silicone rubber and preparation method thereof | |
| CN115260980A (en) | Preparation method of low-yellowing photovoltaic organic silicon adhesive | |
| CN109456727B (en) | Green light-cured STPU resin and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |