CN115287029B - Epoxy sealant and preparation method thereof - Google Patents
Epoxy sealant and preparation method thereof Download PDFInfo
- Publication number
- CN115287029B CN115287029B CN202210810375.9A CN202210810375A CN115287029B CN 115287029 B CN115287029 B CN 115287029B CN 202210810375 A CN202210810375 A CN 202210810375A CN 115287029 B CN115287029 B CN 115287029B
- Authority
- CN
- China
- Prior art keywords
- parts
- aluminum hydroxide
- stirring
- epoxy
- bisphenol
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- 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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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 invention discloses an epoxy sealant, which comprises the following raw materials in parts by weight: 40-80 parts of bisphenol A epoxy resin, 10-30 parts of bisphenol B epoxy resin, 20-40 parts of fumed silica, 1-2 parts of anti-aging agent, 50-100 parts of superfine active calcium carbonate, 1-2 parts of pigment, 2000 10-20 parts of polyethylene glycol, 1-2 parts of 1, 6-hexamethylene diisocyanate, 200-2 parts of polyethylene glycol monomethyl ether, 0.1-0.2 part of catalyst alpha, 1-2 parts of polyisobutene, 1-3 parts of 1, 3-propylene glycol, 1-5 parts of organic treatment nanometer aluminum hydroxide, 0.1-0.2 part of catalyst beta and 1-2 parts of cross-linking agent; the organic treatment of nanometer aluminum hydroxide is achieved by adopting the reaction of nanometer aluminum hydroxide and methyl trichlorosilane, thereby grafting a silicon methyl on the surface of the nanometer aluminum hydroxide. The invention discloses a preparation method of the epoxy sealant.
Description
Technical Field
The invention relates to the technical field of epoxy sealants, in particular to an epoxy sealant and a preparation method thereof.
Background
The automobile industry in China, especially various passenger cars represented by cars, rapidly develops, and the demand of high-quality automobiles for sealant presents a situation of developing to high performance, multiple varieties, serialization and specialization. The sealant is mainly used for filling the configuration gaps to play a role in sealing, and has the functions of leakage prevention, water prevention, vibration prevention, sound insulation, heat insulation and the like.
The epoxy sealant has wide application in the field of automobile manufacture, can simplify the production process, save materials, strengthen the strength of components, and has special effects in the aspects of shock resistance, heat insulation, corrosion resistance, rust resistance, leakage resistance, looseness resistance, noise reduction, dead weight reduction, comfort, safety and the like, and is an indispensable material in automobile production.
The epoxy sealant can be applied to different parts of an automobile, and is particularly most commonly applied to an engine of the automobile so as to solve the problems of water leakage, oil leakage, air leakage and the like of the engine of the automobile. Bisphenol A epoxy resin is the most widely used epoxy resin at present, and contains epoxy groups at two ends and groups such as ether bond, secondary hydroxyl, benzene ring, methylene, isopropyl and the like on the main chain. Epoxy resins are widely used in automotive engine sealants for their excellent adhesion, mechanical properties, corrosion resistance and electrical insulation properties.
Along with the acceleration of the production beat, when the automobile engine part is assembled, the sealant is required to be good in tightness, and the automobile engine is always in a high-temperature state when working, if the high-temperature resistance is unstable, the sealing of the automobile engine is damaged and fails. The epoxy sealant in the prior art cannot conduct heat well, is more unfavorable for heat dissipation due to heat insulation, and can cause poor sealing strength and tensile strength although the heat conduction effect is improved by adding a large amount of heat conduction filler in the prior art.
Therefore, how to improve the epoxy sealant to achieve the ideal heat dissipation performance and ensure the tensile strength and the sealing strength is a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides an epoxy sealant and a preparation method thereof.
An epoxy sealant comprises the following raw materials in parts by weight: 40-80 parts of bisphenol A epoxy resin, 10-30 parts of bisphenol B epoxy resin, 20-40 parts of fumed silica, 1-2 parts of anti-aging agent, 50-100 parts of superfine active calcium carbonate, 1-2 parts of pigment, 2000 10-20 parts of polyethylene glycol, 1-2 parts of 1, 6-hexamethylene diisocyanate, 200-2 parts of polyethylene glycol monomethyl ether, 0.1-0.2 part of catalyst alpha, 1-2 parts of polyisobutene, 1-3 parts of 1, 3-propylene glycol, 1-5 parts of organic treatment nanometer aluminum hydroxide, 0.1-0.2 part of catalyst beta and 1-2 parts of cross-linking agent; the organic treatment of nanometer aluminum hydroxide is achieved by adopting the reaction of nanometer aluminum hydroxide and methyl trichlorosilane, thereby grafting a silicon methyl on the surface of the nanometer aluminum hydroxide.
Preferably, the bisphenol A type epoxy resin has an average functionality of 2 and an epoxy equivalent weight of 100 to 250g/eq; the bisphenol B type epoxy resin has an average functionality of 2 and an epoxy equivalent of 100 to 200e/eq.
Preferably, the catalyst α is at least one of dioctyltin dilaurate, dibutyltin dilaurate, dimethyltin dilaurate, stannous octoate, butyltin oxide and octyltin oxide.
Preferably, the polyisobutene is a low molecular weight polyisobutene, in particular having a molecular weight of from 1000 to 3000.
Preferably, the catalyst beta is at least one of dibutyl tin dilaurate, stannous octoate, tin butyrate, dibutyl tin diacetate and dibutyl tin dioctoate.
Preferably, the cross-linking agent is at least one of aminopropyl trimethoxysilane, aminopropyl triethoxysilane, and aminophenyl trimethoxysilane.
Preferably, the organic treatment nanometer aluminum hydroxide is prepared by the following specific steps: adding nano aluminum hydroxide into cyclohexane for uniform dispersion, adding methyltrichlorosilane at 40-60 ℃, continuously stirring for 10-20h, removing cyclohexane, washing and drying to obtain the organic treatment nano aluminum hydroxide.
Preferably, the mass ratio of the nanometer aluminum hydroxide to the methyltrichlorosilane is 1-5:1-2.
Preferably, the particle size of the nano aluminum hydroxide is 10-500nm, wherein the mass fraction of the nano aluminum hydroxide with the particle size of 10-150nm is 50-70%.
The preparation method of the epoxy sealant comprises the following steps:
s1, mixing bisphenol A type epoxy resin, bisphenol B type epoxy resin, fumed silica, an anti-aging agent, superfine active calcium carbonate and pigment, carrying out vacuum dehydration treatment at 120-150 ℃ for 1-2h, wherein the vacuum degree is 80-90kPa, and cooling to room temperature to obtain premix a;
s2, adding tetrahydrofuran into polyethylene glycol 2000, uniformly stirring, adding 1, 6-hexamethylene diisocyanate, polyethylene glycol monomethyl ether 200 and a catalyst alpha, stirring for 2-4 hours under the protection of nitrogen, adding polyisobutene, and stirring for 4-10 hours at 50-70 ℃ to obtain a prefabricated material b;
s3, adding 1, 3-propylene glycol into the prefabricated material b, stirring for 4-10h, adding the organically treated nano aluminum hydroxide, stirring for 1-2h, adding the premix a and the catalyst beta, stirring for 10-30min, adding the cross-linking agent, stirring for 20-40min, and carrying out vacuum degassing to obtain the epoxy sealant.
The technical effects of the invention are as follows:
the invention adopts polyethylene glycol 2000 as a soft segment, the mutual entanglement of a long chain structure and 1, 6-hexamethylene diisocyanate is beneficial to the formation of physical crosslinking and the development of ductility, and adopts the coordination of polyisobutylene and 1, 3-propylene glycol, the polyisobutylene only has double bonds at the terminal positions, so that the polyisobutylene is only inserted into a main chain at the terminal positions, and the polyisobutylenes are coupled with each other by double bonds, thereby generating a highly entangled network structure, and the elastic deformation performance and the excellent tensile performance of the polyisobutylenes can be effectively enhanced by stretching the polymer chains entangled among molecules to release the hidden length.
The polyisobutene in the epoxy sealant disclosed by the invention is not only ideal to attach to an automobile engine, but also low in molecular weight and strong in molecular chain end mobility, so that the polyisobutene is easier to effectively combine on a contact surface, the adhesive strength of a sizing material is enhanced, and the sealing strength is excellent.
According to the invention, hydroxyl groups of nano aluminum hydroxide are combined with active silicon-chlorine bonds of methyltrichlorosilane, so that the surface of the nano aluminum hydroxide is grafted with a silicon methyl group, the hydrophobic property of the nano aluminum hydroxide is effectively enhanced, the organic treatment nano aluminum hydroxide and a polyisobutene structure are combined in a prefabricated material b, the compatibility of the three is excellent, meanwhile, long chains of the polyisobutene structure and macromolecular structures of the organic treatment nano aluminum hydroxide are fully dispersed, molecular chains are mutually entangled, the heat conductivity is excellent, the thermal stability is enhanced, and the tensile strength is further enhanced.
However, the applicant has found through a plurality of experiments that the mass ratio of the organically treated nano aluminum hydroxide to the polyisobutene cannot exceed 1-5:1-2, otherwise leading to a decrease in thermal conductivity. The applicant believes that, since the thermal conductivity is mainly determined by whether a thermal conduction path can be formed in the system, if the content of the organic nano aluminum hydroxide is increased, the ratio of the organic methyl trichlorosilane is increased, and the thermal resistance is increased due to the existence between the nano aluminum hydroxide and the prefabricated material b, and the thermal conductivity of the product is reduced instead.
Drawings
FIG. 1 is a graph comparing stress-strain curves of epoxy sealants obtained in example 5 and comparative examples 1-2 after curing.
FIG. 2 is a graph comparing thermogravimetric curves of epoxy sealants obtained in example 5 and comparative examples 1-2 after curing.
FIG. 3 is a graph showing the thermal conductivity and adhesive strength of the epoxy sealants obtained in example 5 and comparative examples 1 to 2.
Detailed Description
The invention is further illustrated below in connection with specific embodiments.
Example 1
The preparation method of the epoxy sealant comprises the following steps:
s1, adding 40kg of bisphenol A epoxy resin with the epoxy equivalent of 100g/eq, 10kg of bisphenol B epoxy resin with the epoxy equivalent of 100e/eq, 20kg of fumed silica, 1kg of anti-aging agent BHT, 50kg of superfine activated calcium carbonate and 1kg of pigment into a mixer for dehydration, and carrying out vacuum dehydration treatment at 120 ℃ for 1h, wherein the stirring speed is 100r/min, the vacuum degree is 80kPa, and cooling to room temperature to obtain premix a;
s2, 10kg of polyethylene glycol 2000 is added into an oven, dehydration treatment is carried out for 1h at 100 ℃, 20kg of dried tetrahydrofuran is added into the oven, stirring is carried out uniformly, 1kg of 1, 6-hexamethylene diisocyanate, 1kg of polyethylene glycol monomethyl ether 200 and 0.1kg of dioctyl tin dilaurate are added, stirring is carried out for 2h under the protection of nitrogen, 1kg of low molecular weight polyisobutene with the molecular weight of 1000-3000 is added, and stirring is carried out for 4h at 50 ℃ to obtain a prefabricated material b;
s3, adding 1kg of 1, 3-propylene glycol into the prefabricated material b, stirring for 4 hours, adding 1kg of organic treatment nanometer aluminum hydroxide, stirring for 1 hour, adding the premix a, 0.1kg of stannous octoate, stirring for 10 minutes, adding 1kg of aminopropyl trimethoxysilane, stirring for 20 minutes, and carrying out vacuum degassing to obtain the epoxy sealant.
The organic treatment nanometer aluminum hydroxide is prepared by the following specific steps: adding 1kg of nano aluminum hydroxide with the particle size of 10-500nm into 30kg of cyclohexane, dispersing uniformly, adding 1kg of methyltrichlorosilane at 40 ℃, continuously stirring for 10 hours, standing, pouring out the upper solvent, heating and evaporating to remove the solvent completely, washing with water until no chloride ions exist in the filtrate, and drying to obtain the organic treatment nano aluminum hydroxide.
In the nano aluminum hydroxide, the mass fraction of the nano aluminum hydroxide with the particle size of 10-150nm is 50%.
Example 2
The preparation method of the epoxy sealant comprises the following steps:
s1, adding 80kg of bisphenol A epoxy resin with the epoxy equivalent of 250g/eq, 30kg of bisphenol B epoxy resin with the epoxy equivalent of 200e/eq, 40kg of fumed silica, 2kg of anti-aging agent BHT, 100kg of superfine activated calcium carbonate and 2kg of pigment into a mixer for dehydration, and carrying out vacuum dehydration treatment at 150 ℃ for 2 hours, wherein the stirring speed is 500r/min, the vacuum degree is 90kPa, and cooling to room temperature to obtain premix a;
s2, adding 20kg of polyethylene glycol 2000 into an oven, dehydrating at 120 ℃ for 2 hours, adding 40kg of dried tetrahydrofuran into the oven, stirring uniformly, adding 2kg of 1, 6-hexamethylene diisocyanate, 2kg of polyethylene glycol monomethyl ether 200 and 0.2kg of dimethyl tin dilaurate, stirring for 4 hours under the protection of nitrogen, adding 2kg of low molecular weight polyisobutene with the molecular weight of 1000-3000, and stirring at 70 ℃ for 10 hours to obtain a prefabricated material b;
s3, adding 3kg of 1, 3-propylene glycol into the prefabricated material b, stirring for 10 hours, adding 5kg of organic treatment nanometer aluminum hydroxide, stirring for 2 hours, adding the premix a, 0.2kg of tin butyrate, stirring for 30 minutes, adding 2kg of aminopropyl trimethoxysilane, stirring for 40 minutes, and carrying out vacuum degassing to obtain the epoxy sealant.
The organic treatment nanometer aluminum hydroxide is prepared by the following specific steps: adding 5kg of nano aluminum hydroxide with the particle size of 10-500nm into 60kg of cyclohexane, dispersing uniformly, adding 2kg of methyltrichlorosilane at 60 ℃, continuously stirring for 20h, standing, pouring out the upper solvent, heating and evaporating to remove the solvent completely, washing with water until no chloride ions exist in the filtrate, and drying to obtain the organic treatment nano aluminum hydroxide.
In the nano aluminum hydroxide, the mass fraction of the nano aluminum hydroxide with the particle size of 10-150nm is 70%.
Example 3
The preparation method of the epoxy sealant comprises the following steps:
s1, adding 50kg of bisphenol A epoxy resin with the epoxy equivalent of 180g/eq, 25kg of bisphenol B epoxy resin with the epoxy equivalent of 150e/eq, 25kg of fumed silica, 1.7kg of anti-aging agent BHT, 60kg of superfine activated calcium carbonate and 1.7kg of pigment into a mixer for dehydration, and carrying out vacuum dehydration treatment at 130 ℃ for 1.7h, wherein the stirring speed is 200r/min, the vacuum degree is 88kPa, and cooling to room temperature to obtain premix a;
s2, adding 13kg of polyethylene glycol 2000 into an oven, dehydrating at 115 ℃ for 1.2 hours, adding 35kg of dried tetrahydrofuran into the oven, stirring uniformly, adding 1.3kg of 1, 6-hexamethylene diisocyanate, 1.8kg of polyethylene glycol monomethyl ether 200 and 0.13kg of stannous octoate, stirring for 3.5 hours under the protection of nitrogen, adding 1.2kg of low molecular weight polyisobutene with molecular weight of 1000-3000, and stirring at 55 ℃ for 8 hours to obtain a prefabricated material b;
s3, adding 1.5kg of 1, 3-propylene glycol into the prefabricated material b, stirring for 8 hours, adding 2kg of organic treatment nanometer aluminum hydroxide, stirring for 1.7 hours, adding the premix a, 0.13kg of dibutyltin dilaurate, stirring for 25 minutes, adding 1.3kg of aminophenyltrimethoxysilane, stirring for 35 minutes, and carrying out vacuum degassing to obtain the epoxy sealant.
The organic treatment nanometer aluminum hydroxide is prepared by the following specific steps: adding 4kg of nano aluminum hydroxide with the particle size of 10-500nm into 40kg of cyclohexane, dispersing uniformly, adding 1.3kg of methyltrichlorosilane at 55 ℃, continuously stirring for 18h, standing, pouring out the upper solvent, heating and evaporating to remove the solvent completely, washing with water until no chloride ions exist in the filtrate, and drying to obtain the organic treatment nano aluminum hydroxide.
In the nano aluminum hydroxide, the mass fraction of the nano aluminum hydroxide with the particle size of 10-150nm is 55%.
Example 4
The preparation method of the epoxy sealant comprises the following steps:
s1, adding 70kg of bisphenol A epoxy resin with the epoxy equivalent of 180g/eq, 15kg of bisphenol B epoxy resin with the epoxy equivalent of 150e/eq, 35kg of fumed silica, 1.3kg of anti-aging agent BHT, 80kg of superfine activated calcium carbonate and 1.3kg of pigment into a mixer for dehydration, and carrying out vacuum dehydration treatment at 140 ℃ for 1.3h, wherein the stirring speed is 400r/min, the vacuum degree is 82kPa, and cooling to room temperature to obtain premix a;
s2, adding 17kg of polyethylene glycol 2000 into an oven, dehydrating at 105 ℃ for 1.8 hours, adding 25kg of dried tetrahydrofuran into the oven, stirring uniformly, adding 1.7kg of 1, 6-hexamethylene diisocyanate, 1.2kg of polyethylene glycol monomethyl ether 200 and 0.17kg of octyl tin oxide, stirring for 2.5 hours under the protection of nitrogen, adding 1.8kg of low molecular weight polyisobutene with molecular weight of 1000-3000, and stirring at 65 ℃ for 6 hours to obtain a prefabricated material b;
s3, adding 2.5kg of 1, 3-propylene glycol into the prefabricated material b, stirring for 6 hours, adding 4kg of organic treatment nanometer aluminum hydroxide, stirring for 1.3 hours, adding the premix a, 0.17kg of dibutyltin diacetate, stirring for 15 minutes, adding 1.7kg of aminophenyltrimethoxysilane, stirring for 25 minutes, and carrying out vacuum degassing to obtain the epoxy sealant.
The organic treatment nanometer aluminum hydroxide is prepared by the following specific steps: adding 2kg of nano aluminum hydroxide with the particle size of 10-500nm into 50kg of cyclohexane, dispersing uniformly, adding 1.7kg of methyltrichlorosilane at 45 ℃, continuously stirring for 12h, standing, pouring out the upper solvent, heating and evaporating to remove the solvent completely, washing with water until no chloride ions exist in the filtrate, and drying to obtain the organic treatment nano aluminum hydroxide.
In the nano aluminum hydroxide, the mass fraction of the nano aluminum hydroxide with the particle size of 10-150nm is 65%.
Example 5
The preparation method of the epoxy sealant comprises the following steps:
s1, adding 60kg of bisphenol A epoxy resin with the epoxy equivalent of 180g/eq, 20kg of bisphenol B epoxy resin with the epoxy equivalent of 150e/eq, 30kg of fumed silica, 1.5kg of anti-aging agent BHT, 70kg of superfine activated calcium carbonate and 1.5kg of pigment into a mixer for dehydration, and carrying out vacuum dehydration treatment at 135 ℃ for 1.5 hours, wherein the stirring speed is 300r/min, the vacuum degree is 85kPa, and cooling to room temperature to obtain premix a;
s2, adding 15kg of polyethylene glycol 2000 into an oven, dehydrating at 110 ℃ for 1.5 hours, adding 30kg of dried tetrahydrofuran into the oven, stirring uniformly, adding 1.5kg of 1, 6-hexamethylene diisocyanate, 1.5kg of polyethylene glycol monomethyl ether 200 and 0.15kg of dibutyltin dilaurate, stirring for 3 hours under the protection of nitrogen, adding 1.5kg of low-molecular-weight polyisobutene with molecular weight of 1000-3000, and stirring at 60 ℃ for 7 hours to obtain a prefabricated material b;
s3, adding 2kg of 1, 3-propanediol into the prefabricated material b, stirring for 7h, adding 3kg of organic treatment nanometer aluminum hydroxide, stirring for 1.5h, adding the premix a, 0.15kg of stannous octoate, stirring for 20min, adding 1.5kg of aminopropyl triethoxysilane, stirring for 30min, and carrying out vacuum degassing to obtain the epoxy sealant.
The organic treatment nanometer aluminum hydroxide is prepared by the following specific steps: adding 3kg of nano aluminum hydroxide with the particle size of 10-500nm into 45kg of cyclohexane, dispersing uniformly, adding 1.5kg of methyltrichlorosilane at 50 ℃, continuously stirring for 15h, standing, pouring out the upper solvent, heating and evaporating to remove the solvent completely, washing with water until no chloride ions exist in the filtrate, and drying to obtain the organic treatment nano aluminum hydroxide.
In the nano aluminum hydroxide, the mass fraction of the nano aluminum hydroxide with the particle size of 10-150nm is 60%.
Comparative example 1
The preparation method of the epoxy sealant comprises the following steps:
s1, adding 60kg of bisphenol A epoxy resin with the epoxy equivalent of 180g/eq, 20kg of bisphenol B epoxy resin with the epoxy equivalent of 150e/eq, 30kg of fumed silica, 1.5kg of anti-aging agent BHT, 70kg of superfine activated calcium carbonate and 1.5kg of pigment into a mixer for dehydration, and carrying out vacuum dehydration treatment at 135 ℃ for 1.5 hours, wherein the stirring speed is 300r/min, the vacuum degree is 85kPa, and cooling to room temperature to obtain premix a;
s2, adding 15kg of polyethylene glycol 2000 into an oven, dehydrating at 110 ℃ for 1.5 hours, adding 30kg of dried tetrahydrofuran into the oven, stirring uniformly, adding 1.5kg of 1, 6-hexamethylene diisocyanate, 1.5kg of polyethylene glycol monomethyl ether 200 and 0.15kg of dibutyltin dilaurate, stirring for 3 hours under the protection of nitrogen, adding 1.5kg of low-molecular-weight polyisobutene with molecular weight of 1000-3000, and stirring at 60 ℃ for 7 hours to obtain a prefabricated material b;
s3, adding 2kg of 1, 3-propanediol into the prefabricated material b, stirring for 7h, adding 3kg of nano aluminum hydroxide with the particle size of 10-500nm, stirring for 1.5h, adding the premix a and 0.15kg of stannous octoate, stirring for 20min, adding 1.5kg of aminopropyl triethoxysilane, stirring for 30min, and carrying out vacuum degassing to obtain the epoxy sealant.
In the nano aluminum hydroxide, the mass fraction of the nano aluminum hydroxide with the particle size of 10-150nm is 60%.
Comparative example 2
The preparation method of the epoxy sealant comprises the following steps:
s1, adding 60kg of bisphenol A epoxy resin with the epoxy equivalent of 180g/eq, 20kg of bisphenol B epoxy resin with the epoxy equivalent of 150e/eq, 30kg of fumed silica, 1.5kg of anti-aging agent BHT, 70kg of superfine activated calcium carbonate and 1.5kg of pigment into a mixer for dehydration, and carrying out vacuum dehydration treatment at 135 ℃ for 1.5 hours, wherein the stirring speed is 300r/min, the vacuum degree is 85kPa, and cooling to room temperature to obtain premix a;
s2, adding 15kg of polyethylene glycol 2000 into an oven, dehydrating at 110 ℃ for 1.5 hours, adding 30kg of dried tetrahydrofuran into the oven, uniformly stirring, adding 1.5kg of 1, 6-hexamethylene diisocyanate, 1.5kg of polyethylene glycol monomethyl ether 200 and 0.15kg of dibutyltin dilaurate, stirring for 3 hours under the protection of nitrogen, and stirring at 60 ℃ for 7 hours to obtain a prefabricated material b;
s3, adding 2kg of 1, 3-propanediol into the prefabricated material b, stirring for 7h, adding 3kg of organic treatment nanometer aluminum hydroxide, stirring for 1.5h, adding the premix a, 0.15kg of stannous octoate, stirring for 20min, adding 1.5kg of aminopropyl triethoxysilane, stirring for 30min, and carrying out vacuum degassing to obtain the epoxy sealant.
The organic treatment nanometer aluminum hydroxide is prepared by the following specific steps: adding 3kg of nano aluminum hydroxide with the particle size of 10-500nm into 45kg of cyclohexane, dispersing uniformly, adding 1.5kg of methyltrichlorosilane at 50 ℃, continuously stirring for 15h, standing, pouring out the upper solvent, heating and evaporating to remove the solvent completely, washing with water until no chloride ions exist in the filtrate, and drying to obtain the organic treatment nano aluminum hydroxide.
In the nano aluminum hydroxide, the mass fraction of the nano aluminum hydroxide with the particle size of 10-150nm is 60%.
Transferring the epoxy sealant obtained in the example 5 and the comparative examples 1-2 into a mold with polytetrafluoroethylene material on the surface, leveling, vacuumizing and defoaming until the surface of the sealant is smooth. And then curing to obtain the cured epoxy sealant with a flat surface.
The mechanical properties of each set of cured epoxy sealants were measured using a universal tensile tester at a test environment temperature of 22℃and a uniaxial tensile rate of 20mm/min.
As shown in fig. 1, the tensile strength of the cured test specimen obtained in example 5 was far superior to that of the comparative example, while the tensile elongation at break of the cured test specimen obtained in example 5 was also superior to that of the comparative example, at the same strain elongation.
The applicant believes that: the invention adopts polyethylene glycol 2000 as a soft segment, long chain structures of the polyethylene glycol 2000 are entangled with each other to facilitate the formation of physical crosslinking and the development of ductility, polyisobutylene is matched with 1, 3-propanediol, and only double bonds exist at the terminal positions of the polyisobutylene, so that the polyisobutylene is only inserted into a main chain at the terminal positions, and the polyisobutylenes are coupled with each other through double bonds, so that a highly entangled network structure can be generated, the elastic deformation performance of the polyisobutylene can be effectively enhanced by stretching polymer chains entangled among molecules to release hidden lengths, and the stretchability is excellent; meanwhile, the long chain of the polyisobutene structure and the macromolecular structure of the organically treated nano aluminum hydroxide are fully dispersed, molecular chains are mutually entangled, and the tensile strength is further enhanced.
The thermal stability of each set of samples used in the above test was analyzed using an automatic differential thermogravimetric analyzer.
As shown in fig. 2, the thermal stability of the test specimen after curing using the epoxy sealer obtained in example 5 exceeded that of the comparative example.
The applicant believes that: the invention adopts the hydroxyl of nano aluminum hydroxide to combine with active silicon-chlorine bond of methyl trichlorosilane, thereby grafting silicon methyl on the surface of nano aluminum hydroxide to effectively enhance the hydrophobic property of nano aluminum hydroxide, therefore, the organic treatment nano aluminum hydroxide and the polyisobutene structure are combined in the prefabricated material b, the compatibility of the three is excellent, and simultaneously, the long chain of the polyisobutene structure and the macromolecular structure of the organic treatment nano aluminum hydroxide are fully dispersed, the molecular chains are mutually entangled, and the thermal stability is enhanced.
And (3) measuring the heat conductivity coefficients of all groups of samples used in the test by adopting a DRP-II type heat conductivity coefficient tester, wherein the set temperature of a heating plate is 50 ℃, and the temperature is stable for 30-40min. The sample size was 80mm in diameter and 3mm in height.
The epoxy sealants obtained in example 5 and comparative examples 1 to 2 were defoamed, and were dispensed onto an Al-Ni interface with a dispenser and a size of 5 mm. Times.12.5 mm to prepare adhesive sheets, and after curing, the adhesive strength was measured by a chip pusher.
As shown in fig. 3, the epoxy sealer obtained in example 5 had the highest thermal conductivity and adhesive strength.
The applicant believes that: the invention adopts the hydroxyl of nano aluminum hydroxide to combine with active silicon-chlorine bond of methyl trichlorosilane, thereby grafting a silicon methyl on the surface of the nano aluminum hydroxide, effectively enhancing the hydrophobic property of the nano aluminum hydroxide, organically treating the mutual entanglement of a macromolecular structure of the nano aluminum hydroxide and a long chain of a polyisobutene structure and a molecular chain of a prefabricated material b, having excellent compatibility and being fully dispersed mutually, thereby obviously improving the interface effect between the nano aluminum hydroxide and the prefabricated material b, forming a heat conduction path in the epoxy sealant and improving the heat conduction property.
Meanwhile, the polyisobutene in the epoxy sealant disclosed by the invention is not only ideally attached to a material to be sealed of an automobile engine, but also low in molecular weight and strong in molecular chain end mobility, so that the polyisobutene is more easily attached to a contact surface, the adhesive strength of the adhesive is effectively enhanced, and the sealing strength is excellent.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (6)
1. The epoxy sealant is characterized by comprising the following raw materials in parts by weight: 40-80 parts of bisphenol A epoxy resin, 10-30 parts of bisphenol B epoxy resin, 20-40 parts of fumed silica, 1-2 parts of anti-aging agent, 50-100 parts of superfine active calcium carbonate, 1-2 parts of pigment, 2000 10-20 parts of polyethylene glycol, 1-2 parts of 1, 6-hexamethylene diisocyanate, 200-2 parts of polyethylene glycol monomethyl ether, 0.1-0.2 part of catalyst alpha, 1-2 parts of polyisobutene, 1-3 parts of 1, 3-propylene glycol, 1-5 parts of organic treatment nanometer aluminum hydroxide, 0.1-0.2 part of catalyst beta and 1-2 parts of cross-linking agent;
the organic treatment of nanometer aluminum hydroxide is achieved by adopting the reaction of nanometer aluminum hydroxide and methyltrichlorosilane, thereby grafting a silicon methyl on the surface of the nanometer aluminum hydroxide;
the polyisobutene is low molecular weight polyisobutene, and the specific molecular weight is 1000-3000;
the organic treatment nanometer aluminum hydroxide is prepared by the following specific steps: adding nano aluminum hydroxide into cyclohexane for uniform dispersion, adding methyltrichlorosilane at 40-60 ℃, continuously stirring for 10-20h, removing cyclohexane, washing and drying to obtain organic treated nano aluminum hydroxide;
the mass ratio of the nanometer aluminum hydroxide to the methyltrichlorosilane is 1-5:1-2;
the particle size of the nanometer aluminum hydroxide is 10-500nm, wherein the nanometer aluminum hydroxide with the particle size of 10-150nm accounts for 50-70% of the mass fraction.
2. The epoxy sealer according to claim 1, wherein the bisphenol a epoxy resin has an average functionality of 2 and an epoxy equivalent weight of 100 to 250g/eq; the bisphenol B type epoxy resin has an average functionality of 2 and an epoxy equivalent of 100 to 200e/eq.
3. The epoxy sealer of claim 1 wherein the catalyst α is at least one of dioctyltin dilaurate, dibutyltin dilaurate, dimethyltin dilaurate, stannous octoate, butyltin oxide, and octyltin oxide.
4. The epoxy sealant according to claim 1, wherein the catalyst β is at least one of dibutyltin dilaurate, stannous octoate, tin butyrate, dibutyltin diacetate, dibutyltin dioctoate.
5. The epoxy sealant according to claim 1, wherein the cross-linking agent is at least one of aminopropyl trimethoxysilane, aminopropyl triethoxysilane, and aminophenyl trimethoxysilane.
6. A method of preparing an epoxy sealant according to any one of claims 1 to 5, comprising the steps of:
s1 bisphenol A type epoxy resin, bisphenol B type epoxy resin and gas phaseMixing silicon dioxide, antioxidant, superfine activated calcium carbonate and pigment, vacuum dehydrating at 120-150deg.C for 1-2 hr with vacuum degree of 80-90kPa, cooling to room temperature to obtain premixa；
S2, adding tetrahydrofuran into polyethylene glycol 2000, uniformly stirring, adding 1, 6-hexamethylene diisocyanate, polyethylene glycol monomethyl ether 200 and a catalyst alpha, stirring for 2-4 hours under the protection of nitrogen, adding polyisobutene, and stirring for 4-10 hours at 50-70 ℃ to obtain a prefabricated materialb；
S3, prefabricated materialbAdding 1, 3-propylene glycol, stirring for 4-10 hr, adding organic treated nanometer aluminum hydroxide, stirring for 1-2 hr, adding premixaStirring the catalyst beta for 10-30min, adding the cross-linking agent, stirring for 20-40min, and vacuum degassing to obtain the epoxy sealant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210810375.9A CN115287029B (en) | 2022-07-11 | 2022-07-11 | Epoxy sealant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210810375.9A CN115287029B (en) | 2022-07-11 | 2022-07-11 | Epoxy sealant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115287029A CN115287029A (en) | 2022-11-04 |
| CN115287029B true CN115287029B (en) | 2023-08-08 |
Family
ID=83821681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210810375.9A Active CN115287029B (en) | 2022-07-11 | 2022-07-11 | Epoxy sealant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115287029B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105899565A (en) * | 2013-02-26 | 2016-08-24 | Sika技术股份公司 | Two-component composition |
| CN112154192A (en) * | 2018-07-04 | 2020-12-29 | Sika技术股份公司 | Chemically cross-linked water-based composition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2021013209A (en) * | 2019-05-28 | 2021-12-10 | Sika Tech Ag | Two-component composition with a high degree of strength. |
-
2022
- 2022-07-11 CN CN202210810375.9A patent/CN115287029B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105899565A (en) * | 2013-02-26 | 2016-08-24 | Sika技术股份公司 | Two-component composition |
| CN112154192A (en) * | 2018-07-04 | 2020-12-29 | Sika技术股份公司 | Chemically cross-linked water-based composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115287029A (en) | 2022-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101817529B (en) | Method for preparing modified white carbon black | |
| CN111154453A (en) | Heat-resistant single-component addition type organic silicon adhesive and preparation method thereof | |
| CN113322040B (en) | Adhesive sealant for wet base surface and preparation method and application thereof | |
| CN109535366B (en) | Secondary amino silane modified polyether polymer and preparation method thereof | |
| CN115627084B (en) | Surface treatment method of glass beads and silicone rubber | |
| CN112662203A (en) | Modified silicon dioxide filler, preparation method thereof and resin composition | |
| CN111154412B (en) | Quick-drying silicone adhesive material and preparation method thereof | |
| CN109096945B (en) | Tackifier applied to silicone sealant and preparation method thereof | |
| CN115287029B (en) | Epoxy sealant and preparation method thereof | |
| CN115505367B (en) | High-strength organic silicon adhesive and preparation method thereof | |
| CN112210341A (en) | Double-vulcanization system building sealant and preparation method thereof | |
| CN113956835A (en) | Organosilicon sealant for U-shaped heating pipe and preparation method thereof | |
| CN110776871B (en) | Room-temperature dealcoholized silicone adhesive and preparation method thereof | |
| CN111944476B (en) | Low-modulus two-component ketoxime-removing type organosilicon sealant and preparation method thereof | |
| CN117186828B (en) | Damping vibration attenuation and sound insulation airtight adhesive and preparation method thereof | |
| CN112844994A (en) | Temperature-resistant silica gel leather and preparation method thereof | |
| CN112961638A (en) | Fast-curing high-strength bi-component MS glue and preparation method thereof | |
| CN114133912B (en) | Bi-component silicone structural adhesive with strong initial adhesion | |
| CN116445111B (en) | Hot melt adhesive and preparation method thereof | |
| CN114517016B (en) | High-resilience low-pressure variable rubber compound and preparation method thereof | |
| CN115491165B (en) | Flame-retardant silicone adhesive for hollow glass and preparation method thereof | |
| CN116426242B (en) | Single-component room temperature vulcanization dealcoholized photovoltaic frame sealant | |
| CN114196363B (en) | Low-modulus fireproof flame-retardant assembly type building outer wall joint glue and preparation method thereof | |
| CN115287033B (en) | Automobile windshield glass glue and preparation method thereof | |
| CN112223861B (en) | Energy-saving silicon phenol fireproof insulation board |
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 |