CN114621724A - Bi-component organosilicon sealant and preparation method thereof - Google Patents
Bi-component organosilicon sealant and preparation method thereof Download PDFInfo
- Publication number
- CN114621724A CN114621724A CN202210417641.1A CN202210417641A CN114621724A CN 114621724 A CN114621724 A CN 114621724A CN 202210417641 A CN202210417641 A CN 202210417641A CN 114621724 A CN114621724 A CN 114621724A
- Authority
- CN
- China
- Prior art keywords
- component
- parts
- calcium carbonate
- nano calcium
- raw materials
- 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.)
- Granted
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
- 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
- C09J183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/204—Applications use in electrical or conductive gadgets use in solar cells
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of organic silicon materials, and particularly relates to a two-component organic silicon sealant which comprises the following components in percentage by mass: 1, the component A comprises the following raw materials: 50-100 parts of alpha, omega-dihydroxy polydimethylsiloxane, 50-100 parts of nano calcium carbonate and 0-20 parts of plasticizer; the component B comprises the following raw materials: 100 parts of component B base stock, 0-8 parts of cross-linking agent, 0.5-5 parts of silane coupling agent and 0.1-1 part of catalyst; wherein the component B base material comprises the following raw materials: 100 parts of modified end-capped polysiloxane, 30-80 parts of nano calcium carbonate, 0-20 parts of an incremental filler and 2-5 parts of a water removal protective agent, wherein the modified end-capped polysiloxane is modified oximido polydimethylsiloxane. The two-component organic silicon sealant has high storage stability and quick curing.
Description
Technical Field
The invention belongs to the technical field of organic silicon materials, and particularly relates to a two-component organic silicon sealant and a preparation method thereof.
Background
Under the background of the state that the policy of 'double carbon' is implemented, the photovoltaic energy industry is further rapidly developed. The solar photovoltaic power generation system is a novel power generation system for directly converting solar radiation energy into electric energy, and a solar cell panel is also called a photovoltaic module and is one of core parts in the solar photovoltaic power generation system. The power generation life of the photovoltaic module is generally designed to be 25-30 years, and in the period, the photovoltaic module needs to be subjected to severe weather environments such as solarization, wind blowing, rain, snow and the like, so as to meet the severe use conditions, and the photovoltaic module needs to have excellent ultraviolet resistance and atmospheric aging resistance. Compared with other types of sealants, the single-component organosilicon sealant has excellent weather resistance and ultraviolet resistance, and is the mainstream sealant for the solar photovoltaic module in the current market. The curing mechanism of the single-component organosilicon sealant is that moisture in air is absorbed and cured from the outside to the inside, the curing speed is low, the thickness of the sealant can only be cured by 3-4 mm in 24 hours on average, the requirement of rapid, continuous and automatic production in the photovoltaic industry is difficult to meet, a curing room needs to be placed for 2-3 hours for curing after the sealant is constructed, and the production efficiency is low.
The two-component organosilicon sealant has the characteristic of simultaneous internal and external curing, and is suitable for continuous production. Patents CN112646542A and CN104845377A disclose a two-component sealant for photovoltaic module, which solves the problem of fast curing, but the mixing ratio of the two components needs to be controlled between 6: 1-20: 1, the requirement on the metering precision of the mixing equipment is high when in use, and when the mixing ratio fluctuates, the phenomenon of unstable performance, even non-curing, of the silicone sealant is easily caused, and the application limitation is large.
Patents CN102703022A, CN106147695A and CN106701009A disclose a mixing ratio of 1: 1, the basic polymer of the double-component fast curing organosilicon sealant contains poly-alkoxy end-capped polydimethylsiloxane besides alpha, omega-dihydroxy polydimethylsiloxane, and the three belong to a dealcoholization system, and the technical defects are as follows: the curing performance is gradually reduced along with the prolonging of the storage time, even the curing is not possible, the reliability is low, and the method is difficult to be applied to the photovoltaic industry.
Therefore, the development of the two-component organic silicon sealant which has low requirement on the metering precision of mixing equipment, quick curing and excellent storage stability has important significance.
Disclosure of Invention
The invention aims at providing a two-component organosilicon sealant which has excellent storage stability, is cured quickly, has low requirement on metering precision of mixing equipment and is beneficial to realizing continuous industrial production.
The basic concept of the technical scheme adopted by the invention is as follows:
the two-component organosilicon sealant comprises the following components in percentage by mass of 1: 1, the component A comprises the following raw materials: 50-100 parts of alpha, omega-dihydroxy polydimethylsiloxane, 50-100 parts of nano calcium carbonate and 0-20 parts of plasticizer; the component B comprises the following raw materials: 100 parts of component B base material, 0-8 parts of cross-linking agent, 0.5-5 parts of silane coupling agent and 0.1-1 part of catalyst; wherein the component B base material comprises the following raw materials: 100 parts of modified blocked polysiloxane, 30-80 parts of nano calcium carbonate, 0-20 parts of an incremental filler and 2-5 parts of a water removal protective agent, wherein the modified blocked polysiloxane is one or more of substances shown in formulas 1-3:
wherein n is an integer of 100 to 1500.
In one embodiment, the modified blocked polysiloxane has a kinematic viscosity of 2 to 150 pas at 25 ℃.
As a scheme, the water removal protective agent is phenyl tributyl ketoxime silane.
As a scheme, the nano calcium carbonate is an active nano calcium carbonate with the surface treated as follows: the treating agent is stearic acid accounting for 2-2.5% of the weight of the nano calcium carbonate and sodium dodecyl benzene sulfonate accounting for 1-1.25%, and the calcium carbonate and the treating agent are mixed in a stirrer at 50-100 ℃ for 60-120min to finally obtain the active nano calcium carbonate with the particle size of 20-90 nm.
Optionally, the extender filler is one of ground calcium carbonate, silica micropowder and aluminum hydroxide.
As an alternative, the catalyst H is an organic tin carboxylate and its chelate, optionally selected from one or more of dibutyl tin dilaurate, dibutyl tin diacetate, dioctyl tin dilaurate, dibutyl tin dilauryl sulfide, stannous octoate, dibutyl tin acetylacetonate, dibutyl tin ethylacetoacetate.
In one embodiment, the plasticizer is an inert polysiloxane, preferably methyl-terminated polydimethylsiloxane, and has a kinematic viscosity of 0.1 to 20 pas at 25 ℃.
In one embodiment, the cross-linking agent comprises one or more of methyl tributyrinoxime silane, vinyl tributyrinoxime silane, phenyl tributyrinoxime silane and tetrabutoximino silane.
The silane coupling agent comprises one or more of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-aminoethyl-gamma-aminopropyltrimethoxysilane, octyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane.
As a scheme, the component A is prepared from the following raw materials: 80-100 parts of alpha, omega-dihydroxy polydimethylsiloxane, 60-100 parts of nano calcium carbonate and 5-20 parts of plasticizer; the component B comprises the following raw materials: 100 parts of component B base material, 3-6 parts of cross-linking agent, 2-5 parts of silane coupling agent and 0.2-0.5 part of catalyst; wherein the component B base material comprises the following raw materials: 100 parts of modified blocked polysiloxane, 60-80 parts of nano calcium carbonate, 10-20 parts of an incremental filler and 2-5 parts of a water removal protective agent.
The invention provides an application of a two-component organosilicon sealant, wherein the two-component organosilicon sealant is used in the photovoltaic, electronic or automobile field, wherein A, B components are mixed according to the mass ratio of 1: 1 and mixing and using.
The invention also provides a preparation method of the two-component organosilicon sealant, which comprises the following steps:
preparation of component A: adding alpha, omega-dihydroxy polydimethylsiloxane, nano calcium carbonate and a plasticizer into a stirrer with a heating system and a decompression system, heating to 120-130 ℃, stirring for 2-3 hours under the condition that the vacuum degree is 0.085-0.099, and cooling to room temperature after dehydration;
preparation of component B: adding the modified end-capped polysiloxane, the water removal protective agent, the nano calcium carbonate and the incremental filler into a stirrer with a heating and pressure reducing system, heating to 110-130 ℃, and stirring for 2-3 hours under the condition that the vacuum degree is 0.085-0.099 to prepare a component B base material; cooling the base material of the component B to room temperature, adding a cross-linking agent, a coupling agent and a catalyst, and stirring at room temperature under reduced pressure for 30-60 min to obtain a component B;
mixing the component A and the component B according to the mass ratio of 1: 1 to obtain the bi-component organosilicon sealant.
Compared with the prior art, the invention has the following technical advantages:
1. the two-component organosilicon sealant provided by the invention is fast to cure, and the mass or volume ratio of the two components is 1: 1, the requirement on the metering precision of mixing equipment is low.
2. The component B of the two-component organosilicon sealant adopts the modified oximido polydimethylsiloxane, and compared with a dealcoholization system (such as a comparative example 1) adopted in the prior art, the two-component organosilicon sealant has better storage stability and can be stored for 12 months.
3. The two-component organic silicon sealant adopts the modified oximido polydimethylsiloxane to be used together with other formula components, compared with the multi-alkoxy end-capped polydimethylsiloxane in the prior art, the two-component organic silicon sealant has higher reaction activity and faster deep curing speed, is basically cured within 2 hours after mixed glue application, and meets the requirement of continuous production of photovoltaic modules.
4. According to the component B base material of the two-component organic silicon sealant, the phenyl tributyrinoxime silane is used as a water removal protective agent, the modified oximido polydimethylsiloxane is protected in the dehydration process, and the problem that the conventional water removal protective agent (such as vinyl trimethoxy silane) is hydrolyzed to generate methanol, so that the storage of a sizing material is unstable is solved.
5. The preparation method of the bi-component organosilicon sealant has simple process, is beneficial to operation and has high production efficiency.
6. The bi-component organic silicon sealant has high reliability, is particularly suitable for the photovoltaic field, and is beneficial to realizing the continuous production of photovoltaic components.
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 are 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 inventive step, are within the scope of protection of the invention.
In the following examples, the "parts" are parts by weight, which represents a charge ratio relationship, when uniform units such as g or kg are used in the same case.
The chemical agents or raw materials used in the examples of the present invention are commercially available unless otherwise specified.
As a specific example, the nano calcium carbonate used in the following examples 1 to 5 has a particle size of 20 to 90 nm.
As a case, the density of the a-and B-components of the present invention is close to 1: 1, the density ratio is 0.9 to 1.1, for example, 0.9, 0.92, 0.95, 0.97, 1, 1.02, 1.05, 1.08, 1.1.
The modified blocked polysiloxanes used in the following examples are one or more of the materials shown in formulas 1-3:
wherein n is an integer of 100 to 1500.
The modified blocked polysiloxanes of formulas 1-3 above can be prepared by the following method:
respectively carrying out stirring reaction on 100 parts of alpha, omega-dihydroxy polydimethylsiloxane and 1-3 parts of methyl tributyl ketoxime silane (the product corresponds to the formula 1) or tetrabutoxime silane (the product corresponds to the formula 2) or vinyl tributyroxime silane (the product corresponds to the formula 3) for 1-2 hours at the temperature of 20-50 ℃ and under the vacuum degree of 0.085-0.099.
Example 1
Preparation of a component A:
adding 100 parts of 20 Pa.s alpha, omega-dihydroxy polydimethylsiloxane, 100 parts of nano calcium carbonate and 5 parts of 0.35 Pa.s methyl-terminated polydimethylsiloxane into a stirrer with a heating and pressure reducing system, heating to 120 ℃, stirring for 3 hours under the conditions of a vacuum degree of 0.085-0.099, and cooling to room temperature after dehydration to obtain a component A;
b, preparation of a component:
100 parts of 20Pa s modified terminated polysiloxane has the following structure, wherein the value of n is 1000:
adding 80 parts of nano calcium carbonate, 20 parts of heavy calcium carbonate and 2 parts of phenyl tributyl ketoxime silane into a stirrer with a heating and pressure reducing system, heating to 120 ℃, and stirring for 3 hours under the condition that the vacuum degree is 0.085-0.099 to prepare a component B base material;
cooling the component B base material to room temperature, adding 5 parts of methyl tributyl ketoxime silane, 2 parts of gamma-aminopropyl triethoxysilane, 1 part of gamma-glycidoxypropyl trimethoxysilane and 0.2 part of dibutyl tin dilaurate, and stirring for 60min under the conditions of room temperature and vacuum degree of 0.085-0.099 to obtain a component B;
mixing the component A and the component B according to the mass ratio of 1: 1 to obtain the bi-component organic silicon sealant.
Example 2
Preparation of component A
Adding 100 parts of 20 Pa.s alpha, omega-dihydroxy polydimethylsiloxane, 100 parts of nano calcium carbonate and 5 parts of 0.35 Pa.s methyl-terminated polydimethylsiloxane into a stirrer with a heating and pressure reducing system, heating to 120 ℃, stirring for 3 hours under the conditions of vacuum degree of 0.085-0.099, and cooling to room temperature after dehydration to obtain a component A;
b, preparation of a component:
taking 100 parts of 20Pa & s modified end-capped polysiloxane, wherein the structure is as follows, wherein n takes the value of 1000:
adding 80 parts of nano calcium carbonate, 20 parts of silica powder and 3 parts of phenyltributyroximo silane into a stirrer with a heating and pressure reducing system, heating to 120 ℃, and stirring for 3 hours under the condition that the vacuum degree is 0.085-0.099 to prepare a component B base material;
cooling the component B base material to room temperature, adding 5 parts of methyl tributyl ketoxime silane, 2 parts of gamma-aminopropyl trimethoxy silane, 1 part of gamma-glycidoxypropyl trimethoxy silane and 0.2 part of dioctyl tin dilaurate, and stirring for 60min under the conditions of room temperature and vacuum degree of 0.085-0.099 to prepare a component B;
mixing the component A and the component B according to the mass ratio of 1: 1 to obtain the bi-component organic silicon sealant.
Example 3
Preparation of a component A:
adding 100 parts of 20Pa s alpha, omega-dihydroxy polydimethylsiloxane, 100 parts of nano calcium carbonate and 5 parts of 0.35Pa s methyl-terminated polydimethylsiloxane into a stirrer with a heating and pressure reducing system, heating to 120 ℃, reducing pressure and stirring for 3 hours, and cooling to room temperature after dehydration to obtain a component A;
b, preparation of a component:
100 parts of 20Pa & s modified end-capped polysiloxane has the following structure, wherein n is 1000:
adding 80 parts of nano calcium carbonate, 20 parts of aluminum hydroxide and 5 parts of phenyltributyroximo silane into a stirrer with a heating and pressure reducing system, heating to 120 ℃, reducing pressure and stirring for 3 hours to prepare a B component base material, cooling the base material to room temperature, adding 5 parts of methyltributanotoximo silane, 2 parts of N-aminoethyl-gamma-aminopropyltrimethoxysilane octyltrimethoxysilane, 1 part of gamma-methacryloxypropyltrimethoxysilane and 0.2 part of dibutyltin acetoacetate, and stirring for 60 minutes under the condition of normal temperature and vacuum degree of 0.085-0.099 to prepare a component B;
mixing the component A and the component B according to the mass ratio of 1: 1 to obtain the bi-component organic silicon sealant.
Example 4
Preparation of a component A:
adding 100 parts of 20 Pa.s alpha, omega-dihydroxy polydimethylsiloxane, 70 parts of nano calcium carbonate and 20 parts of 1.0 Pa.s methyl-terminated polydimethylsiloxane into a stirrer with a heating and pressure reducing system, heating to 120 ℃, stirring for 3 hours under the conditions of a vacuum degree of 0.085-0.099, and cooling to room temperature after dehydration to obtain a component A;
b, preparation of a component:
100 parts of 80Pa & s modified end-capped polysiloxane has the following structure, wherein n is 1500:
adding 60 parts of nano calcium carbonate, 10 parts of heavy calcium carbonate and 4 parts of phenyltributylketoxime silane into a stirrer with a heating and pressure reducing system, heating to 120 ℃, and stirring for 3 hours under the condition that the vacuum degree is 0.085-0.099 to prepare a component B base material;
cooling the component B base material to room temperature, adding 3 methyl tributyroximo silane, 2 parts of vinyl tributyroximo silane, 1 part of gamma-aminopropyltriethoxysilane, 1 part of gamma-glycidoxypropyltrimethoxysilane and 0.5 part of dibutyl tin dilaurate, and stirring for 60min under the conditions of room temperature vacuum degree of 0.085-0.099 to obtain a component B;
mixing the component A and the component B according to the mass ratio of 1: 1 to obtain the bi-component organic silicon sealant.
Example 5
Preparation of a component A:
adding 100 parts of 20 Pa.s alpha, omega-dihydroxy polydimethylsiloxane, 70 parts of nano calcium carbonate and 20 parts of 1.0 Pa.s methyl-terminated polydimethylsiloxane into a stirrer with a heating and pressure reducing system, heating to 120 ℃, stirring for 3 hours under the conditions of a vacuum degree of 0.085-0.099, and cooling to room temperature after dehydration to obtain a component A;
b, preparation of a component:
100 parts of 80Pa s modified terminated polysiloxane has the following structure, wherein n is 1500:
adding 60 parts of nano calcium carbonate, 10 parts of heavy calcium carbonate and 4-phenyl-tributyrinoxime silane into a stirrer with a heating and pressure reducing system, heating to 120 ℃, and stirring for 3 hours under the condition that the vacuum degree is 0.085-0.099 to prepare a component B base material;
cooling the component B base material to room temperature, adding 3 methyl tributyroximo silane, 2 parts of phenyl tributyroximo silane, 1 part of gamma-aminopropyl trimethoxy silane, 1 part of gamma-glycidoxypropyl trimethoxy silane and 0.5 part of dioctyl tin dilaurate, and stirring for 60min under the conditions of room temperature and vacuum degree of 0.085-0.099 to obtain a component B;
mixing the component A and the component B according to the mass ratio of 1: 1 to obtain the bi-component organic silicon sealant.
Example 6
The difference from the embodiment 1 is that the nano calcium carbonate is activated calcium carbonate with surface treated by stearic acid, and the specific method is as follows: the treating agent is stearic acid accounting for 2 percent of the mass of the nano calcium carbonate and sodium dodecyl benzene sulfonate accounting for 1 percent of the mass of the nano calcium carbonate, and the treating process is that the calcium carbonate and the treating agent are mixed in a stirrer for 100min at the temperature of 90 ℃ to obtain the active nano calcium carbonate with the particle size of 20-90 nm.
Comparative example 1
The only difference from example 1 is that the modified blocked polysiloxane of component B is replaced by alkoxy blocked polysiloxane of the following structure, wherein n is 1000:
while the crosslinker methyltributanonoximosilane was replaced by methyltrimethoxysilane, the rest remained the same as in example 1.
Comparative example 2
The only difference from example 1 is that the water removal protectant phenyltributyrinoxime silane in the B component binder was replaced with vinyltrimethoxysilane, the others being in accordance with example 1.
Comparative example 3
The only difference from example 1 is that the phenyltributyroximosilane in the B component binder was removed.
After the base material is cooled to room temperature, the viscosity of the base material is obviously thickened and has a cross-linking sign because no water removal protective agent is added in the base material dehydration process, and the preparation of the component B cannot be continued.
Test examples
The performance of the organosilicon sealants of the embodiments 1-6 and the comparative examples 1-3 is tested under the same condition, and the specific method comprises the following steps:
1) testing the surface drying time and the deep curing rate of the obtained organosilicon sealant according to the national standard GB/T13477-2002;
2) testing the hardness of the obtained organosilicon sealant according to the national standard GB/T531.1-2008;
3) testing the tensile strength and the elongation at break of the obtained organosilicon sealant according to the national standard GB/T528-2009;
4) the silicone sealant prepared was stored in a hose at room temperature for 1 year and the conditions during storage were monitored.
The test results are specifically shown in table 1.
TABLE 1
Compared with the performance data of the comparative example 1 and the comparative example 1, the component B adopts the modified oximido polydimethylsiloxane as the base polymer, the performance change difference of the organosilicon sealant is small before and after the organosilicon sealant is stored at room temperature for one year, and the organosilicon sealant is more stable to store, while the alkoxy-terminated polysiloxane adopted in the comparative example 1 is a scheme commonly adopted in the market at present, the performance difference before and after the organosilicon sealant is large, and the storage stability is poor.
Compared with the performance data of the component B, the performance data of the component B in the comparative example 1 and the component B in the comparative example 2 show that the modified oximido polydimethylsiloxane is protected by adopting the phenyltributyroximo silane as the water removal protective agent in the water removal process, the product has small performance change difference after being stored at room temperature for one year, and is more stable in storage, while the component B in the comparative example 2 adopts the vinyltrimethoxysilane, so that the component B is easy to hydrolyze to generate methanol, and the rubber material is unstable in storage and poor in storage stability.
As can be seen from comparison of examples 1 and 3, if a water removal protective agent, such as phenyl tributyrinoxime silane or vinyl trimethoxy silane, is not used in the process of removing low content of the B component base material, the base material is easily self-crosslinked in the process of heating and dehydrating due to high activity of the modified oximido polydimethylsiloxane, so that the B component can not be prepared continuously, and a two-component silicone sealant product can not be obtained.
Compared with the example 1, the mechanical property of the activated nano calcium carbonate adopting the optimized treatment is relatively better.
Claims (10)
1. The two-component organic silicon sealant comprises the following components in percentage by mass: 1 and a component B, wherein the component A comprises the following raw materials: 50-100 parts of alpha, omega-dihydroxy polydimethylsiloxane, 50-100 parts of nano calcium carbonate and 0-20 parts of plasticizer; the component B comprises the following raw materials: 100 parts of component B base stock, 0-8 parts of cross-linking agent, 0.5-5 parts of silane coupling agent and 0.1-1 part of catalyst; wherein the component B base material comprises the following raw materials: 100 parts of modified blocked polysiloxane, 30-80 parts of nano calcium carbonate, 0-20 parts of an incremental filler and 2-5 parts of a water removal protective agent, wherein the modified blocked polysiloxane is one or more of substances shown in formulas 1-3:
wherein n is an integer of 100 to 1500.
2. The two-component silicone sealant according to claim 1, wherein the modified blocked polysiloxane has a kinematic viscosity of 2 to 150 Pa-s at 25 ℃.
3. The two-component silicone sealant of claim 1 wherein the water scavenging protectant is phenyl tributyrinoxime silane;
optionally, the nano calcium carbonate is an active nano calcium carbonate with the surface treated as follows: the treating agent is stearic acid accounting for 2-2.5% of the weight of the nano calcium carbonate and sodium dodecyl benzene sulfonate accounting for 1-1.25%, and the calcium carbonate and the treating agent are mixed in a stirrer at 50-100 ℃ for 60-120min to finally obtain the active nano calcium carbonate with the particle size of 20-90 nm;
optionally, the extender filler is one of ground calcium carbonate, silica micropowder and aluminum hydroxide.
4. The two-part silicone sealant according to claim 1, wherein the catalyst H is a tin organic carboxylate and its chelate, optionally selected from one or more of dibutyl tin dilaurate, dibutyl tin diacetate, dioctyl tin dilaurate, di (dodecyl sulfur) dibutyl tin, stannous octoate, dibutyl tin acetylacetonate, dibutyl tin ethyl acetoacetate.
5. The two-component silicone sealant according to claim 1, wherein the plasticizer is an inert polysiloxane, preferably methyl terminated polydimethylsiloxane, and has a kinematic viscosity at 25 ℃ of 0.1 to 20 Pa-s.
6. The two-component silicone sealant according to claim 1, wherein the cross-linking agent comprises one or more of methyl tributyrinoxime silane, vinyl tributyrinoxime silane, phenyl tributyrinoxime silane, and tetrabutoximino silane.
7. The two-part silicone sealant according to claim 1, wherein the silane coupling agent comprises one or more of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-aminoethyl-gamma-aminopropyltrimethoxysilane, octyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and gamma-methacryloxypropyltrimethoxysilane.
8. The two-component silicone sealant according to claim 1, wherein the component a is prepared from the following raw materials: 80-100 parts of alpha, omega-dihydroxy polydimethylsiloxane, 60-100 parts of nano calcium carbonate and 5-20 parts of plasticizer; the component B comprises the following raw materials: 100 parts of component B base material, 3-6 parts of cross-linking agent, 2-5 parts of silane coupling agent and 0.2-0.5 part of catalyst; wherein the component B base material comprises the following raw materials: 100 parts of modified end-capped polysiloxane, 60-80 parts of nano calcium carbonate, 10-20 parts of an incremental filler and 2-5 parts of a water removal protective agent.
9. The use of two-component silicone sealants according to any one of claims 1 to 8, wherein the two-component silicone sealant is used in the photovoltaic, electronic or automotive field, wherein A, B components are mixed in a mass ratio of 1: 1 and mixing and using.
10. The method of preparing a two-part silicone sealant according to any one of claims 1-8 comprising the steps of:
preparation of component A: adding alpha, omega-dihydroxy polydimethylsiloxane, nano calcium carbonate and a plasticizer into a stirrer with a heating system and a decompression system, heating to 120-130 ℃, stirring for 2-3 hours under the condition that the vacuum degree is 0.085-0.099, and cooling to room temperature after dehydration;
preparation of component B: adding the modified end-capped polysiloxane, the water removal protective agent, the nano calcium carbonate and the incremental filler into a stirrer with a heating and pressure reducing system, heating to 110-130 ℃, and stirring for 2-3 hours under the condition that the vacuum degree is 0.085-0.099 to prepare a component B base material; cooling the base material of the component B to room temperature, adding a cross-linking agent, a coupling agent and a catalyst, and stirring at room temperature under reduced pressure for 30-60 min to obtain a component B;
the component A and the component B are mixed according to the mass ratio of 1: 1 to obtain the bi-component organic silicon sealant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210417641.1A CN114621724B (en) | 2022-04-20 | 2022-04-20 | Double-component organic silicon sealant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210417641.1A CN114621724B (en) | 2022-04-20 | 2022-04-20 | Double-component organic silicon sealant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114621724A true CN114621724A (en) | 2022-06-14 |
| CN114621724B CN114621724B (en) | 2023-07-28 |
Family
ID=81905730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210417641.1A Active CN114621724B (en) | 2022-04-20 | 2022-04-20 | Double-component organic silicon sealant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114621724B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115678492A (en) * | 2022-11-23 | 2023-02-03 | 江西天永诚高分子材料有限公司 | Solar photovoltaic module two-component sealant and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007177033A (en) * | 2005-12-27 | 2007-07-12 | Momentive Performance Materials Japan Kk | Room temperature-curable polyorganosiloxane composition |
| CN101402845A (en) * | 2008-11-11 | 2009-04-08 | 北京市化学工业研究院 | Process for producing flame-proof fluid sealant for construction |
| CN101511943A (en) * | 2006-08-30 | 2009-08-19 | Sika技术股份公司 | Silicone composition |
| CN102516931A (en) * | 2011-12-07 | 2012-06-27 | 北京天山新材料技术股份有限公司 | Ketoxime-alcohol removal type room-temperature vulcanized silicon rubber sealant and preparation method thereof |
| CN103013430A (en) * | 2012-12-24 | 2013-04-03 | 成都硅宝科技股份有限公司 | Environment-friendly organosilicone sealant and manufacturing method thereof |
| CN107880837A (en) * | 2017-10-30 | 2018-04-06 | 广州市白云化工实业有限公司 | Exfoliated silane modified polyether adhesive of shock resistance and preparation method thereof |
| CN109627773A (en) * | 2018-12-29 | 2019-04-16 | 湖北回天新材料股份有限公司 | A kind of single-component room-temperature-vulsilicone silicone rubber and preparation method |
| CN110591638A (en) * | 2019-11-04 | 2019-12-20 | 镇江博慎新材料有限公司 | Low-proportion bi-component dealcoholized organosilicon sealant and preparation method and application thereof |
| CN111057517A (en) * | 2019-12-31 | 2020-04-24 | 广州机械科学研究院有限公司 | Bi-component fast curing type organic silicon structural adhesive and preparation method thereof |
| CN113789149A (en) * | 2021-09-24 | 2021-12-14 | 中天东方氟硅材料有限公司 | Single-component organic silicon molding repair daub and preparation method thereof |
-
2022
- 2022-04-20 CN CN202210417641.1A patent/CN114621724B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007177033A (en) * | 2005-12-27 | 2007-07-12 | Momentive Performance Materials Japan Kk | Room temperature-curable polyorganosiloxane composition |
| CN101511943A (en) * | 2006-08-30 | 2009-08-19 | Sika技术股份公司 | Silicone composition |
| CN101402845A (en) * | 2008-11-11 | 2009-04-08 | 北京市化学工业研究院 | Process for producing flame-proof fluid sealant for construction |
| CN102516931A (en) * | 2011-12-07 | 2012-06-27 | 北京天山新材料技术股份有限公司 | Ketoxime-alcohol removal type room-temperature vulcanized silicon rubber sealant and preparation method thereof |
| CN103013430A (en) * | 2012-12-24 | 2013-04-03 | 成都硅宝科技股份有限公司 | Environment-friendly organosilicone sealant and manufacturing method thereof |
| CN107880837A (en) * | 2017-10-30 | 2018-04-06 | 广州市白云化工实业有限公司 | Exfoliated silane modified polyether adhesive of shock resistance and preparation method thereof |
| CN109627773A (en) * | 2018-12-29 | 2019-04-16 | 湖北回天新材料股份有限公司 | A kind of single-component room-temperature-vulsilicone silicone rubber and preparation method |
| CN110591638A (en) * | 2019-11-04 | 2019-12-20 | 镇江博慎新材料有限公司 | Low-proportion bi-component dealcoholized organosilicon sealant and preparation method and application thereof |
| CN111057517A (en) * | 2019-12-31 | 2020-04-24 | 广州机械科学研究院有限公司 | Bi-component fast curing type organic silicon structural adhesive and preparation method thereof |
| CN113789149A (en) * | 2021-09-24 | 2021-12-14 | 中天东方氟硅材料有限公司 | Single-component organic silicon molding repair daub and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115678492A (en) * | 2022-11-23 | 2023-02-03 | 江西天永诚高分子材料有限公司 | Solar photovoltaic module two-component sealant and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114621724B (en) | 2023-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110982482B (en) | Low-modulus high-elongation silicone sealant with good adhesion and preparation method thereof | |
| CN108264840B (en) | Novel anti-pollution flashover coating and preparation method thereof | |
| CN114621724A (en) | Bi-component organosilicon sealant and preparation method thereof | |
| CN110734730A (en) | silane modified polyether two-component sealant and preparation method thereof | |
| CN108546543A (en) | Organosilicon sealant and its preparation method and application | |
| CN109181623B (en) | Silicone sealant for fast curing photovoltaic module and preparation method thereof | |
| CN113337245A (en) | Dealcoholized photovoltaic module sealant and preparation method thereof | |
| CN113512393A (en) | Soaking-resistant flame-retardant single-component silane modified polyether sealant and preparation method thereof | |
| CN109880566B (en) | Electronic material with high thermal stability and preparation method thereof | |
| CN116426227A (en) | Light conversion adhesive film containing composite light conversion agent, preparation method thereof and photovoltaic module | |
| CN113897171B (en) | Preparation method of high-displacement dealcoholized flame-retardant fireproof sealant | |
| CN108047968B (en) | Low-modulus high-volume-resistivity silicone structural adhesive | |
| CN109666448A (en) | A kind of photovoltaic module dealcoholized type sealant and preparation method thereof | |
| CN112480860B (en) | Single-component silicone sealant with excellent yellowing resistance and weather resistance and preparation method thereof | |
| CN115093779B (en) | Solvent-free transparent waterproof coating and preparation method thereof | |
| CN115785757A (en) | Insulating coating with low interface adhesion and preparation method thereof | |
| CN114958293A (en) | Low-odor coated dealcoholized transparent flowing sealant for electronic and electric appliances | |
| CN114316897A (en) | Silicone sealant and preparation method thereof | |
| CN114525105A (en) | Two-component organic silicon pouring sealant for photovoltaic junction box and preparation method thereof | |
| CN109456727B (en) | Green light-cured STPU resin and preparation method and application thereof | |
| CN113736428B (en) | Environment-friendly low-modulus sealant and preparation method thereof | |
| CN115368399B (en) | Preparation method and application of efficient stabilizer for dealcoholized room temperature vulcanized silicone rubber | |
| CN116083025A (en) | MS (MS) adhesive with good low-temperature extrudability and preparation method thereof | |
| CN115678494B (en) | High-temperature-resistant silicone adhesive and preparation method thereof | |
| CN114369246B (en) | Hydrogenated polybutadiene modified silicone 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 |