CN111393802A - SiO (silicon dioxide)2Modified epoxy resin toughened by grafted polyamide curing agent and preparation method thereof - Google Patents
SiO (silicon dioxide)2Modified epoxy resin toughened by grafted polyamide curing agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of epoxy resin, and discloses SiO2The modified epoxy resin toughened by the grafted polyamide curing agent comprises the following formula raw materials and components: epoxy resin, SiO2Grafted polyamide curing agent and defoaming agent. The SiO2Grafted polyamide curing agent toughening modified epoxy resin, nano porous SiO2The specific surface area is larger, and the nano SiO can be increased2The surface hydroxyl content improves the grafting rate of the epoxy silane coupling agent, the epoxy group and the amino group of organic amine carry out ring-opening reaction, and the organic amine is used for grafting the nano SiO2The terminal amino group of (A) is used as a chemical reaction site, and Michael addition is carried out on the terminal amino group and acrylateReacting to obtain SiO2Grafted polyamide, using it as curing agent, making lots of amino and imino groups and epoxy resin open-loop cross-linked and cured to make nano SiO2Covalent grafting is introduced into the matrix of the epoxy resin coating material, so that nano SiO is avoided2The problems of agglomeration and sedimentation enhance the tensile strength and elongation at break of the material.
Description
Technical Field
The invention relates to the technical field of epoxy resin, in particular to SiO2A grafted polyamide curing agent toughening modified epoxy resin and a preparation method thereof.
Background
With the continuous development of the research of the composite material, the inorganic nano material is introduced into an organic polymer material system to form an inorganic-organic composite material system, so that the inorganic-organic composite material system has the advantages of the multifunction of the organic resin-based composite material, the height and the high temperature resistance of the inorganic nano material, and the like, and has a wide development prospect.
Epoxy resin is a thermosetting resin which is widely applied, the main varieties of the epoxy resin comprise structural adhesive, high temperature resistant adhesive, conductive adhesive, sealant latent curing adhesive and the like, and the epoxy resin has important application in the fields of civil construction, electronic and electric appliances, aerospace and the like, but the epoxy resin coating film has larger brittleness and has low mechanical properties such as toughness, tensile strength and the like, the existing epoxy resin modification method mainly comprises methods such as curing agent modification, reactive diluent modification, filling material modification and the like, nano inorganic materials such as nano silicon dioxide, graphene, carbon nano tubes and the like can be introduced into an epoxy resin matrix, and the nano silicon dioxide can be agglomerated and settled in the epoxy resin matrix by filling through a simple mechanical mixing method, so that the mechanical properties of the materials are seriously influenced.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides SiO2The grafted polyamide curing agent toughening modified epoxy resin and the preparation method thereof solve the problem that the mechanical properties such as tensile strength and the like of the epoxy resin are not high, and simultaneously solve the problem that nano silicon dioxide is easy to agglomerate and settle in an epoxy resin matrix.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: SiO (silicon dioxide)2The grafted polyamide curing agent toughening modified epoxy resin comprises the following raw materials and components: epoxy resin, SiO2The mass ratio of the graft polyamide curing agent to the defoaming agent is 100:30-50: 0.2-0.8.
Preferably, the SiO2The preparation method of the grafted polyamide curing agent toughening modified epoxy resin comprises the following steps:
(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 3-5:1, adding hexadecyl trimethyl ammonium bromide, dropwise adding ammonia water to adjust the pH value of the solution to 9-10, then adding tetraethoxysilane, the mass ratio of the tetraethoxysilane to the hexadecyl trimethyl ammonium bromide is 6-8:1, stirring at a constant speed for reaction for 5-10h, centrifugally separating the solution to remove the solvent, and separating a solid productDispersing in ethanol solvent, heating to 40-70 deg.C in a constant temperature water bath, stirring at constant speed for 12-24h, filtering, washing and drying, placing the solid product in a muffle furnace, calcining at 300-400 deg.C for 2-3h to obtain nano porous SiO2。
(2) Adding toluene solvent and nano-porous SiO into a reaction bottle2Uniformly dispersing by ultrasonic wave, adding epoxy silane coupling agent, heating to 60-90 ℃ in a constant-temperature water bath kettle, uniformly stirring for reaction for 10-20h, filtering, washing and drying to obtain the epoxidized nano SiO2。
(3) Introducing nitrogen into a reaction bottle, adding N, N-dimethylformamide solvent and epoxidized nano SiO2Adding organic amine after uniform ultrasonic dispersion, placing the mixture in a constant-temperature water bath kettle, heating the mixture to 50-80 ℃, uniformly stirring the mixture for reaction for 6-12 hours, reducing the temperature to 30-40 ℃, adding methyl acrylate, uniformly stirring the mixture for reaction for 3-8 hours, heating the mixture to 80-120 ℃, reacting the mixture for 20-30 hours, placing the solution in an ice water bath for cooling, adding distilled water until a large amount of precipitate is separated out, filtering, washing and drying the mixture to prepare SiO2And (3) a polyamide grafting curing agent.
(4) Adding epoxy resin, defoaming agent and SiO into acetone solvent2Grafting a polyamide curing agent, pouring the solution into a film forming mold after ultrasonic dispersion is uniform, and curing to form a film to prepare SiO2The grafted polyamide curing agent toughens and modifies the epoxy resin material.
Preferably, the constant-temperature water bath kettle comprises a heat preservation layer, a water bath is arranged inside the heat preservation layer, a base fixedly connected with the water bath and a reaction bottle is arranged above the base, and a support rod, a regulating valve and a regulating valve are fixedly connected inside the base.
Preferably, the epoxy silane coupling agent is any one of 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane, and nanoporous SiO2The mass ratio of (A) to (B) is 0.5-3: 10.
Preferably, the organic amine is any one of ethylenediamine, diethylenetriamine or triethylenetetramine, and epoxidized nano SiO2The mass ratio of the organic amine to the methyl acrylate is 1:2-4: 1.5-2.5.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the SiO2The grafted polyamide curing agent toughening modified epoxy resin takes cetyl trimethyl ammonium bromide as a template agent to obtain the nano porous SiO2Has abundant mesoporous structure and large specific surface area, thereby increasing the nano SiO2The hydroxyl content on the surface is improved, and the epoxy silane coupling agent to nano SiO is improved2The grafting rate of (2) is that a large amount of epoxy groups and amino groups of organic amine carry out ring-opening reaction, and then organic amine is used for grafting nano SiO2The terminal amino group is used as a chemical reaction site and is subjected to Michael addition reaction with the alkenyl group of the acrylate to prepare SiO2The grafted polyamide is used as a curing agent, a large number of amino and imino groups and epoxy groups of epoxy resin are subjected to ring-opening crosslinking curing, and nano SiO is obtained2Covalent grafting is introduced into the matrix of the epoxy resin coating material, so that nano SiO is avoided2Problems of agglomeration and sedimentation, uniformly dispersed nano SiO2Has obvious toughening effect on the epoxy resin coating, and greatly enhances the tensile strength and the elongation at break of the material.
Drawings
FIG. 1 is a schematic front view of a thermostatic water bath;
FIG. 2 is an enlarged view of the support rod;
fig. 3 is a schematic view of adjustment lever adjustment.
1-constant temperature water bath; 2-insulating layer; 3-water bath; 4-a base; 5-reaction flask; 6-supporting rods; 7-adjusting valve; 8-adjusting rod.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: SiO (silicon dioxide)2The grafted polyamide curing agent toughening modified epoxy resin comprises the following raw materials and components: epoxy resin, SiO2The mass ratio of the graft polyamide curing agent to the defoaming agent is 100:30-50: 0.2-0.8.
SiO2The preparation method of the grafted polyamide curing agent toughening modified epoxy resin comprises the following steps:
(1) adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 3-5:1, adding hexadecyl trimethyl ammonium bromide, dropwise adding ammonia water to adjust the pH value of the solution to 9-10, then adding tetraethoxysilane, the mass ratio of the tetraethoxysilane to the hexadecyl trimethyl ammonium bromide is 6-8:1, stirring at a constant speed for 5-10 hours, centrifugally separating the solution to remove the solvent, dispersing a solid product in the ethanol solvent, placing the solution in a constant-temperature water bath kettle, wherein the constant-temperature water bath kettle comprises a heat insulation layer, a water bath is arranged in the heat insulation layer, a base is fixedly connected with the water bath, a reaction bottle is arranged above the base, a support rod is fixedly connected in the base, an adjusting valve is movably connected with the support rod, an adjusting valve is movably connected with the adjusting rod, heating is carried out to 40, calcining for 2-3h at the temperature of 300-2。
(2) Adding toluene solvent and nano-porous SiO into a reaction bottle2Adding epoxy silane coupling agent after ultrasonic dispersion, wherein the epoxy silane coupling agent is any one of 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane, and nano porous SiO2The mass ratio of the epoxy nano SiO is 0.5-3:10, the epoxy nano SiO is prepared by heating the mixture to 60-90 ℃ in a constant temperature water bath kettle, stirring the mixture at a constant speed for reaction for 10-20h, filtering, washing and drying the mixture2。
(3) Introducing nitrogen into a reaction bottle, adding N, N-dimethylformamide solvent and epoxidized nano SiO2Adding organic amine after ultrasonic dispersion, wherein the organic amine is any one of ethylenediamine, diethylenetriamine or triethylene tetramine, placing the mixture in a constant-temperature water bath kettle, heating to 50-80 ℃, uniformly stirring for reaction for 6-12h, reducing the temperature to 30-40 ℃, adding methyl acrylate and epoxidized nano SiO2The mass ratio of the organic amine to the methyl acrylate is 1:2-4:1.5-2.5, the mixture is stirred at a constant speed to react for 3-8h, the temperature is increased to 80-120 ℃, the reaction lasts for 20-30h, the solution is placed in an ice water bath to be cooled, distilled water is added until a large amount of precipitate is separated out, and the mixture is filteredFiltering, washing and drying to prepare SiO2And (3) a polyamide grafting curing agent.
(4) Adding epoxy resin, defoaming agent and SiO into acetone solvent2Grafting a polyamide curing agent, pouring the solution into a film forming mold after ultrasonic dispersion is uniform, and curing to form a film to prepare SiO2The grafted polyamide curing agent toughens and modifies the epoxy resin material.
Example 1
(1) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 3:1, adding hexadecyl trimethyl ammonium bromide, dropwise adding ammonia water to adjust the pH value of the solution to 9, adding tetraethoxysilane, the mass ratio of the solid product to the cetyl trimethyl ammonium bromide is 6:1, the mixture is stirred at a constant speed for reaction for 5 hours, the solution is centrifugally separated to remove the solvent, the solid product is dispersed in the ethanol solvent, in the constant-temperature water bath kettle, the constant-temperature water bath kettle comprises a heat insulation layer, a water bath is arranged in the heat insulation layer, a base is fixedly connected with the water bath, a reaction bottle is arranged above the base, a supporting rod is fixedly connected in the base, a regulating valve is movably connected, a regulating rod is movably connected with the regulating valve, the base is heated to 40 ℃, the base is stirred at a constant speed for 12 hours, the base is filtered, washed and dried, a solid product is placed in a muffle furnace, and the nano porous SiO is prepared by calcining for 2 hours at 300 ℃.2。
(2) Adding toluene solvent and nano-porous SiO into a reaction bottle2After ultrasonic dispersion is uniform, adding epoxy silane coupling agent 3-glycidyl ether oxypropyl trimethoxy silane and nano porous SiO2The mass ratio of the components is 0.5:10, the mixture is heated to 60 ℃ in a constant-temperature water bath kettle, stirred at a constant speed for reaction for 10 hours, filtered, washed and dried to prepare the epoxidized nano SiO2。
(3) Introducing nitrogen into a reaction bottle, adding N, N-dimethylformamide solvent and epoxidized nano SiO2Adding ethylenediamine after ultrasonic dispersion, placing in a constant temperature water bath, heating to 50 deg.C, stirring at uniform speed for 6 hr, cooling to 30-40 deg.C, adding methyl acrylate and epoxidized nano SiO2The mass ratio of the ethylenediamine to the methyl acrylate is 1:2:1.5, the mixture is stirred at a constant speed to react for 3 to 8 hours, the temperature is raised to 80 ℃, the reaction is carried out for 20 hours, and the solution is obtainedCooling in ice water bath, adding distilled water until a large amount of precipitate is separated out, filtering, washing and drying to obtain SiO2And (3) a polyamide grafting curing agent.
(4) Adding epoxy resin, defoaming agent and SiO into acetone solvent2Grafting a polyamide curing agent, wherein the mass ratio of the three is 100:0.2:30, pouring the solution into a film forming mold after ultrasonic dispersion is uniform, and curing to form a film to prepare SiO2The grafted polyamide curing agent toughens and modifies the epoxy resin material 1.
Example 2
(1) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 3.6:1, adding hexadecyl trimethyl ammonium bromide, dropwise adding ammonia water to adjust the pH value of the solution to 10, adding tetraethoxysilane, the mass ratio of the solid product to the cetyl trimethyl ammonium bromide is 6.5:1, the mixture is stirred at a constant speed for reaction for 5 hours, the solution is centrifugally separated to remove the solvent, the solid product is dispersed in the ethanol solvent, in the constant-temperature water bath kettle, the constant-temperature water bath kettle comprises a heat insulation layer, a water bath is arranged in the heat insulation layer, a base is fixedly connected with the water bath, a reaction bottle is arranged above the base, a supporting rod is fixedly connected in the base, a regulating valve is movably connected in the base, a regulating rod is movably connected in the regulating valve, the base is heated to 70 ℃, the base is stirred for 24 hours at a constant speed, the base is filtered, washed and dried, a solid product is placed in a muffle furnace, and the nano porous SiO is prepared by calcining for 3 hours at 300.2。
(2) Adding toluene solvent and nano-porous SiO into a reaction bottle2After ultrasonic dispersion is uniform, adding epoxy silane coupling agent, epoxy silane coupling agent 3-glycidyl ether oxypropyl triethoxysilane, and nano porous SiO2The mass ratio of the epoxy nano SiO is 1:10, the epoxy nano SiO is prepared by heating the mixture to 60 ℃ in a constant temperature water bath kettle, stirring the mixture at a constant speed for reaction for 20 hours, filtering, washing and drying2。
(3) Introducing nitrogen into a reaction bottle, adding N, N-dimethylformamide solvent and epoxidized nano SiO2Adding diethylenetriamine after ultrasonic dispersion, placing the mixture into a constant-temperature water bath kettle, heating the mixture to 80 ℃, stirring the mixture at a constant speed for reaction for 10 hours, reducing the temperature to 40 ℃, adding methyl acrylate, and epoxidizingNano SiO2The mass ratio of diethylenetriamine to methyl acrylate is 1:3:1.8, stirring at a constant speed for reaction for 8 hours, heating to 120 ℃, reacting for 30 hours, placing the solution in an ice water bath for cooling, adding distilled water until a large amount of precipitate is separated out, filtering, washing and drying to prepare SiO2And (3) a polyamide grafting curing agent.
(4) Adding epoxy resin, defoaming agent and SiO into acetone solvent2Grafting a polyamide curing agent, wherein the mass ratio of the three is 100:0.4:38, pouring the solution into a film forming mould after the ultrasonic dispersion is uniform, and curing to form a film to prepare SiO2And 2, toughening the modified epoxy resin material by the grafted polyamide curing agent.
Example 3
(1) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 4.2:1, adding hexadecyl trimethyl ammonium bromide, dropwise adding ammonia water to adjust the pH value of the solution to 10, adding tetraethoxysilane, the mass ratio of the solid product to the cetyl trimethyl ammonium bromide is 7:1, the mixture is stirred at a constant speed for reaction for 5 to 10 hours, the solution is centrifugally separated to remove the solvent, the solid product is dispersed in the ethanol solvent, in the constant-temperature water bath kettle, the constant-temperature water bath kettle comprises a heat insulation layer, a water bath is arranged in the heat insulation layer, a base is fixedly connected with the water bath, a reaction bottle is arranged above the base, a supporting rod is fixedly connected in the base, a regulating valve is movably connected in the base, a regulating rod is movably connected in the regulating valve, the base is heated to 65 ℃, the base is stirred at a constant speed for 20 hours, the base is filtered, washed and dried, a solid product is placed in a muffle furnace, and the nano porous SiO is prepared by calcining for 2.5 hours at 350.2。
(2) Adding toluene solvent and nano-porous SiO into a reaction bottle2Adding epoxy silane coupling agent after ultrasonic dispersion, wherein the epoxy silane coupling agent is 3-glycidyl ether oxypropyl triethoxysilane and nano porous SiO2The mass ratio of (2.2: 10) is heated to 75 ℃ in a constant-temperature water bath kettle, stirred at a constant speed for reaction for 15 hours, filtered, washed and dried to prepare the epoxidized nano SiO2。
(3) Introducing nitrogen into a reaction bottle, adding N, N-dimethylformamide solvent and epoxidized nano SiO2Uniform ultrasonic dispersionThen adding triethylene tetramine, placing the mixture into a constant-temperature water bath kettle, heating the mixture to 65 ℃, uniformly stirring the mixture for reaction for 10 hours, reducing the temperature to 35 ℃, then adding methyl acrylate and epoxidized nano SiO2The mass ratio of triethylene tetramine to methyl acrylate is 1:3.2:2.2, the mixture is stirred at a constant speed to react for 5 hours, the temperature is increased to 100 ℃, the reaction is carried out for 25 hours, the solution is placed in an ice water bath to be cooled, distilled water is added until a large amount of precipitate is separated out, and the solution is filtered, washed and dried to prepare SiO2And (3) a polyamide grafting curing agent.
(4) Adding epoxy resin, defoaming agent and SiO into acetone solvent2Grafting a polyamide curing agent, wherein the mass ratio of the three is 100:0.6:40, pouring the solution into a film forming mold after ultrasonic dispersion is uniform, and curing to form a film to prepare SiO2And 3, toughening the modified epoxy resin material by using the grafted polyamide curing agent.
Example 4
(1) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 5:1, adding hexadecyl trimethyl ammonium bromide, dropwise adding ammonia water to adjust the pH value of the solution to 10, adding tetraethoxysilane, the mass ratio of the solid product to the cetyl trimethyl ammonium bromide is 8:1, the mixture is stirred at a constant speed for reaction for 10 hours, the solution is centrifugally separated to remove the solvent, the solid product is dispersed in the ethanol solvent, in the constant-temperature water bath kettle, the constant-temperature water bath kettle comprises a heat insulation layer, a water bath is arranged in the heat insulation layer, a base is fixedly connected with the water bath, a reaction bottle is arranged above the base, a supporting rod is fixedly connected in the base, a regulating valve is movably connected in the base, a regulating rod is movably connected in the regulating valve, the base is heated to 70 ℃, the base is stirred for 24 hours at a constant speed, the base is filtered, washed and dried, a solid product is placed in a muffle furnace, and the nano porous SiO is prepared by calcining for 3 hours at 400.2。
(2) Adding toluene solvent and nano-porous SiO into a reaction bottle2Adding epoxy silane coupling agent after ultrasonic dispersion is uniform, wherein the epoxy silane coupling agent is 3-glycidyl ether oxypropyl trimethoxy silane and nano porous SiO2The mass ratio of the epoxy nano SiO is 3:10, the epoxy nano SiO is prepared by heating the materials to 90 ℃ in a constant temperature water bath kettle, stirring the materials at a constant speed for reaction for 20 hours, filtering, washing and drying2。
(3) Introducing nitrogen into a reaction bottle, adding N, N-dimethylformamide solvent and epoxidized nano SiO2Adding diethylenetriamine after ultrasonic dispersion, placing the mixture into a constant-temperature water bath kettle, heating the mixture to 80 ℃, stirring the mixture at a constant speed for reaction for 12 hours, reducing the temperature to 30-40 ℃, adding methyl acrylate and epoxidized nano SiO2Reacting for 3-8h at a constant speed with stirring, heating to 120 ℃, reacting for 30h, cooling the solution in ice water bath, adding distilled water until a large amount of precipitate is separated out, filtering, washing and drying to obtain SiO2And (3) a polyamide grafting curing agent.
(4) Adding epoxy resin, defoaming agent and SiO into acetone solvent2Grafting a polyamide curing agent, wherein the mass ratio of the three is 100:0.8:50, pouring the solution into a film forming mold after ultrasonic dispersion is uniform, and curing to form a film to prepare SiO2And 4, toughening the modified epoxy resin material by the grafted polyamide curing agent.
Comparative example 1
(1) Adding a mixed solvent of distilled water and ethanol into a reaction bottle, wherein the volume ratio of the distilled water to the ethanol is 2:1, adding hexadecyl trimethyl ammonium bromide, dropwise adding ammonia water to adjust the pH value of the solution to 10, adding tetraethoxysilane, the mass ratio of the solid product to the cetyl trimethyl ammonium bromide is 5:1, the mixture is stirred at a constant speed for reaction for 10 hours, the solution is centrifugally separated to remove the solvent, the solid product is dispersed in the ethanol solvent, in the constant-temperature water bath kettle, the constant-temperature water bath kettle comprises a heat insulation layer, a water bath is arranged in the heat insulation layer, a base is fixedly connected with the water bath, a reaction bottle is arranged above the base, a supporting rod is fixedly connected in the base, a regulating valve is movably connected in the base, a regulating rod is movably connected in the regulating valve, the base is heated to 70 ℃, the base is stirred for 24 hours at a constant speed, the base is filtered, washed and dried, a solid product is placed in a muffle furnace, and the nano porous SiO is prepared by calcining for 3 hours at 300.2。
(2) Adding toluene solvent and nano-porous SiO into a reaction bottle2Adding epoxy silane coupling agent after ultrasonic dispersion, wherein the epoxy silane coupling agent is 3-glycidyl ether oxypropyl triethoxysilane and nano porous SiO2In a mass ratio of0.2:10, heating to 90 ℃ in a constant-temperature water bath kettle, uniformly stirring for reaction for 20 hours, filtering, washing and drying to prepare the epoxidized nano SiO2。
(3) Introducing nitrogen into a reaction bottle, adding N, N-dimethylformamide solvent and epoxidized nano SiO2Adding ethylenediamine after ultrasonic dispersion, placing in a constant temperature water bath kettle, heating to 90 deg.C, stirring at uniform speed for 12 hr, cooling to 30-40 deg.C, adding methyl acrylate and epoxidized nano SiO2The mass ratio of the ethylenediamine to the methyl acrylate is 1:1.5:4, the mixture is stirred at a constant speed for reaction for 3-8h, the temperature is raised to 120 ℃, the reaction is carried out for 20-30h, the solution is placed in an ice water bath for cooling, distilled water is added until a large amount of precipitate is separated out, and the SiO is obtained by filtering, washing and drying2And (3) a polyamide grafting curing agent.
(4) Adding epoxy resin, defoaming agent and SiO into acetone solvent2Grafting a polyamide curing agent, wherein the mass ratio of the three is 100:0.5:15, pouring the solution into a film forming mold after ultrasonic dispersion is uniform, and curing to form a film to prepare SiO2The grafted polyamide curing agent toughens and modifies the epoxy resin comparative material 1.
SiO test in examples 1-5 Using WEW-1000D Microcomputer Screen display type tensile tester2The tensile strength and the elongation at break of the modified epoxy resin material toughened by the grafted polyamide curing agent are in GB/T1040.2-2006.
In summary, the SiO2The grafted polyamide curing agent toughening modified epoxy resin takes cetyl trimethyl ammonium bromide as a template agent to obtain the nano porous SiO2Has abundant mesoporous structure and large specific surface area, thereby increasing the nano SiO2The hydroxyl content on the surface is improved, and the epoxy silane coupling agent to nano SiO is improved2The grafting rate of (2) is that a large amount of epoxy groups and amino groups of organic amine carry out ring-opening reaction, and then organic amine is used for grafting nano SiO2With the terminal amino group as a chemical reaction site with acrylic acidThe alkenyl of the ester is subjected to Michael addition reaction to prepare SiO2The grafted polyamide is used as a curing agent, a large number of amino and imino groups and epoxy groups of epoxy resin are subjected to ring-opening crosslinking curing, and nano SiO is obtained2Covalent grafting is introduced into the matrix of the epoxy resin coating material, so that nano SiO is avoided2Problems of agglomeration and sedimentation, uniformly dispersed nano SiO2Has obvious toughening effect on the epoxy resin coating, and greatly enhances the tensile strength and the elongation at break of the material.
Claims (5)
1. SiO (silicon dioxide)2The grafted polyamide curing agent toughening modified epoxy resin comprises the following raw materials and components, and is characterized in that: epoxy resin, SiO2The mass ratio of the graft polyamide curing agent to the defoaming agent is 100:30-50: 0.2-0.8.
2. An SiO as claimed in claim 12The grafted polyamide curing agent toughening modified epoxy resin is characterized in that: the SiO2The preparation method of the grafted polyamide curing agent toughening modified epoxy resin comprises the following steps:
(1) adding hexadecyl trimethyl ammonium bromide into a mixed solvent of distilled water and ethanol with the volume ratio of 3-5:1, dropwise adding ammonia water to adjust the pH value of the solution to 9-10, then adding ethyl orthosilicate with the mass ratio of the hexadecyl trimethyl ammonium bromide to 6-8:1, reacting for 5-10h, centrifugally separating to remove the solvent, dispersing a solid product into the ethanol solvent, heating to 40-70 ℃ in a constant-temperature water bath kettle for reacting for 12-24h, filtering, washing and drying, placing the solid product into a muffle furnace, and performing heat preservation and calcination for 2-3h at the temperature of 300 ℃ to 400 ℃ to prepare the nano porous SiO2；
(2) Adding nano porous SiO into toluene solvent2Uniformly dispersing by ultrasonic, adding epoxy silane coupling agent, heating to 60-90 ℃, reacting for 10-20h, filtering, washing and drying to obtain the epoxidized nano SiO2；
(3) Adding and epoxidizing nano SiO into N, N-dimethylformamide solvent in nitrogen atmosphere2Adding organic amine after ultrasonic dispersion, and placing at constant temperatureHeating to 50-80 deg.C in water bath, reacting for 6-12h, cooling to 30-40 deg.C, adding methyl acrylate, reacting for 3-8h, heating to 80-120 deg.C, reacting for 20-30h, cooling, precipitating, filtering, washing, and drying to obtain SiO2A grafted polyamide curing agent;
(4) adding epoxy resin, defoaming agent and SiO into acetone solvent2Grafting a polyamide curing agent, pouring the solution into a film forming mold after ultrasonic dispersion is uniform, and curing to form a film to prepare SiO2The grafted polyamide curing agent toughens and modifies the epoxy resin material.
3. An SiO as claimed in claim 22The grafted polyamide curing agent toughening modified epoxy resin is characterized in that: the constant-temperature water bath kettle comprises a heat preservation layer, a water bath tank is arranged inside the heat preservation layer, a water bath tank fixedly connected base and a reaction bottle are arranged above the base, and a support rod, a regulating valve and a regulating valve movably connected inside the base are movably connected with a regulating rod.
4. An SiO as claimed in claim 22The grafted polyamide curing agent toughening modified epoxy resin is characterized in that: the epoxy silane coupling agent is any one of 3-glycidyl ether oxypropyl trimethoxysilane or 3-glycidyl ether oxypropyl triethoxysilane, and nano porous SiO2The mass ratio of (A) to (B) is 0.5-3: 10.
5. An SiO as claimed in claim 22The grafted polyamide curing agent toughening modified epoxy resin is characterized in that: the organic amine is any one of ethylenediamine, diethylenetriamine or triethylene tetramine, and epoxidized nano SiO2The mass ratio of the organic amine to the methyl acrylate is 1:2-4: 1.5-2.5.
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