CN114214025B - Novel double-component silicone structural sealant and preparation method thereof - Google Patents
Novel double-component silicone structural sealant and preparation method thereof Download PDFInfo
- Publication number
- CN114214025B CN114214025B CN202111528381.7A CN202111528381A CN114214025B CN 114214025 B CN114214025 B CN 114214025B CN 202111528381 A CN202111528381 A CN 202111528381A CN 114214025 B CN114214025 B CN 114214025B
- Authority
- CN
- China
- Prior art keywords
- parts
- component
- calcium carbonate
- structural sealant
- nano calcium
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
Abstract
The application relates to the technical field of silicone structural sealants, and particularly discloses a novel double-component silicone structural sealant and a preparation method thereof. The novel double-component silicone structural sealant comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 30-70 parts of nano calcium carbonate, 20-55 parts of base adhesive and 2-35 parts of simethicone; the component B comprises the following raw materials in parts by weight: 10-30 parts of carbon black, 3-15 parts of fumed silica, 20-40 parts of dimethyl silicone oil, 10-50 parts of a first cross-linking agent, 10-45 parts of a second cross-linking agent, 10-45 parts of a coupling agent and 0.01-0.14 part of a catalyst; wherein the second crosslinking agent is propyl trimethoxy silane oligomer with a polymerization degree of 4-6. The two-component silicone structural sealant has the advantages of excellent water-immersed adhesion performance and excellent ageing resistance.
Description
Technical Field
The application relates to the technical field of silicone structural sealants, in particular to a novel two-component silicone structural sealant and a preparation method thereof.
Background
The silicone sealant belongs to an organosilicon product, a polymer main chain mainly comprises silicon-oxygen-silicon bonds, and a cross-linking agent reacts with a base polymer to form a net-shaped Si-O-Si skeleton structure in the curing process.
Silicone sealants can be generally classified into two major types, one-component and two-component, one-component silicone sealants, the curing of which is chemically reactive by contact with moisture in the air; two-component means that the silicone gum is divided into two groups A, B, either of which alone does not form a cure, but the two groups of gums cure once mixed.
When the two-component silicone structural sealant is used, the two components are uniformly mixed, and then the sealant is injected into a sealant part within a certain time. The curing speed of the two-component silicone structural sealant can be adjusted within a certain range, so that a satisfactory curing effect is achieved.
In view of the above-described related art, the applicant has found that the two-component silicone structural sealant is poor in water-immersion adhesion property after curing.
Disclosure of Invention
In order to improve the water-soaking adhesive property of the two-component silicone structural sealant, the application provides a novel two-component silicone structural sealant and a preparation method thereof.
In a first aspect, the present application provides a novel two-component silicone structural sealant, which adopts the following technical scheme: a novel double-component silicone structural sealant comprises a component A and a component B,
the component A comprises the following raw materials in parts by weight:
30-70 parts of nano calcium carbonate, 20-55 parts of base adhesive and 2-35 parts of simethicone;
the component B comprises the following raw materials in parts by weight:
10-30 parts of carbon black, 3-15 parts of fumed silica, 20-40 parts of dimethyl silicone oil, 10-50 parts of a first cross-linking agent, 10-45 parts of a second cross-linking agent, 10-45 parts of a coupling agent and 0.01-0.14 part of a catalyst;
wherein the second crosslinking agent is propyl trimethoxy silane oligomer, and the structural formula is as follows:
where n=4-10.
By adopting the technical scheme, the propyl trimethoxy silane oligomer is a polymer with polar groups on the main chain and nonpolar groups on the side chains, and the propyl trimethoxy silane oligomer has more reaction crosslinking points. The propyl trimethoxy silane oligomer with a certain proportion is added into the double-component silicone structure sealant, so that the surface reaction crosslinking points of the propyl trimethoxy silane oligomer are more, the activity is high, the crosslinking curing speed is high, the surface drying time of the sealant is improved, the use amount of a catalyst can be correspondingly reduced, and the overall curing speed of the double-component silicone structure sealant is improved. In addition, the crosslinking density of the sealant can be improved, the bonding strength and the elongation of the sealant are improved, and the ultraviolet aging resistance of the sealant with the double-component structure is improved. The polar and nonpolar groups on the propyl trimethoxy silane oligomer can also reduce the surface tension of the object to be coated, improve the hydrophobic property and improve the water-soaking adhesive property of the double-component silicone structural sealant.
Preferably, the component A comprises the following raw materials in parts by weight:
40-60 parts of nano calcium carbonate, 30-50 parts of base adhesive and 5-30 parts of simethicone;
the component B comprises the following raw materials in parts by weight:
15-20 parts of carbon black, 5-10 parts of fumed silica, 25-30 parts of dimethyl silicone oil, 15-40 parts of a first cross-linking agent, 15-40 parts of a second cross-linking agent, 15-40 parts of a coupling agent and 0.01-0.1 part of a catalyst.
By adopting the technical scheme, the raw material proportion is further optimized, and the overall performance of the double-component silicone structural sealant is improved.
Preferably, the preparation method of the propyl trimethoxy silane oligomer comprises the following steps:
A1. 1600-1700 parts of propyl trimethoxy silane, 200-230 parts of methanol and 18-48 parts of concentrated hydrochloric acid are uniformly mixed to obtain a mixed solution A, the mixed solution A is stirred and heated to 40-50 ℃, 88-183 parts of water and 212-400 parts of methanol are added into the mixed solution A in a dropwise manner, and the propyl trimethoxy silane is hydrolyzed.
A2. After the propyl trimethoxy silane is completely hydrolyzed, heating to 110-130 ℃, carrying out polymerization reaction for 2-4h, then carrying out reduced pressure distillation to collect methanol, and cooling to room temperature to obtain the colorless transparent propyl trimethoxy silane oligomer.
By adopting the technical scheme, the hydrolysis of the propyl trimethoxy silane is promoted under the auxiliary action of methanol, and the hydrolysis is carried out.
Preferably, the particle size of the nano calcium carbonate is 30-100nm, and the volatile matters are less than or equal to 0.5%.
By adopting the technical scheme, the nano calcium carbonate has excellent tensile strength, elongation at break and ageing resistance, the nano calcium carbonate is filled in a system of the structural sealant, the adhesive property and ageing resistance of the structural sealant can be improved, the particle size is in the range of 30-100nm, and the volatile matters are less than or equal to 0.5 percent of nano, so that the increase of hydroxyl on the surface of the calcium carbonate and the tendency of mutual aggregation caused by the overhigh volatile matters can be avoided, and the dispersion property of the nano calcium carbonate is improved.
Preferably, the weight ratio of the particle size of the nano calcium carbonate to the particle size of 80-100nm is (1-3): 1.
by adopting the technical scheme, the grain size grading of the nano calcium carbonate is limited, and the nano calcium carbonate within the grain size grading range can be dispersed in the structural sealant system more uniformly and compactly, so that the anti-aging performance of the structural sealant is improved.
Preferably, the nano calcium carbonate is modified by the following treatment method:
and (3) carrying out surface treatment on the nano calcium carbonate by using a silane coupling agent.
By adopting the technical scheme, the nano calcium carbonate is easy to agglomerate and poor in fluidity, and the silane coupling agent is used for wrapping the nano calcium carbonate, so that the probability of agglomeration of the nano calcium carbonate can be reduced, and the dispersibility of the nano calcium carbonate in a structural sealant system is improved.
Preferably, before the silane coupling agent is modified, the nano calcium carbonate is soaked in a phosphate solution for surface treatment, and then is filtered and dried.
The nano calcium carbonate has fewer surface hydroxyl groups and is usually weak in alkalinity, so that the silane coupling agent has poor bonding on the surface of the calcium carbonate; the surface treatment is carried out on the nano calcium carbonate by using phosphate, the phosphate group can be used as a living point for reacting with the silane coupling agent, the silane coupling agent is coated on the surface of the nano calcium carbonate through chemical action, and the binding force between the silane coupling agent and the nano calcium carbonate is improved.
Preferably, the silane coupling agent is a triamino silane.
By adopting the technical scheme, the number of the amino functional groups in the triamino silane is large, and the amino functional groups can improve the inorganic-organic interface adhesive force in the structural sealant system, so that the soaking adhesive property is improved.
Preferably, the viscosity of the base adhesive at 25 ℃ is 500-80000 mpa.s, and the volatile matter is less than or equal to 0.5%.
By adopting the technical scheme, the parameters of the base adhesive are limited, and the base adhesive can be better matched with the cross-linking agent for curing, so that the adhesive property is improved.
In a second aspect, the present application provides a method for preparing a novel two-component silicone structural sealant, which adopts the following technical scheme:
a preparation method of a novel double-component silicone structural sealant comprises the following steps:
uniformly mixing nano calcium carbonate, base gum and dimethyl silicone oil according to parts by weight at 50-90 ℃ under the condition of vacuum degree (-0.09 Mpa) -0.1Mpa, and independently packaging to obtain a component A;
uniformly stirring carbon black according to parts by weight under the conditions of 110-150 ℃ and vacuum degree (-0.09 Mpa) - (-0.1 Mpa), then adding a first cross-linking agent and a second cross-linking agent, stirring and mixing under the conditions of vacuum degree-0.09 Mpa-0.1 Mp, then adding fumed silica, uniformly mixing, finally adding a coupling agent and a catalyst, uniformly mixing under the conditions of vacuum degree-0.09 Mpa-0.1 Mp, and individually packaging to obtain the component B.
By adopting the technical scheme, the scheme is simple to operate, has no special requirement on processing equipment, and is suitable for mass production.
In summary, the present application has the following beneficial effects:
1. as the propyl trimethoxy silane oligomer is adopted as the cross-linking agent to be matched with other components such as base rubber and the like, the deep curing speed is improved, the bonding strength of the prepared structural sealant under standard conditions can reach 1.65-2.91MPa, the bonding strength after soaking can reach 1.28-2.36MPa, the bonding performance and the soaking bonding performance are excellent, the thermal weight loss after heat aging treatment is 0.4-2.3%, and the ageing resistance is excellent.
2. In the application, the nano calcium carbonate is preferably subjected to surface modification treatment, the bonding strength of the prepared structural sealant under standard conditions can reach 2.67-2.91MPa, the bonding strength after soaking can reach 2.15-2.36MPa, and the soaking bonding performance is further improved.
Detailed Description
The present application is described in further detail below with reference to examples.
Preparation examples of starting materials and intermediates
Raw materials
The base adhesive is 107 base adhesives;
the volatile matter of the fumed silica is less than or equal to 0.5 percent, and the specific surface area is 130-200m 2 In this example, the volatile matter was 0.2% and the specific surface area was 150m 2 /g；
The first cross-linking agent is any one of methyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, methyl orthosilicate and ethyl orthosilicate, and methyltriethoxysilane is selected in the embodiment;
the coupling agent is any one of aminopropyl triethoxysilane, aminopropyl trimethoxysilane, glycidol ether oxypropyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane and N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane, and the aminopropyl triethoxysilane is selected in the embodiment;
the catalyst is dibutyl tin dilaurate;
the mass percentage concentration of the concentrated hydrochloric acid is 37%;
the phosphate is 1006P isomerism deca alcohol polyoxyethylene ether phosphate;
other raw materials are all commercially available.
Preparation example
Preparation example 1
The preparation method of the propyl trimethoxy silane oligomer comprises the following steps:
A1. 1600g of propyl trimethoxy silane, 200g of methanol and 18g of concentrated hydrochloric acid are added into a 3000ml three-neck flask, the mixture is uniformly mixed to obtain a mixed solution A, a reflux condenser, a thermometer and a constant pressure dropping funnel are arranged on the three-neck flask, the mixed solution A is stirred and heated to 50 ℃, 88g of water and 212g of methanol are dripped into the mixed solution A through the constant pressure dropping funnel, and the propyl trimethoxy silane is hydrolyzed;
A2. after the propyl trimethoxy silane is completely hydrolyzed, heating to 110 ℃, carrying out polymerization reaction for 2 hours, then carrying out reduced pressure distillation to collect methanol, and cooling to room temperature to obtain colorless and transparent propyl trimethoxy silane oligomer;
the polymerization degree of the polymer was 4, and the nuclear magnetic resonance hydrogen spectrum showed absorption peaks at 0.592ppm, 0.922ppm, 1.425ppm and 3.503 ppm.
Preparation example 2
The preparation method of the propyl trimethoxy silane oligomer comprises the following steps:
A1. 1700g of propyl trimethoxy silane, 230g of methanol and 48g of concentrated hydrochloric acid are added into a 3000ml three-neck flask, the mixture is uniformly mixed to obtain a mixed solution A, a reflux condenser, a thermometer and a constant pressure dropping funnel are arranged on the three-neck flask, the mixed solution A is stirred and heated to 40 ℃, and 186g of water and 400g of methanol are dripped into the mixed solution A through the constant pressure dropping funnel to hydrolyze the propyl trimethoxy silane;
A2. after the propyl trimethoxy silane is completely hydrolyzed, heating to 130 ℃, carrying out polymerization reaction for 4 hours, then carrying out reduced pressure distillation to collect methanol, and cooling to room temperature to obtain colorless and transparent propyl trimethoxy silane oligomer;
the polymerization degree of the polymer was 6, and the nuclear magnetic resonance hydrogen spectrum showed absorption peaks at 0.590ppm, 0.924ppm, 1.422ppm and 3.499 ppm.
Preparation example 3
The preparation method of the propyl trimethoxy silane oligomer comprises the following steps:
A1. 1700g of propyl trimethoxy silane, 200g of methanol and 48g of concentrated hydrochloric acid are added into a 3000ml three-neck flask, the mixture is uniformly mixed to obtain a mixed solution A, a reflux condenser, a thermometer and a constant pressure dropping funnel are arranged on the three-neck flask, the mixed solution A is stirred and heated to 50 ℃, 746g of water and 700g of methanol are dripped into the mixed solution A through the constant pressure dropping funnel, and the propyl trimethoxy silane is hydrolyzed;
A2. after the propyl trimethoxy silane is completely hydrolyzed, heating to 130 ℃, carrying out polymerization reaction for 4 hours, then carrying out reduced pressure distillation to collect methanol, and cooling to room temperature to obtain colorless and transparent propyl trimethoxy silane oligomer;
the polymerization degree of the polymer was 24, and the nuclear magnetic resonance hydrogen spectrum showed absorption peaks at 0.591ppm, 0.920ppm, 1.420ppm and 3.501 ppm.
Preparation example 4
The preparation method of the propyl trimethoxy silane oligomer comprises the following steps:
A1. 1700g of propyl trimethoxy silane, 200g of methanol and 48g of concentrated hydrochloric acid are added into a 3000ml three-neck flask, the mixture is uniformly mixed to obtain a mixed solution A, a reflux condenser, a thermometer and a constant pressure dropping funnel are arranged on the three-neck flask, the mixed solution A is stirred and heated to 50 ℃, 932g of water and 970g of methanol are dripped into the mixed solution A through the constant pressure dropping funnel, and the hydrolysis of propyl trimethoxy silane is carried out;
A2. after the propyl trimethoxy silane is completely hydrolyzed, heating to 130 ℃, carrying out polymerization reaction for 4 hours, then carrying out reduced pressure distillation to collect methanol, and cooling to room temperature to obtain colorless and transparent propyl trimethoxy silane oligomer;
the polymerization degree of the polymer was 30, and the nuclear magnetic resonance hydrogen spectrum showed absorption peaks at 0.592ppm, 0.923ppm, 1.421ppm and 3.499 ppm.
Preparation example 5
The preparation method of the modified nano calcium carbonate comprises the following steps:
1000g of nano calcium carbonate is weighed, soaked in a solution of a silane coupling agent KH570 for 30min, filtered, and the solid is dried at 85 ℃ to obtain the modified nano calcium carbonate.
Preparation example 6
Unlike in preparation example 4, the silane coupling agent in preparation example 5 was triaminosilane YC-618.
Preparation example 7
The preparation method of the modified nano calcium carbonate comprises the following steps:
B1. weighing 1000g of nano calcium carbonate, soaking in a phosphate solution for 30min, filtering, and drying the solid at 85 ℃ to obtain preliminary modified nano calcium carbonate;
B2. and (3) immersing the preliminary modified nano calcium carbonate obtained in the step (B1) in a triamino silane YC-618 solution for 30min, filtering, and drying the solid at 85 ℃ to obtain the modified nano calcium carbonate.
Examples
Examples 1 to 5
The novel double-component silicone structural sealant comprises the following preparation methods:
s1, adding nano calcium carbonate, base gum and dimethyl silicone oil into a reaction kettle according to the raw material ratio in the table 1, stirring for 1.5 hours in a planetary dispersing machine at 50 ℃ under the condition that the vacuumizing vacuum degree is minus 0.09Mpa, and packaging the obtained mixture singly to obtain a component A;
wherein the grain diameter of the nano calcium carbonate is 30-the weight ratio of 60nm to 60-70nm is 1:1, volatile matter is 0.2%; the viscosity of the base adhesive at 25 ℃ is 12000 mpa.s, and the volatile matter is 0.2%;
adding carbon black into a reaction kettle according to the raw material ratio in Table 1, stirring for 10min in a planetary dispersing machine at 110 ℃ under the condition that the vacuumizing degree is minus 0.09Mpa, then adding a first crosslinking agent and a second crosslinking agent, namely propyl trimethoxy silane oligomer, stirring for 30min under the condition that the vacuumizing degree is minus 0.09Mpa, adding fumed silica, stirring for 30min, finally adding a coupling agent and a catalyst, stirring for 60min under the condition that the vacuumizing degree is minus 0.09Mpa, and packaging the obtained mixture singly to obtain a component B;
wherein the propyltrimethoxysilane oligomer was from preparation 1.
TABLE 1 raw materials proportioning table (100 g) in examples 1-5
Example 2 the temperature condition in step S1 is 90℃and the vacuum degree is-0.1 MPa; in the step S2, the temperature condition is 150 ℃ and the vacuum degree is-0.1 Mpa.
Example 6
Unlike example 3, the propyltrimethoxysilane oligomer in example 6 was from preparation 2.
Examples 7 to 11
Unlike example 3, examples 7 to 11 are different in the size grading of the nano calcium carbonate particles, and are shown in Table 2.
Table 2 Table 3 and examples 7-11 nanometer calcium carbonate particle size grading Table (100 g)
| Example 3 | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | |
| 30-60nm | 25.0 | 0 | 25.0 | 34.0 | 37.5 | 16.0 |
| 80-100nm | 0 | 25.0 | 25.0 | 16.0 | 12.5 | 34.0 |
| 60-70nm | 25.0 | 25.0 | 0 | 0 | 0 | 0 |
Examples 12 to 14
Unlike example 9, examples 12-14 replaced nano calcium carbonate with an equivalent amount of modified nano calcium carbonate from preparations 5-7, respectively.
Comparative example
Comparative example 1
Unlike example 1, the methyltrimethoxysilane oligomer of comparative example 1 was derived from preparation example 3.
Comparative example 2
Unlike example 1, the methyltrimethoxysilane oligomer of comparative example 2 was derived from preparation example 4.
Comparative example 3
Unlike example 1, the second crosslinking agent in comparative example 3 was methyl orthosilicate.
Performance test
Detection method
The thermal weight loss, the tensile bond strength at 23 ℃ and the elongation at maximum tensile bond strength, and the tensile bond strength after soaking are detected according to the method and the requirements in the construction silicone structural sealant GB16776-2005, wherein the weight ratio of the component A to the component B is 9: 1.
TABLE 3 Performance test results
As can be seen from the combination of examples 1 to 14 and comparative examples 1 to 3 and the combination of table 3, the tensile strength under the standard conditions in examples 1 to 14, the elongation at maximum tensile strength, and the adhesive strength after soaking are all better than those in comparative examples 1 to 3, which indicates that the adhesive property and the soaking adhesive property of the two-component silicone structural sealant prepared by the present application are better; in addition, the thermal weight loss after the heat aging treatment in examples 1-14 was smaller than that in comparative examples 1-3, indicating that the two-component silicone structural sealants prepared in this application were more excellent in aging resistance.
By combining example 1 with comparative examples 1-3 and combining Table 3, it can be seen that the tensile strength under standard conditions and the elongation at maximum tensile strength, the bond strength after soaking, and the thermal weight loss are all better than those of comparative examples 1-3, which means that the bonding property, the soaking bonding property, and the aging resistance of the structural sealant prepared by using the propyltrimethoxysilane oligomer prepared in this application as the second crosslinking agent are better, while the bonding property, the soaking bonding property, and the aging resistance of the structural sealant prepared by using other crosslinking agents or the polymerization degree of the prepared propyltrimethoxysilane polymer outside the polymerization degree defined in this application are all significantly reduced, probably because the propyltrimethoxysilane oligomer prepared in this application can have better matching effect with other components such as the base adhesive, thereby improving the deep curing effect and improving the bonding property, the soaking bonding property, and the aging resistance.
As can be seen from the combination of examples 3 and examples 7 to 11 and the combination of table 3, the adhesive properties, the water-immersed adhesive properties, and the aging resistance of the structural sealants also changed with the change of the nano calcium carbonate particle size gradation, wherein examples 8 to 10 are more preferable, which indicates that the adhesive properties, the water-immersed adhesive properties, and the aging resistance of the prepared structural sealants are more preferable in the nano calcium carbonate gradation range of the present application.
As can be seen from the combination of examples 9 and examples 12 to 14 and table 3, the adhesive properties, the water-immersed adhesive properties, and the aging resistance of examples 12 to 14 are superior to those of example 9, probably because the dispersion properties of the nano calcium carbonate can be improved after the modification treatment of the nano calcium carbonate, so that the nano calcium carbonate is dispersed more uniformly in the structural sealant system.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (10)
1. The novel double-component silicone structural sealant comprises an A component and a B component, and is characterized in that:
the component A comprises the following raw materials in parts by weight:
30-70 parts of nano calcium carbonate, 20-55 parts of 107 base adhesive and 2-35 parts of dimethyl silicone oil;
the component B comprises the following raw materials in parts by weight:
10-30 parts of carbon black, 3-15 parts of fumed silica, 20-40 parts of dimethyl silicone oil, 10-50 parts of a first cross-linking agent, 10-45 parts of a second cross-linking agent, 10-45 parts of a coupling agent and 0.01-0.14 part of a catalyst;
the first cross-linking agent is selected from any one of methyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, methyl orthosilicate and ethyl orthosilicate;
wherein the second crosslinking agent is propyl trimethoxy silane oligomer, and the structural formula is as follows:
where n=4-6.
2. The novel two-component silicone structural sealant according to claim 1, wherein: the component A comprises the following raw materials in parts by weight:
40-60 parts of nano calcium carbonate, 30-50 parts of base adhesive and 5-30 parts of simethicone;
the component B comprises the following raw materials in parts by weight:
15-20 parts of carbon black, 5-10 parts of fumed silica, 25-30 parts of dimethyl silicone oil, 15-40 parts of a first cross-linking agent, 15-40 parts of a second cross-linking agent, 15-40 parts of a coupling agent and 0.01-0.1 part of a catalyst.
3. The novel two-component silicone structural sealant according to claim 1, wherein: the preparation method of the propyl trimethoxy silane oligomer comprises the following steps:
A1. uniformly mixing 1600-1700 parts of propyl trimethoxy silane, 200-230 parts of methanol and 18-48 parts of concentrated hydrochloric acid to obtain a mixed solution A, stirring the mixed solution A, heating to 40-50 ℃, adding 88-183 parts of water and 212-400 parts of methanol into the mixed solution A in a dropwise manner, and hydrolyzing the propyl trimethoxy silane;
A2. after the propyl trimethoxy silane is completely hydrolyzed, heating to 110-130 ℃, carrying out polymerization reaction for 2-4h, then carrying out reduced pressure distillation to collect methanol, and cooling to room temperature to obtain the colorless transparent propyl trimethoxy silane oligomer.
4. The novel two-component silicone structural sealant according to claim 1, wherein: the grain diameter of the nano calcium carbonate is 30-100nm, and the volatile matters are less than or equal to 0.5%.
5. The novel two-component silicone structural sealant according to claim 4, wherein: the weight ratio of the grain diameter of the nano calcium carbonate to 80-100nm is (1-3): 1.
6. the novel two-component silicone structural sealant according to claim 1, wherein:
the nano calcium carbonate is modified, and the treatment method comprises the following steps:
and (3) carrying out surface treatment on the nano calcium carbonate by using a silane coupling agent.
7. The novel two-component silicone structural sealant according to claim 6, wherein: before the silane coupling agent is modified, the nano calcium carbonate is soaked in a phosphate solution for surface treatment, and then is filtered and dried.
8. The novel two-component silicone structural sealant according to claim 6, wherein: the silane coupling agent is triamino silane.
9. The novel two-component silicone structural sealant according to claim 1, wherein: the viscosity of the base adhesive at 25 ℃ is 500-80000 mPa.s, and the volatile matters are less than or equal to 0.5%.
10. A method for preparing the novel two-component silicone structural sealant according to any one of claims 1 to 9, comprising the following steps:
uniformly mixing nano calcium carbonate, base gum and dimethyl silicone oil according to parts by weight at 50-90 ℃ under the condition of vacuum degree (-0.09 MPa) - (-0.1 MPa), and independently packaging to obtain a component A;
uniformly stirring carbon black and simethicone at 110-150 ℃ under the condition of vacuum degree (-0.09 MPa) - (-0.1 MPa), then adding a first cross-linking agent and a second cross-linking agent, stirring and mixing under the condition of vacuum degree (-0.09 MPa) - (-0.1 MPa), then adding fumed silica, uniformly mixing, finally adding a coupling agent and a catalyst, uniformly mixing under the condition of vacuum degree (-0.09 MPa) - (-0.1 MPa), and packaging independently to obtain the component B.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111528381.7A CN114214025B (en) | 2021-12-14 | 2021-12-14 | Novel double-component silicone structural sealant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111528381.7A CN114214025B (en) | 2021-12-14 | 2021-12-14 | Novel double-component silicone structural sealant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114214025A CN114214025A (en) | 2022-03-22 |
| CN114214025B true CN114214025B (en) | 2023-04-28 |
Family
ID=80701955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111528381.7A Active CN114214025B (en) | 2021-12-14 | 2021-12-14 | Novel double-component silicone structural sealant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114214025B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN116041963A (en) * | 2023-03-09 | 2023-05-02 | 成都佳驰电子科技股份有限公司 | Waterproof wave-absorbing silica gel film with high tearing strength and low hardness and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139464A (en) * | 2006-06-05 | 2008-03-12 | 信越化学工业株式会社 | Room temperature-curable organopolysiloxane composition |
| CN105647462A (en) * | 2016-02-26 | 2016-06-08 | 广州市白云化工实业有限公司 | Condensed type two-component silicone sealant and preparation method thereof |
| CN108822790A (en) * | 2018-06-26 | 2018-11-16 | 广州集泰化工股份有限公司 | Low modulus silicone weatherproof sealant of a kind of single-component dealcoholization-type and preparation method thereof |
| CN111303829A (en) * | 2020-04-14 | 2020-06-19 | 广州广通新材料有限公司 | Low-VOC (volatile organic compound) organosilicon sealant and preparation method thereof |
| CN112552868A (en) * | 2020-12-14 | 2021-03-26 | 广州集泰化工股份有限公司 | Ultrahigh-transparency silicone structural sealant and preparation method thereof |
| CN113087737A (en) * | 2021-04-16 | 2021-07-09 | 湖北江瀚新材料股份有限公司 | Preparation method of isooctyltriethoxysilane oligomer |
| CN113684003A (en) * | 2021-09-03 | 2021-11-23 | 广州市白云化工实业有限公司 | Bi-component room temperature vulcanized silicone rubber composition |
-
2021
- 2021-12-14 CN CN202111528381.7A patent/CN114214025B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139464A (en) * | 2006-06-05 | 2008-03-12 | 信越化学工业株式会社 | Room temperature-curable organopolysiloxane composition |
| CN105647462A (en) * | 2016-02-26 | 2016-06-08 | 广州市白云化工实业有限公司 | Condensed type two-component silicone sealant and preparation method thereof |
| CN108822790A (en) * | 2018-06-26 | 2018-11-16 | 广州集泰化工股份有限公司 | Low modulus silicone weatherproof sealant of a kind of single-component dealcoholization-type and preparation method thereof |
| CN111303829A (en) * | 2020-04-14 | 2020-06-19 | 广州广通新材料有限公司 | Low-VOC (volatile organic compound) organosilicon sealant and preparation method thereof |
| CN112552868A (en) * | 2020-12-14 | 2021-03-26 | 广州集泰化工股份有限公司 | Ultrahigh-transparency silicone structural sealant and preparation method thereof |
| CN113087737A (en) * | 2021-04-16 | 2021-07-09 | 湖北江瀚新材料股份有限公司 | Preparation method of isooctyltriethoxysilane oligomer |
| CN113684003A (en) * | 2021-09-03 | 2021-11-23 | 广州市白云化工实业有限公司 | Bi-component room temperature vulcanized silicone rubber composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114214025A (en) | 2022-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114214025B (en) | Novel double-component silicone structural sealant and preparation method thereof | |
| CN111154453B (en) | Heat-resistant single-component addition type organic silicon adhesive and preparation method thereof | |
| CN102093837B (en) | One-component high temperature-resistant gasket-free sealant and preparation method thereof | |
| CN110577747B (en) | Room temperature vulcanized fluorosilicone rubber and preparation method thereof | |
| CN102093721B (en) | Single-component alcohol/ketoxime-removed room temperature vulcanizing silicone rubber and preparation method thereof | |
| CN109135660A (en) | A kind of dealcoholized type bi-component sealant and preparation method thereof | |
| CN111394052B (en) | Dealcoholized condensed type double-component room temperature vulcanized silicone rubber and preparation method thereof | |
| CN106810573A (en) | One kind is combined silane coupled adhesion promoters and preparation method thereof | |
| CN110387128B (en) | Self-adhesive single-component addition type silicone rubber and preparation method thereof | |
| CN112239645A (en) | Silicone adhesive with antibacterial and mildewproof effects and preparation method thereof | |
| CN112143451A (en) | Single-component dealcoholized room temperature vulcanized silicone sealant and preparation method thereof | |
| CN110205084B (en) | Quick-curing type organosilicon sealant | |
| CN115627084A (en) | Surface treatment method of glass beads and silicone rubber | |
| CN112210341B (en) | Double-vulcanization system building sealant and preparation method thereof | |
| CN112094434B (en) | Preparation method and application of silicon-alkoxy-containing borosilicate siloxane modified white carbon black | |
| CN116589973B (en) | High-temperature-resistant COB packaging adhesive and preparation method thereof | |
| CN110951443B (en) | Single-component organic silica gel for bonding multiple materials and preparation method thereof | |
| CN110257002B (en) | Two-component silicone sealant for projection lamp | |
| CN112920765B (en) | Acetone-removing type organic silicon sealant and preparation method thereof | |
| CN111269578B (en) | High-strength room temperature vulcanized silicone rubber with stable storage and preparation method thereof | |
| CN112143258B (en) | Preparation method and application of borosilicate siloxane modified white carbon black containing silicon-chlorine bonds | |
| CN110776871B (en) | Room-temperature dealcoholized silicone adhesive and preparation method thereof | |
| CN113789057A (en) | One-pack type modified liquid silicone rubber, composition for forming same, and application thereof | |
| CN112239643A (en) | Neutral transparent silicone adhesive and preparation method thereof | |
| CN114133912B (en) | Bi-component silicone structural adhesive with strong initial adhesion |
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 |