CN115404041A - Self-leveling long-acting mildew-proof silicone adhesive and preparation method thereof - Google Patents
Self-leveling long-acting mildew-proof silicone adhesive and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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Abstract
The application discloses a self-leveling long-acting mildew-proof silicone adhesive and a preparation method thereof, wherein the silicone adhesive comprises the following raw materials in parts by weight: 107-base glue: 100 parts of (A); modified fumed silica: 5-15 parts; plasticizer: 10-35 parts; a crosslinking agent: 2-9 parts; coupling agent: 0.3-2 parts; mildew preventive: 0.1 to 1.5 portions; organotin catalyst: 0.01 to 0.05 portion; the modified fumed silica is obtained by mixing and reacting fumed silica, methoxy silicone oil and a pyrophosphoric acid type monoalkoxy titanate coupling agent in a mass ratio of 100 (250-400) to 0.1-3. The silicone adhesive prepared by the method has excellent fixed-extension cohesiveness, self-leveling property, waterproofness and long-acting mildew-proof effect.
Description
Technical Field
The application relates to the field of silicone sealant, in particular to a self-leveling long-acting mildew-proof silicone adhesive and a preparation method thereof.
Background
The silicone sealant is an organosilicon adhesive prepared by taking hydroxyl-terminated polysiloxane as a base adhesive and adding a plasticizer, a coupling agent, a crosslinking agent and a catalyst. The cured product forms a reticular Si-O-Si framework structure, has excellent waterproof performance and weather resistance, and is widely applied to the field of waterproof sealing.
However, in some waterproof sealing construction of irregular caulking seams, the existing silicone sealant has poor fixed-stretching bonding performance due to poor tensile strength and elongation, and is easy to generate cohesive failure during construction, so that the waterproof sealing performance is not guaranteed.
Disclosure of Invention
In order to improve the tensile strength and the elongation of the silicone sealant and ensure the waterproof sealing effect of the silicone adhesive, the application provides the self-leveling long-acting mildew-proof silicone adhesive and the preparation method thereof.
In a first aspect, the application provides a self-leveling long-acting mildew-proof silicone adhesive, which comprises the following raw materials in parts by weight:
107 base glue: 100 parts of (A);
modified fumed silica: 5-15 parts;
plasticizer: 10-35 parts;
a crosslinking agent: 2-9 parts;
coupling agent: 0.3-2 parts;
mildew preventive: 0.1 to 1.5 portions;
organotin catalyst: 0.01 to 0.05 portion;
the modified fumed silica is obtained by mixing and reacting fumed silica, methoxy silicone oil and a pyrophosphoric acid type monoalkoxy titanate coupling agent in a mass ratio of 100 (250-400) to 0.1-3.
The fumed silica has excellent reinforcing effect, can effectively improve the strength and elasticity of a silicone sealant system, improves the fixed-extension cohesiveness of silicone adhesive, and is favorable for waterproof sealing of irregular caulked seams, especially wide caulked seams.
It should be noted that the fumed silica surface contains a large amount of silanol groups, so that the fumed silica is easy to adsorb each other and form a network structure in the silicone adhesive through hydrogen bonding, the viscosity of the adhesive is greatly increased, and the fluidity of the adhesive is reduced. Therefore, the surface modification is carried out on the fumed silica by adopting the methoxy silicone oil and the pyrophosphoric acid type monoalkoxy titanate coupling agent, so that the polarity of the fumed silica is effectively reduced, and the tackifying effect of the fumed silica is inhibited, so that the self-leveling property of the silicone adhesive is remarkably improved, and the penetrating and sealing effect of the silicone adhesive on caulking seams is guaranteed.
Specifically, the methoxy silicone oil can be hydrolyzed to generate a silanol group, and then reacts with the silanol group on the surface of the fumed silica to form an ether bond or through hydrogen bonding, so that the methoxy silicone oil is adsorbed on the surface of the fumed silica to play a steric hindrance role while consuming the silanol group, and the formation of a tackifying network structure is inhibited. And the pyrophosphoric acid type monoalkoxy titanate coupling agent can also be bonded with the fumed silica through the reaction of alkoxy and the fumed silica, and the connection between the pyrophosphoric acid type monoalkoxy titanate coupling agent and the 107-based adhesive is improved through the coupling effect. In addition, the pyrophosphate group of the pyrophosphate type monoalkoxy titanate coupling agent can also absorb free water in the air, inhibit the water absorption and tackifying effects of the fumed silica, and further ensure the self-leveling property, permeability and waterproof sealing property of the silicone adhesive.
Typically, but not limitatively, the 107-based gum is a hydroxyl terminated polysiloxane having a viscosity of 20000 to 80000mpa · s; the plasticizer is methyl silicone oil with the viscosity of 50-1000mpa & s; activity of methoxy Silicone oilThe content of radicals corresponds to 8.0% of the content of hydroxyl radicals; the surface area of the fumed silica is 130-300m 2 The preferred type is Cabot LM-150.
Preferably, the coupling agent at least comprises an epoxy modified silane coupling agent, and the epoxy modified silane coupling agent is obtained by mixing and reacting an aminosilane coupling agent, isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and epoxy resin in a solvent according to the mass ratio of 1 (2-3) to (0.5-1).
By adopting the technical scheme, the oligomeric product is obtained by the mutual reaction or polycondensation of an aminosilane coupling agent, isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and epoxy resin, si-OMe contained in a molecular chain can be chemically bonded with-OH on the surface of a building material, and a non-polar group Si-Pr on a side chain can reduce the surface tension of the building material and improve the hydrophobic property. And amino and epoxy in the molecular chain have a crosslinking effect, so that 107-base glue and gas-like silicon dioxide can be crosslinked to form a more compact body structure, and the waterproofness and the water-soaking definite-elongation cohesiveness of the silicone sealant are effectively improved.
Preferably, the epoxy modified resin is prepared by the following method:
step 1: dissolving an aminosilane coupling agent, isopropyl tri (dioctyl pyrophosphate acyloxy) titanate and epoxy resin in a mass ratio of (2-3) to (0.5-1) in an alcohol solvent, heating to 80-120 ℃ for reaction to obtain an intermediate product;
step 2: and (3) carrying out reduced pressure distillation, recovering the alcohol solvent in the intermediate product, continuously heating to 140-150 ℃, continuously reacting, and cooling after the reaction is finished to obtain the epoxy modified silane coupling agent.
By adopting the technical scheme, the modified silane coupling agent with the epoxy group and the amino group is prepared, the coupling effect is achieved, the mutual crosslinking of all the components can be promoted, the crosslinking density and compactness of the silicone adhesive are improved, and the waterproofness and the water-soaked stretching cohesiveness of the silicone adhesive are further improved.
Preferably, the coupling agent also comprises an auxiliary silane coupling agent, and the mass ratio of the epoxy modified silane coupling agent to the auxiliary silane coupling agent is (1-2) to (1-2); the auxiliary silane coupling agent is one or a combination of an epoxy silane coupling agent and an amino silane coupling agent.
By adopting the auxiliary silane coupling agent, the curing speed attenuation of the silicone sealant can be prevented, the storage stability of the silicone sealant is improved, and the surface drying speed of the silicone sealant is guaranteed. The mechanism may be that the silane coupling agent is modified with epoxy to decrease the stability, which leads to the deterioration of the curing speed of the silicone adhesive with the increase of the storage time and the increase of the tack-free time. By adopting the conventional aminosilane coupling agent or epoxy silane coupling agent for compounding, the storage stability of the modified epoxy silane coupling agent can be obviously improved, the surface drying time is stabilized, and the cost is effectively reduced.
Preferably, the auxiliary silane coupling agent is one of gamma-aminopropyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, gamma- (2, 3-glycidoxy) propyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, or a combination thereof.
By adopting the amino silane coupling agent or the epoxy silane coupling agent, the storage stability of the silicone adhesive is obviously improved, and the attenuation trend of the curing speed of the silicone adhesive is inhibited.
Preferably, the crosslinking agent is one or more of methyl tributyl ketoximino silane, vinyl tributyrinoxime silane, tetrabutynin ketoximino silane, phenyl tributyrinoxime silane, methyl vinyl dibutyrinoxime silane, dimethyl dibutyrinoxime silane, methyl vinyl bis (methyl isobutyl ketoximo) silane and methyl vinyl diacetoneaximo silane.
By adopting the cross-linking agent, the cross-linking and curing of the silicone adhesive are effectively realized.
Preferably, the mildew preventive adopts a Longsha ZPT environment-friendly powder mildew preventive and a Longsha mildew preventive Densil DN in a mass ratio of 1.
By adopting the technical scheme, the two mildewcides are matched together, so that the long-acting antibacterial and mildewproof effect of the silicone sealant can be effectively realized.
Preferably, the raw material of the long-acting mildew-proof silicone adhesive further comprises 0.5-2 parts of amino modified graphene oxide.
By adopting the technical scheme, the graphene oxide has excellent antibacterial and mildewproof effects, and the amino group is grafted and modified on the surface of the graphene oxide, so that the chemical bonding between the graphene oxide and the epoxy modified silane coupling agent can be promoted, the connection fastness of the graphene oxide is improved, and the long-acting mildewproof effect of the silicone adhesive is enhanced; on the other hand, the dispersion of the graphene oxide can be promoted, and the mildew-proof effect can be fully exerted.
Preferably, the amino-modified graphene oxide is prepared by the following method:
adding graphene oxide into water, uniformly dispersing, adjusting the pH value to 4-5, adding carbodiimide hydrochloride and N-hydroxysuccinimide, and uniformly stirring; and then adding a diamine compound, carrying out amidation reaction under a heating condition, and filtering, washing and drying after the reaction is finished to obtain the amino modified graphene oxide.
By adopting the technical scheme, under the activation of carbodiimide hydrochloride and N-hydroxysuccinimide, carboxyl in graphene oxide can generate amidation reaction with amino of diamine compounds, so that the amino is introduced into the graphene oxide, and the reaction of the graphene oxide and a coupling agent containing epoxy groups is promoted.
Preferably, the particle size of the graphene oxide is 10 to 300nm, and more preferably 50 to 150nm.
In a second aspect, the present application provides a method for preparing a self-leveling long-acting mildew-proof silicone adhesive, which comprises the following steps:
under the vacuum condition, mixing and stirring the 107-base rubber and the plasticizer uniformly, then adding the cross-linking agent and the modified fumed silica in sequence and stirring uniformly; and finally, adding the epoxy modified silane coupling agent, the auxiliary silane coupling agent and the catalyst, and uniformly stirring to obtain the epoxy modified silane coupling agent.
By adopting the technical scheme, the silicone sealant with excellent tensile strength, elongation and definite-elongation adhesion is prepared, and the waterproof sealing performance of the silicone sealant to irregular caulked joints is effectively improved.
In summary, the present application has the following beneficial effects:
1. according to the application, the methoxy silicone oil and the pyrophosphoric acid type monoalkoxy titanate coupling agent are mixed and modified to prepare the fumed silica, so that the tensile strength, the elongation and the fixed-elongation cohesiveness of the silicone adhesive are effectively improved on the premise of ensuring the self-leveling property of the silicone adhesive.
2. According to the preparation method, the epoxy modified silane coupling agent obtained by mixing and reacting the aminosilane coupling agent, the isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and the epoxy resin is adopted, so that the water-soaking stretching cohesiveness of the silicone adhesive can be effectively improved.
3. According to the silicone adhesive, the amino silane coupling agent and/or the epoxy silane coupling agent are/is matched with the epoxy modified silane coupling agent, so that the storage stability of the silicone adhesive can be effectively improved, and the attenuation of the curing speed of the silicone adhesive is inhibited.
4. The long-acting antibacterial mildew-proof effect of the silicone adhesive can be effectively enhanced by adopting the amino modified graphene oxide.
Detailed Description
Preparation example of modified fumed silica
Preparation example 1-1, a modified fumed silica, the preparation method is as follows:
1000g of carbopol LM-150 fumed silica and 3000g of mpa.s methoxy silicone oil (active group content: 8.0% of hydroxyl group content) are added into a reaction kettle; heating to 60 deg.C, and adding dropwise 20g of pyrophosphoric acid type monoalkoxy titanate coupling agent. And after the addition is finished, continuously stirring for 60 minutes to obtain the modified fumed silica.
Preparation examples 1 to 2, a modified fumed silica, the preparation method is as follows:
1000g of carbopol LM-150 fumed silica and 2500g of mpa.s methoxy silicone oil (active group content: 8.0% of hydroxyl group content) are added into a reaction kettle; heating to 60 deg.C, and adding dropwise 30g of pyrophosphoric acid type monoalkoxy titanate coupling agent. And after the addition is finished, continuously stirring for 120 minutes to obtain the modified fumed silica.
Preparation examples 1 to 3, a modified fumed silica, the preparation method was as follows:
1000g portions of Cabot LM-150 fumed silica and 4000g portions of mpa.s methoxy silicone oil (active group content: 8.0 percent of hydroxyl group content) are added into a reaction kettle; heating to 60 deg.C, and adding 1g pyrophosphoric acid type monoalkoxy titanate coupling agent dropwise. And after the addition is finished, continuously stirring for 60 minutes to obtain the modified fumed silica.
Preparation example of epoxy-modified silane coupling agent
Preparation example 2-1, an epoxy-modified silane coupling agent, was prepared as follows:
step 1: 500g of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, 1000g of isopropyltris (dioctylphosphato) titanate, 285g of E51 epoxy resin and 450g of methanol were added to a three-necked flask, and the mixture was stirred and uniformly dispersed. And (3) installing a reflux condenser tube, a thermometer and a constant-pressure dropping funnel on the three-neck flask, heating to 110 ℃ under stirring, and carrying out reflux reaction for 3 hours to obtain an intermediate product.
Step 2: and (3) carrying out reduced pressure distillation, recovering methanol in the intermediate product, continuously heating to 140 ℃, continuously reacting for 2 hours, and cooling to room temperature after the reaction is finished to obtain the epoxy modified silane coupling agent.
Preparation example 2-2, an epoxy-modified silane coupling agent, was prepared as follows:
step 1: 500g of gamma-aminopropyltriethoxysilane, 1500g of isopropyltris (dioctylphosphato) titanate, 500g of E51 epoxy resin and 800g of ethanol are added into a three-neck flask, a reflux condenser tube, a thermometer and a constant pressure dropping funnel are arranged on the three-neck flask, the temperature is raised to 120 ℃ under stirring, and reflux reaction is carried out for 3 hours, thus obtaining an intermediate product.
Step 2: and (3) carrying out reduced pressure distillation, recovering ethanol in the intermediate product, continuously heating to 140 ℃, continuously reacting for 3 hours, and cooling to room temperature after the reaction is finished to obtain the epoxy modified silane coupling agent.
Preparation examples 2 to 3, an epoxy-modified silane coupling agent, was prepared as follows:
step 1: 500g of N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, 1000g of isopropyltris (dioctylphosphato) titanate, 250g of E51 epoxy resin and 800g of ethanol were added into a three-necked flask, a reflux condenser, a thermometer and a dropping funnel with constant pressure were installed on the three-necked flask, the temperature was raised to 80 ℃ with stirring, and a reflux reaction was carried out for 2 hours to obtain an intermediate product.
Step 2: and (3) carrying out reduced pressure distillation, recovering ethanol in the intermediate product, continuously heating to 150 ℃, continuously reacting for 2 hours, and cooling to room temperature after the reaction is finished to obtain the epoxy modified silane coupling agent.
Preparation example 2-4, an epoxy-modified silane coupling agent, was different from preparation example 2-1 in that an equivalent amount of an aminosilane coupling agent was used instead of an epoxy resin.
Preparation example 2-5, an epoxy-modified silane coupling agent, was different from preparation example 2-1 in that an equivalent amount of an aminosilane coupling agent was used instead of isopropyltris (dioctylpyrophosphate) titanate.
Preparation examples 2-6, an epoxy-modified silane coupling agent, differs from preparation example 2-1 in that an equivalent amount of epoxy resin is used instead of the aminosilane coupling agent.
Preparation example of amino group-modified graphene oxide
Preparation example 3-1, an amino-modified graphene oxide was prepared as follows:
adding 100g of graphene oxide and 5L of water into a reaction kettle, uniformly stirring and dispersing, adding hydrochloric acid to adjust the pH value to 4, adding 400g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 200g of N-hydroxysuccinimide, uniformly stirring, heating the solution to 65 ℃, adding 900g of hexamethylenediamine, carrying out amidation reaction under a heating condition, and filtering, washing and drying after the reaction is finished to obtain the amino modified graphene oxide.
Preparation example 3-2, an amino-modified graphene oxide was prepared as follows:
adding 100g of graphene oxide and 7.5L of water into a reaction kettle, stirring and uniformly dispersing, adding hydrochloric acid to adjust the pH value to 5, adding 600g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 300g of N-hydroxysuccinimide, uniformly stirring, heating the solution to 65 ℃, adding 1000g of hexamethylenediamine, carrying out amidation reaction under a heating condition, and filtering, washing and drying after the reaction is finished to obtain the amino modified graphene oxide.
Examples
Example 1, a self-leveling long-acting mold-resistant silicone adhesive was prepared as follows:
adding 100 kg of 107 base rubbers and 15 kg of methyl silicone oil into a planetary dispersion machine, and stirring at high speed for 10 minutes under a vacuum condition (the vacuum degree is-0.09 MPa to-0.1 MPa); adding 5 kg of vinyl tributyrinoxime silane crosslinking agent, vacuumizing (the vacuum degree is-0.09 MPa to-0.1 MPa), and stirring for 20 minutes; and then, adding 10 kg of the modified fumed silica prepared in preparation examples 1-1 and 1 kg of the amino-modified oxidized graphene prepared in preparation examples 3-1, vacuumizing (the vacuum degree is-0.09 Mpa to-0.1 Mpa), stirring for 20 minutes, finally, adding 0.6 kg of an mildew inhibitor (the weight ratio of the mildew inhibitor to the environmental-friendly powdered dragon sand ZPT powder mildew inhibitor and the mildew inhibitor Densil DN is 1), 0.5 kg of the epoxy modified silane coupling agent prepared in preparation examples 2-1, 0.5 kg of an auxiliary silane coupling agent (the weight ratio is 1.
Example 2, a self-leveling long-acting mold-resistant silicone adhesive was prepared as follows:
adding 100 kg of 107 base rubbers and 10 kg of methyl silicone oil into a planetary dispersion machine, and stirring at high speed for 10 minutes under a vacuum condition (the vacuum degree is-0.09 MPa to-0.1 MPa); adding 2 kg of methyl tributyrinoxime silane crosslinking agent, vacuumizing (the vacuum degree is-0.09 MPa to-0.1 MPa), and stirring for 20 minutes; and adding 35 kg of the modified fumed silica prepared in preparation examples 1-2 and 2 kg of the amino-modified graphene oxide prepared in preparation examples 3-2, vacuumizing (the vacuum degree is-0.09 Mpa to-0.1 Mpa), stirring for 20 minutes, finally adding 0.1 kg of mildew preventive (the weight ratio of the mildew preventive to the environmental-friendly powdery mildew preventive for the dragon sand ZPT and the dragon sand mildew preventive Densil DN is 1) and 1 kg of the epoxy-modified silane coupling agent prepared in preparation examples 2-2, 0.1 kg of auxiliary silane coupling agent (N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane) and 0.01 kg of dioctyltindilaurate, and stirring for 10 minutes.
Example 3, a self-leveling long-acting mold-resistant silicone adhesive was prepared as follows:
adding 107 kg of base rubber and 35 kg of methyl silicone oil into a planetary dispersion machine, and stirring at a high speed for 10 minutes under a vacuum condition (the vacuum degree is-0.09 MPa to-0.1 MPa); adding 9 kg of methyl tributyrinoxime silane crosslinking agent, vacuumizing (the vacuum degree is-0.09 MPa to-0.1 MPa), and stirring for 20 minutes; and adding 5 kg of the modified fumed silica prepared in preparation examples 1-3 and 0.5 kg of the amino-modified graphene oxide prepared in preparation examples 3-1, vacuumizing (the vacuum degree is-0.09 Mpa to-0.1 Mpa), stirring for 20 minutes, finally adding 1.5 kg of mildew preventive (the environment-friendly powdery mildew preventive for the jacket ZPT and the jacket mildew preventive Densil with the mass ratio of 1: 1), 0.1 kg of epoxy-modified silane coupling agent prepared in preparation examples 2-3, 1 kg of auxiliary silane coupling agent (gamma-urethane (2, 3-epoxypropoxy) propyltriethoxysilane) and 0.05 kg of dioctyltin dilaurate, and stirring for 10 minutes.
Example 4, a self-leveling, long-lasting mildewproof silicone adhesive, was different from example 1 in that the epoxy-modified silane coupling agent prepared in preparation example 2-1 was replaced with the epoxy-modified silane coupling agent prepared in preparation example 2-4 in an equal amount.
Example 5 a self-leveling long-lasting mildewproof silicone adhesive was distinguished from example 1 in that the epoxy-modified silane coupling agent prepared in preparation example 2-1 was replaced with the epoxy-modified silane coupling agent prepared in preparation example 2-5 in the same amount.
Example 6 a self-leveling long-lasting mildewproof silicone adhesive is different from example 1 in that the epoxy-modified silane coupling agent prepared in preparation example 2-1 is replaced by an equal amount of the epoxy-modified silane coupling agent prepared in preparation example 2-6.
Example 7, a self-leveling long-lasting mildewproof silicone adhesive, was different from example 1 in that the epoxy-modified silane coupling agent prepared in preparation example 2-1 was used in an equal amount in place of the auxiliary silane coupling agent.
Example 8, a self-leveling long-lasting mildewproof silicone adhesive, differs from example 1 in that an equal amount of auxiliary silane coupling agent (gamma-aminopropyltriethoxysilane and gamma- (2, 3-glycidoxy) in a mass ratio of 1.
Example 9, a self-leveling long-acting mildew-resistant silicone adhesive is different from example 1 in that an equivalent amount of Densil DN, a dragon sand mildew preventive, is used instead of amino-modified graphene oxide.
Example 10, a self-leveling long-acting mold-proof silicone adhesive, differs from example 1 in that an equal amount of modified graphene oxide is used instead of amino-modified graphene oxide.
Comparative example
Comparative example 1, a self-leveling long-acting mildew-proof silicone adhesive, which is different from example 1 in that in the preparation process of the modified fumed silica, equal amount of methoxy silicone oil is adopted to replace a pyrophosphoric acid type monoalkoxy titanate coupling agent.
Comparative example 2, a self-leveling long-acting mildew-proof silicone adhesive, which is different from example 1 in that the same amount of unmodified fumed silica is adopted to replace the modified fumed silica.
Comparative example 3, a self-leveling long-acting mildew-proof silicone adhesive, which is different from example 1 in that the modified fumed silica is replaced by the equivalent amount of the pyrophosphoric acid type monoalkoxy titanate coupling agent and the methoxy silicone oil modified nano calcium carbonate.
Performance test
The properties of the silicone adhesive were tested according to the JC/T885-2016, and the results are shown in Table 1.
TABLE 1 test results of Silicone adhesive Properties
The self-leveling long-acting mildew-proof silicone adhesive is applied to the field of waterproof sealing of irregular caulking joints, and the surface drying time needs to be controlled within 20 minutes so as to adapt to the construction environment.
And (4) analyzing results:
(1) By combining examples 1 to 10 and comparative examples 1 to 3 with table 1, it can be seen that the application can significantly improve the tensile strength and the elongation of the silicone adhesive by using fumed silica modified by methoxy silicone oil and pyrophosphoric acid type monoalkoxy titanate coupling agent, thereby ensuring the fixed-elongation cohesive property (including the fixed-elongation cohesive property, the fixed-elongation cohesive property after water inflow and the cohesive property after 25-grade cold-drawing hot-pressing).
(2) By combining example 1 and examples 4 to 6 with table 1, it can be seen that the epoxy modified silane coupling agent prepared by using an aminosilane coupling agent, isopropyl tris (dioctyl pyrophosphato) titanate and an epoxy resin can significantly improve the tensile adhesion of the silicone adhesive after soaking. The reason for this is probably that the epoxy modified silane coupling agent containing epoxy group and amino group can be obtained after the three are heated and reacted, so that the mutual crosslinking of all the components can be promoted, the crosslinking density and compactness of the cured silicone adhesive can be finally improved, and the waterproofness and the water-soaked definite-elongation cohesiveness of the cured silicone adhesive can be further improved.
(3) By combining the embodiment 1 and the embodiments 7 to 8 and combining the table 1, the waterproof property and the water-soaked stretching and bonding property of the silicone adhesive can be improved on the premise of ensuring the storage stability of the silicone adhesive by adopting the epoxy modified silane coupling agent and the auxiliary silane coupling agent to be matched together. The reason for this is probably that the stability of the silane coupling agent subjected to modification reaction such as the epoxy-modified silane coupling agent is poor, and the curing rate of the silicone adhesive is reduced with the increase of storage time, and the surface drying time is greatly increased, which is not favorable for construction operation. Therefore, the stability of the raw materials of the coupling agent can be effectively improved by adopting the conventional epoxy silane coupling agent or amino silane coupling agent, and the excellent surface drying time and the water-soaking definite-elongation binding property of the silicone adhesive are ensured.
(4) By combining the embodiment 1 and the embodiments 9 to 10 and combining the table 1, it can be seen that the long-acting mildew-proof performance of the silicone adhesive can be effectively improved by further adopting the amino modified graphene oxide on the basis of the mildew preventive. The principle of the method may be that graphene oxide with the bacteriostatic action can react and bond with the epoxy modified silane coupling agent after being modified by amino, so that the dispersion of the graphene oxide is promoted, the adhesion firmness of the graphene oxide is improved, and the long-acting mildew-proof effect of the graphene oxide is realized.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The self-leveling long-acting mildew-proof silicone adhesive is characterized by comprising the following raw materials in parts by weight:
107 base glue: 100 parts of a binder;
modified fumed silica: 5-15 parts;
plasticizer: 10-35 parts;
a crosslinking agent: 2-9 parts of a solvent;
coupling agent: 0.3-2 parts;
mildew preventive: 0.1 to 1.5 portions;
organotin catalyst: 0.01 to 0.05 portion;
the modified fumed silica is obtained by mixing and reacting fumed silica, methoxy silicone oil and a pyrophosphoric acid type monoalkoxy titanate coupling agent in a mass ratio of 100 (250-400) to 0.1-3.
2. The self-leveling long-acting mildew-proof silicone adhesive as claimed in claim 1, wherein the coupling agent at least comprises an epoxy modified silane coupling agent, and the epoxy modified silane coupling agent is obtained by mixing and reacting an aminosilane coupling agent, isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and epoxy resin in a solvent according to a mass ratio of 1 (2-3) to (0.5-1).
3. The self-leveling long-acting mildew-proof silicone adhesive according to claim 2, wherein the epoxy modified resin is prepared by the following method:
step 1: dissolving an aminosilane coupling agent, isopropyl tri (dioctyl pyrophosphate acyloxy) titanate and epoxy resin in a mass ratio of (2-3) to (0.5-1) in an alcohol solvent, heating to 80-120 ℃ for reaction to obtain an intermediate product;
step 2: and (3) carrying out reduced pressure distillation, recovering the alcohol solvent in the intermediate product, continuously heating to 140-150 ℃, continuously reacting, and cooling after the reaction is finished to obtain the epoxy modified silane coupling agent.
4. The self-leveling long-acting mildew-proof silicone adhesive according to claim 3, wherein the coupling agent further comprises an auxiliary silane coupling agent, and the mass ratio of the epoxy modified silane coupling agent to the auxiliary silane coupling agent is (1-2) to (1-2); the auxiliary silane coupling agent is one or a combination of an epoxy silane coupling agent and an amino silane coupling agent.
5. The self-leveling long-acting mildew-proof silicone adhesive according to claim 2, wherein the auxiliary silane coupling agent is one of gamma-aminopropyltriethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, gamma- (2, 3-glycidoxy) propyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, or a combination thereof.
6. The self-leveling long-acting mildew-proof silicone adhesive according to claim 1, wherein the cross-linking agent is one or more of methyl tributyrinoxime silane, vinyl tributyrinoxime silane, tetrabutyralminoximino silane, phenyltributyrinoxime silane, methyl vinyl dibutyloximino silane, dimethyl dibutyloximino silane, methyl vinyl bis (methyl isobutyl ketoximino) silane and methyl vinyl diacetone ketoximino silane.
7. The self-leveling long-acting mildew-proof silicone adhesive according to claim 1, wherein the mildew-proof agent is a Longsha ZPT environment-friendly powder mildew-proof agent and a Longsha mildew-proof agent Densil DN in a mass ratio of 1.
8. The self-leveling long-acting mildew-proof silicone adhesive according to claim 2, wherein the raw materials of the long-acting mildew-proof silicone adhesive further comprise 0.5-2 parts of amino-modified graphene oxide.
9. The self-leveling long-acting mildew-proof silicone adhesive according to claim 8, wherein the amino-modified graphene oxide is prepared by the following method:
adding graphene oxide into water, uniformly dispersing, adjusting the pH value to 4-5, adding carbodiimide hydrochloride and N-hydroxysuccinimide, and uniformly stirring; and then adding a diamine compound, carrying out amidation reaction under a heating condition, and filtering, washing and drying after the reaction is finished to obtain the amino modified graphene oxide.
10. The preparation method of the self-leveling long-acting mildew-proof silicone adhesive according to any one of claims 1 to 9, characterized by comprising the following steps:
under the vacuum pumping condition, mixing and stirring the 107-base adhesive and the plasticizer uniformly, then adding the cross-linking agent and the modified fumed silica in sequence and stirring uniformly; and finally, adding the epoxy modified silane coupling agent, the auxiliary silane coupling agent and the catalyst, and uniformly stirring to obtain the epoxy modified silane coupling agent.
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