CN115404041B - 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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- CN115404041B CN115404041B CN202211202007.2A CN202211202007A CN115404041B CN 115404041 B CN115404041 B CN 115404041B CN 202211202007 A CN202211202007 A CN 202211202007A CN 115404041 B CN115404041 B CN 115404041B
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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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- C08G59/14—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
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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 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 adhesive: 100 parts; modified fumed silica: 5-15 parts; and (3) a plasticizer: 10-35 parts; crosslinking agent: 2-9 parts; coupling agent: 0.3-2 parts; mildew preventive: 0.1 to 1.5 parts; organotin catalyst: 0.01 to 0.05 part; the modified gas-phase white carbon black is obtained by mixing and reacting gas-phase white carbon black, methoxy silicone oil and pyrophosphoric acid type monoalkoxy titanate coupling agent with the mass ratio of (250-400) to (0.1-3). The silicone adhesive prepared by the application has excellent stretching cohesiveness, self-leveling property, water resistance and long-acting mildew-proof effect.
Description
Technical Field
The application relates to the field of silicone sealants, in particular to a self-leveling long-acting mildew-proof silicone sealant and a preparation method thereof.
Background
The silicone sealant is an organic silica gel 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 Si-O-Si skeleton structure has excellent waterproof performance and weather resistance, and may be used widely in waterproof sealing field.
However, in the waterproof sealing construction of some irregular caulking joints, the tensile strength and the elongation of the traditional silicone sealant are poor, so that the fixed-extension adhesive property of the traditional silicone sealant is poor, cohesive failure is easy to occur during construction, and the waterproof sealing property 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 sealant, the application provides a self-leveling long-acting mildew-proof silicone sealant and a 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 adhesive: 100 parts;
modified fumed silica: 5-15 parts;
and (3) a plasticizer: 10-35 parts;
crosslinking agent: 2-9 parts;
coupling agent: 0.3-2 parts;
mildew preventive: 0.1 to 1.5 parts;
organotin catalyst: 0.01 to 0.05 part;
the modified gas-phase white carbon black is obtained by mixing and reacting gas-phase white carbon black, methoxy silicone oil and pyrophosphoric acid type monoalkoxy titanate coupling agent with the mass ratio of (250-400) to (0.1-3).
The gas-phase white carbon black has excellent reinforcing effect, can effectively improve the strength and elasticity of a silicone sealant system, improves the stretching adhesion of silicone sealant, and is favorable for waterproof sealing of irregular caulking joints, particularly caulking joints with wider widths.
It should be noted that the surface of the fumed silica 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 under the action of hydrogen bond bonding, the viscosity of the adhesive is greatly increased, and the flowability of the adhesive is reduced. Therefore, the application adopts methoxy silicone oil and pyrophosphoric acid type monoalkoxy titanate coupling agent to carry out surface modification on the gas-phase white carbon black, so that the polarity of the gas-phase white carbon black is effectively reduced, the tackifying effect of the gas-phase white carbon black is inhibited, the self-leveling property of the silicone adhesive is obviously improved, and the penetration and sealing effect of the silicone adhesive on caulking joints are ensured.
Specifically, methoxy silicone oil can be hydrolyzed to generate silanol groups, and then reacts with silanol groups on the surface of gas-phase white carbon black to form ether bonds or bond through hydrogen bonds, so that the silanol groups are consumed, and meanwhile, the methoxy silicone oil is adsorbed on the surface of the white carbon black to play a steric hindrance role, so that the formation of a tackifying network structure is inhibited. The pyrophosphoric acid type monoalkoxy titanate coupling agent can also be bonded through the reaction of alkoxy and gas-phase white carbon black, and the connection between the pyrophosphoric acid type monoalkoxy titanate coupling agent and 107 base rubber is improved through the coupling effect. In addition, the pyrophosphoric acid ester group of the pyrophosphoric acid type monoalkoxy titanate coupling agent can absorb free water in air, inhibit the water absorption and tackifying effects of the gas-phase white carbon black, and further ensure the self-leveling property, permeability and waterproof sealing property of the silicone adhesive.
Typically, but not by way of limitation, the 107 base gum is a hydroxyl terminated polysiloxane having a viscosity of 20000 to 80000 mpa.s; the plasticizer is methyl silicone oil with the viscosity of 50-1000 mpa.s; the active group content of the methoxy silicone oil is 8.0% of the hydroxyl group content; the surface area of the gas phase white carbon black is 130-300m 2 Preferably, the model is cabot LM-150.
Preferably, the coupling agent at least comprises an epoxy modified silane coupling agent, wherein the epoxy modified silane coupling agent is prepared by mixing and reacting an aminosilane coupling agent, isopropyl tri (dioctyl pyrophosphoric acid acyloxy) titanate and epoxy resin in a solvent, wherein the mass ratio of the aminosilane coupling agent to the isopropyl tri (dioctyl pyrophosphoric acid acyloxy) titanate is 1 (2-3) (0.5-1).
By adopting the technical scheme, the oligomeric product is obtained by mutual reaction or polycondensation of an aminosilane coupling agent, isopropyl tri (dioctyl pyrophosphoryl oxy) 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 nonpolar group Si-Pr on a side chain can reduce the surface tension of the building material and improve the hydrophobicity. The amino and epoxy groups in the molecular chain have a crosslinking effect, so that the 107 base adhesive and the meteorological silica can be crosslinked to form a more compact body type structure, and the waterproofness and the soaking stretching cohesiveness of the silicone sealant are effectively improved.
Preferably, the epoxy modified resin is prepared according to the following method:
step 1: the preparation method comprises the steps of (1) (2-3) (0.5-1) dissolving an aminosilane coupling agent, isopropyl tri (dioctyl pyrophosphoryl oxy) titanate and epoxy resin in an alcohol solvent, heating to 80-120 ℃ for reaction to obtain an intermediate product;
step 2: and (3) distilling under reduced pressure, 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 epoxy groups and amino groups is prepared, so that the mutual crosslinking of all components can be promoted while the coupling effect is achieved, the crosslinking density and compactness of the silicone adhesive are improved, and the waterproofness and the water immersion 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): 1-2; the auxiliary silane coupling agent adopts one or a combination of epoxy silane coupling agent and amino silane coupling agent.
By adopting the auxiliary silane coupling agent, the curing speed of the silicone sealant can be prevented from being attenuated, the storage stability of the silicone sealant is improved, and the surface drying speed of the silicone sealant is ensured. The mechanism is probably that the stability of the silane coupling agent is reduced after the silane coupling agent is modified by epoxy, so that the curing speed of the silicone adhesive is reduced along with the extension of the storage time, and the surface drying time is increased. By adopting the conventional aminosilane coupling agent or epoxy silane coupling agent for compounding, the storage stability of the epoxy silane coupling agent can be remarkably improved, the surface drying time is stabilized, and the cost is effectively reduced.
Preferably, the auxiliary silane coupling agent is one of gamma-aminopropyl triethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane, gamma- (2, 3-epoxypropoxy) propyl triethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane 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 is restrained.
Preferably, the cross-linking agent adopts one or more of methyl tributyl ketoxime silane, vinyl tributyl ketoxime silane, tetrabutyl ketoxime silane, phenyl tributyl ketoxime silane, methyl vinyl dibutyl ketoxime silane, dimethyl dibutyl ketoxime silane, methyl vinyl di (methyl isobutyl ketoxime) silane and methyl vinyl diacetone oxime 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 with the mass ratio of 1:1.
By adopting the technical scheme, the two mildew preventive agents are matched together, so that the long-acting antibacterial mildew preventive effect of the silicone sealant can be effectively realized.
Preferably, the raw materials of the long-acting mildew-proof silicone adhesive further comprise 0.5-2 parts of amino modified graphene oxide.
By adopting the technical scheme, the graphene oxide has excellent antibacterial and mildew-proof 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 mildew-proof effects of the silicone adhesive are enhanced; on the other hand, the dispersion of the graphene oxide can be promoted, and the full play of the mildew-proof effect of the graphene oxide can be promoted.
Preferably, the amino modified graphene oxide is prepared according to the following method:
adding graphene oxide into water for uniform dispersion, adjusting the pH value to 4-5, adding carbodiimide hydrochloride and N-hydroxysuccinimide, and stirring uniformly; then adding diamine compound, carrying out amidation reaction under heating condition, filtering, washing with water and drying after the reaction is completed, thus obtaining the amino modified graphene oxide.
By adopting the technical scheme, under the activation of carbodiimide hydrochloride and N-hydroxysuccinimide, the carboxyl in the graphene oxide can be subjected to amidation reaction with the amino of the diamine compound, so that the amino is introduced into the graphene oxide, and the reaction of the amino and the coupling agent containing epoxy groups is promoted.
The particle diameter of the graphene oxide is preferably 10 to 300nm, 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 includes the following steps:
under the condition of vacuumizing, mixing and stirring the 107 base rubber and the plasticizer uniformly, and then sequentially adding the cross-linking agent and the modified fumed silica and stirring uniformly; finally adding the epoxy modified silane coupling agent, the auxiliary silane coupling agent and the catalyst, and stirring uniformly to obtain the epoxy modified silane coupling agent.
By adopting the technical scheme, the silicone sealant with excellent tensile strength, elongation and stretching cohesiveness is prepared, and the waterproof tightness of the silicone sealant to irregular caulking is effectively improved.
In summary, the 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 adopted to mix the modified gas-phase white carbon black, so that the tensile strength, the elongation and the stretching cohesiveness of the silicone adhesive are effectively improved on the premise of guaranteeing the self-leveling property of the silicone adhesive.
2. According to the epoxy modified silane coupling agent obtained by mixing and reacting the amino silane coupling agent, the isopropyl tri (dioctyl pyrophosphoric acid acyloxy) titanate and the epoxy resin, the soaking and stretching cohesiveness of the silicone adhesive can be effectively improved.
3. According to the preparation method, 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 can be restrained.
4. According to the application, the amino-modified graphene oxide is adopted, so that the long-acting antibacterial and mildew-proof effects of the silicone adhesive can be effectively enhanced.
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% corresponding to hydroxyl content) are added into a reaction kettle; heating to 60 ℃, and dripping 20g of pyrophosphoric acid type monoalkoxy titanate coupling agent. And after the material addition is finished, stirring is continued for 60 minutes to obtain the modified gas-phase white carbon black.
Preparation examples 1-2, a modified fumed silica, are prepared as follows:
1000g of carbopol LM-150 fumed silica and 2500g of mpa.s methoxy silicone oil (the content of active groups is 8.0 percent of that of hydroxyl groups) are added into a reaction kettle; heating to 60 ℃, and dripping 30g of pyrophosphoric acid type monoalkoxy titanate coupling agent. And after the material addition is finished, stirring is continued for 120 minutes to obtain the modified gas-phase white carbon black.
Preparation examples 1-3, a modified fumed silica, are prepared as follows:
1000g of carbopol LM-150 fumed silica and 4000g of mpa.s methoxy silicone oil (the content of active groups is 8.0 percent of that of hydroxyl groups) are added into a reaction kettle; heating to 60 ℃, and dripping 1g of pyrophosphoric acid type monoalkoxy titanate coupling agent. And after the material addition is finished, stirring is continued for 60 minutes to obtain the modified gas-phase white carbon black.
Preparation example of epoxy-modified silane coupling agent
Preparation example 2-1, an epoxy modified silane coupling agent, is prepared according to the following method:
step 1: 500g N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane, 1000g isopropyl tri (dioctyl pyrophosphoryloxy) titanate, 284 g E51 epoxy resin and 450g methanol are added into a three-neck flask, and stirred and dispersed uniformly. And a reflux condenser, a thermometer and a constant pressure dropping funnel are arranged on the three-neck flask, the temperature is raised to 110 ℃ under stirring, and the reflux reaction is carried out for 3 hours, so as to obtain an intermediate product.
Step 2: and (3) distilling under reduced pressure, recovering methanol in the intermediate product, continuously heating to 140 ℃, continuously reacting for 2 hours, and cooling to room temperature after the reaction is completed, thus obtaining the epoxy modified silane coupling agent.
Preparation example 2-2, an epoxy modified silane coupling agent, is prepared according to the following method:
step 1: 500g of gamma-aminopropyl triethoxysilane, 1500g of isopropyl tri (dioctyl pyrophosphoric acid acyloxy) titanate, 500g of E51 epoxy resin and 800g of ethanol are added into a three-neck flask, a reflux condenser, a thermometer and a constant pressure dropping funnel are arranged on the three-neck flask, the temperature is raised to 120 ℃ under stirring, and the reflux reaction is carried out for 3 hours, so that an intermediate product is obtained.
Step 2: and (3) distilling under reduced pressure, 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 2-3, an epoxy modified silane coupling agent, were prepared as follows:
step 1: 500g N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane, 1000g isopropyl tri (dioctyl pyrophosphoryloxy) titanate, 250g E51 epoxy resin and 800g 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 80 ℃ under stirring, and the intermediate product is obtained after reflux reaction for 2 hours.
Step 2: and (3) distilling under reduced pressure, recovering ethanol in the intermediate product, continuously heating to 150 ℃, continuously reacting for 2 hours, and cooling to room temperature after the reaction is completed, thus obtaining the epoxy modified silane coupling agent.
Preparation examples 2-4, an epoxy-modified silane coupling agent, differ from preparation example 2-1 in that an equivalent amount of an aminosilane coupling agent was used instead of the epoxy resin.
Preparation example 2-5, an epoxy-modified silane coupling agent, differs from preparation example 2-1 in that an equivalent amount of an aminosilane coupling agent was used instead of isopropyl tris (dioctyl pyrophosphoryloxy) titanate.
Preparation examples 2-6, an epoxy-modified silane coupling agent, differ from preparation example 2-1 in that an equivalent amount of epoxy resin was used instead of the aminosilane coupling agent.
Preparation example of amino-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, stirring and dispersing uniformly, 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, stirring uniformly, heating the solution to 65 ℃, then adding 900g of hexamethylenediamine, carrying out amidation reaction under the heating condition, and filtering, washing and drying after the reaction is completed 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 dispersing uniformly, 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, heating the solution to 65 ℃ after stirring uniformly, then adding 1000g of hexamethylenediamine, carrying out amidation reaction under the heating condition, and filtering, washing and drying after the reaction is completed to obtain the amino modified graphene oxide.
Examples
Example 1, a self-leveling long-acting mildew-proof silicone adhesive, was prepared according to the following steps:
100 kg of 107 base rubber and 15 kg of methyl silicone oil are added into a planetary dispersing machine, and the mixture is stirred for 10 minutes at high speed under the condition of vacuumizing (the vacuum degree is minus 0.09Mpa to minus 0.1 Mpa); after 5 kg of vinyl tributyl ketoxime silane cross-linking agent is added, vacuumizing (the vacuum degree is minus 0.09Mpa to minus 0.1 Mpa) and stirring is carried out for 20 minutes; 10 kg of modified gas-phase white carbon black prepared in preparation example 1-1 and 1 kg of amino modified graphene oxide prepared in preparation example 3-1 are added, vacuumizing (vacuum degree is minus 0.09Mpa to minus 0.1 Mpa) is carried out for stirring for 20 minutes, finally 0.6 kg of mildew preventive (the mildew preventive of the Longsha ZPT environment-friendly powder and the mildew preventive of the Longsha Densil DN in mass ratio of 1:1), 0.5 kg of epoxy modified silane coupling agent prepared in preparation example 2-1, 0.5 kg of auxiliary silane coupling agent (gamma-aminopropyl triethoxysilane and gamma (2, 3-glycidoxy) propyl trimethoxysilane with mass ratio of 1:1) and 0.02 kg of dibutyltin dilaurate are added, and stirring is carried out for 10 minutes, thus obtaining the modified carbon black.
Example 2, a self-leveling long-acting mildew-proof silicone adhesive, was prepared according to the following steps:
100 kg of 107 base rubber and 10 kg of methyl silicone oil are added into a planetary dispersing machine, and the mixture is stirred for 10 minutes at high speed under the condition of vacuumizing (the vacuum degree is minus 0.09Mpa to minus 0.1 Mpa); 2 kg of methyltributylketon oximido silane crosslinking agent is added, and then the mixture is vacuumized (the vacuum degree is minus 0.09Mpa to minus 0.1 Mpa) and stirred for 20 minutes; and then 35 kg of the modified gas-phase white carbon black prepared in preparation example 1-2 and 2 kg of the amino modified graphene oxide prepared in preparation example 3-2 are added, the mixture is vacuumized (the vacuum degree is minus 0.09Mpa to minus 0.1 Mpa) and stirred for 20 minutes, and finally 0.1 kg of mildew preventive (the mildew preventive of the Longsha ZPT environment-friendly powder and the mildew preventive of the Longsha Densil DN in a mass ratio of 1:1), 1 kg of the epoxy modified silane coupling agent prepared in preparation example 2-2, 0.1 kg of the auxiliary silane coupling agent (N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane) and 0.01 kg of dioctyl tin dilaurate are added and stirred for 10 minutes to obtain the modified carbon black.
Example 3, a self-leveling long-acting mildew-proof silicone adhesive, was prepared according to the following steps:
100 kg of 107 base rubber and 35 kg of methyl silicone oil are added into a planetary dispersing machine, and the mixture is stirred for 10 minutes at high speed under the condition of vacuumizing (the vacuum degree is-0.09 Mpa to-0.1 Mpa); after 9 kg of methyltributylketon oximido silane crosslinking agent is added, vacuumizing (the vacuum degree is minus 0.09Mpa to minus 0.1 Mpa) and stirring for 20 minutes; and 5 kg of modified gas-phase white carbon black prepared in preparation example 1-3 and 0.5 kg of amino modified graphene oxide prepared in preparation example 3-1 are added, the mixture is vacuumized (the vacuum degree is minus 0.09Mpa to minus 0.1 Mpa) and stirred for 20 minutes, and finally 1.5 kg of mildew preventive (the mildew preventive of the environment-friendly powder ZPT of the Longsha and the mildew preventive of the Longsha) with the mass ratio of 1:1, 0.1 kg of epoxy modified silane coupling agent prepared in preparation example 2-3, 1 kg of auxiliary silane coupling agent (gamma (2, 3-glycidoxy) propyl triethoxysilane) and 0.05 kg of dioctyltin dilaurate are added and stirred for 10 minutes to obtain the modified epoxy silane coupling agent.
Example 4, a self-leveling, long-acting, mold-resistant 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 2-4 in equal amounts.
Example 5, a self-leveling long-acting 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 2-5 in the same amount.
Example 6, a self-leveling long-acting 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 2-6 in the same amount.
Example 7, a self-leveling long-acting mildewproof silicone adhesive, was different from example 1 in that the epoxy-modified silane coupling agent prepared in the same amount of preparation example 2-1 was used instead of the auxiliary silane coupling agent.
Example 8, a self-leveling long-acting 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 equivalent amount of auxiliary silane coupling agent (gamma-aminopropyl triethoxysilane and gamma- (2, 3-glycidoxy) in a mass ratio of 1:1).
Example 9, a self-leveling long-acting mildewproof silicone adhesive, differs from example 1 in that an equivalent amount of the Dragon sand mildewproof agent Densil DN was used instead of the amino modified graphene oxide.
Example 10, a self-leveling long-acting mildewproof silicone adhesive, differs from example 1 in that the same 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, is different from example 1 in that in the preparation process of modified fumed silica, equal amount of methoxy silicone oil is used for replacing pyrophosphoric acid monoalkoxy titanate coupling agent.
Comparative example 2, a self-leveling long-acting mildewproof silicone adhesive, differs from example 1 in that an equivalent amount of unmodified fumed silica was used instead of modified fumed silica.
Comparative example 3, a self-leveling long-acting mildew-proof silicone adhesive, differs from example 1 in that an equivalent amount of pyrocarbonic acid type monoalkoxy titanate coupling agent and methoxy silicone oil modified nano calcium carbonate are used to replace modified fumed silica.
Performance test
The properties of the silicone adhesive were tested according to JC/T885-2016, and the test results are shown in Table 1.
TABLE 1 Silicone adhesive Performance test results
It should be noted that the self-leveling long-acting mildew-proof silicone adhesive is applied to the waterproof sealing field of irregular caulking, and the surface drying time is controlled within 20 minutes so as to adapt to the construction environment.
Analysis of results:
(1) By combining examples 1-10 and comparative examples 1-3 and combining Table 1, the application can obviously improve the tensile strength and elongation of the silicone adhesive by adopting the gas-phase white carbon black modified by methoxy silicone oil and pyrophosphoric acid type monoalkoxy titanate coupling agent, thereby guaranteeing the stretching cohesiveness (comprising stretching cohesiveness, stretching cohesiveness after water inlet and cohesiveness after 25-level cold-drawing hot pressing).
(2) As can be seen from the combination of example 1 and examples 4 to 6 and the combination of table 1, the epoxy-modified silane coupling agent prepared by using the aminosilane coupling agent, isopropyl tri (dioctyl pyrophosphoryloxy) titanate and 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 groups and amino groups can be obtained after the three materials are heated and reacted, so that the mutual crosslinking of 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 immersion stretching adhesion of the cured silicone adhesive can be further improved.
(3) It can be seen from the combination of examples 1 and examples 7 to 8 and the combination of Table 1 that the use of the epoxy-modified silane coupling agent and the auxiliary silane coupling agent in combination can improve the water repellency and the water immersion elongation adhesiveness of the silicone adhesive while ensuring the storage stability of the silicone adhesive. The reason for this is probably that the silane coupling agent subjected to the modification reaction such as the epoxy-modified silane coupling agent is poor in stability, so that the curing speed of the silicone adhesive is reduced with the increase of the storage time, the surface drying time is greatly increased, and the construction operation is not facilitated. Therefore, the stability of the raw materials of the coupling agent can be effectively improved by adopting the conventional epoxy silane coupling agent or the conventional amino silane coupling agent, and the silicone adhesive is ensured to have excellent surface drying time and water immersion stretching adhesion.
(4) As can be seen by combining the embodiment 1 and the embodiments 9-10 and combining the table 1, the application further adopts the amino modified graphene oxide on the basis of the mildew preventive, so that the long-acting mildew preventive performance of the silicone adhesive can be effectively improved. The principle of the method is that graphene oxide with bacteriostasis can be bonded with the epoxy modified silane coupling agent through reaction 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 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 (8)
1. The self-leveling long-acting mildew-proof silicone adhesive is characterized by comprising the following raw materials in parts by weight:
107 base adhesive: 100 parts;
modified fumed silica: 5-15 parts;
and (3) a plasticizer: 10-35 parts;
crosslinking agent: 2-9 parts;
coupling agent: 0.3-2 parts;
mildew preventive: 0.1 to 1.5 parts;
organotin catalyst: 0.01 to 0.05 part;
the modified gas-phase white carbon black is obtained by mixing and reacting gas-phase white carbon black, methoxy silicone oil and pyrophosphoric acid type monoalkoxy titanate coupling agent with the mass ratio of (250-400) to (0.1-3);
the coupling agent comprises an epoxy modified silane coupling agent and an auxiliary silane coupling agent in a mass ratio of (1-2), wherein the epoxy modified silane coupling agent is obtained by mixing and reacting an aminosilane coupling agent, isopropyl tri (dioctyl pyrophosphoric acid acyloxy) titanate and epoxy resin in a solvent in a mass ratio of (1-2) to (0.5-1);
the auxiliary silane coupling agent adopts one or a combination of epoxy silane coupling agent and amino silane coupling agent.
2. The self-leveling long-acting mildew-proof silicone adhesive according to claim 1, wherein the epoxy modified silane coupling agent is prepared by the following method:
step 1: the preparation method comprises the steps of (1) (2-3) (0.5-1) dissolving an aminosilane coupling agent, isopropyl tri (dioctyl pyrophosphoryl oxy) titanate and epoxy resin in an alcohol solvent, heating to 80-120 ℃ for reaction to obtain an intermediate product;
step 2: and (3) distilling under reduced pressure, 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.
3. The self-leveling long-acting mildew-proof silicone adhesive according to claim 1, wherein the auxiliary silane coupling agent is one of gamma-aminopropyl triethoxysilane, gamma- (2, 3-glycidoxy) propyl trimethoxysilane, gamma- (2, 3-glycidoxy) propyl triethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl triethoxysilane or a combination thereof.
4. The self-leveling long-acting mildew-proof silicone adhesive according to claim 1, wherein the cross-linking agent is one or more of methyl tributyl ketoxime silane, vinyl tributyl ketoxime silane, tetrabutyl ketoxime silane, phenyl tributyl ketoxime silane, methyl vinyl diacetone oxime silane, dimethyl diacetone oxime silane, methyl vinyl di (methyl isobutyl ketoxime) silane and methyl vinyl diacetone oxime silane.
5. 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 with a mass ratio of 1:1.
6. The self-leveling long-acting mildew-proof silicone adhesive according to claim 1, wherein the raw materials of the long-acting mildew-proof silicone adhesive further comprise 0.5-2 parts of amino-modified graphene oxide.
7. The self-leveling long-acting mildew-proof silicone adhesive according to claim 6, wherein the amino-modified graphene oxide is prepared by the following method:
adding graphene oxide into water for uniform dispersion, adjusting the pH value to 4-5, adding carbodiimide hydrochloride and N-hydroxysuccinimide, and stirring uniformly; then adding diamine compound, carrying out amidation reaction under heating condition, filtering, washing with water and drying after the reaction is completed, thus obtaining the amino modified graphene oxide.
8. The preparation method of the self-leveling long-acting mildew-proof silicone adhesive according to any one of claims 1 to 7, which is characterized by comprising the following steps:
under the condition of vacuumizing, mixing and stirring the 107 base rubber and the plasticizer uniformly, and then sequentially adding the cross-linking agent and the modified fumed silica and stirring uniformly; and finally adding the mildew preventive, the epoxy modified silane coupling agent, the auxiliary silane coupling agent and the catalyst, and stirring uniformly to obtain the epoxy modified silane coupling agent.
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| US4417009A (en) * | 1979-08-29 | 1983-11-22 | Kenrich Petrochemicals, Inc. | Pyrophosphato titanate adducts |
| CN102964701B (en) * | 2012-11-14 | 2014-06-11 | 安徽江威精密制造有限公司 | Butyl rubber for wrapping capacitor case |
| CN104232012A (en) * | 2014-10-14 | 2014-12-24 | 泸州北方化学工业有限公司 | Mold-proof silicone sealant and preparation method thereof |
| CN109162103A (en) * | 2018-08-09 | 2019-01-08 | 合肥五凡工程设计有限公司 | A kind of mould proof warm-keeping wool blended yarns |
| CN114479473A (en) * | 2022-01-24 | 2022-05-13 | 镇江高美新材料有限公司 | Antistatic liquid silicone rubber and preparation method thereof |
| CN114644771A (en) * | 2022-04-15 | 2022-06-21 | 山东金阳光医药包装有限公司 | Polyvinyl chloride medicine package sheet with anti-fouling and antibacterial functions and preparation method thereof |
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