CN106751480B - Layered inorganic filler/epoxy resin nano composite material and preparation method thereof - Google Patents
Layered inorganic filler/epoxy resin nano composite material and preparation method thereof Download PDFInfo
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5033—Amines aromatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
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- 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
- C08K3/02—Elements
- C08K3/04—Carbon
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- 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
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- 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
Abstract
The invention relates to a layered inorganic filler/epoxy resin nano composite material and a preparation method thereof, in particular to a nano composite material which is composed of epoxy resin, a curing agent and a layered inorganic nano filler modified by a prepolymer of the epoxy resin and the curing agent and is obtained by heating and curing, and a preparation method thereof. Specifically, the layered inorganic nano filler is organically modified by using a prepolymer of epoxy resin and a curing agent, and is mixed with the epoxy resin and the curing agent by mechanical stirring and/or ball milling, and then is heated, cured and molded. The prepolymer of epoxy matrix is adopted to modify the inorganic layered filler, so that the compatibility and the interface strength between the filler and the matrix can be effectively improved. Therefore, the nano composite material prepared by the method has excellent barrier property and mechanical property (high strength and high modulus), can be used alone or compounded with fibers to prepare fiber reinforced composite materials, and is widely applied to the fields of high-barrier, high-toughness packaging materials, high-temperature or low-temperature resistant fuel storage tanks and the like.
Description
Technical Field
The invention relates to a layered inorganic filler/epoxy resin nano composite material and a preparation method thereof, in particular to a nano composite material which is composed of epoxy resin, a curing agent and a layered inorganic nano filler modified by the epoxy resin and a curing agent prepolymer and has excellent barrier property and mechanical property and a preparation method thereof.
Background
The epoxy resin is a thermosetting material with excellent properties, contains two or more than two epoxy groups in the molecule, can generate epoxy ring-opening reaction with a curing agent, and is crosslinked and cured to form a high polymer material with a three-dimensional network structure. Commonly used curing agents include amine curing agents, anhydride curing agents, anionic and cationic polymeric curing agents, and the like. Because of its excellent properties such as high bonding strength, low shrinkage, good stability, excellent electrical insulation, high mechanical strength and good processability, it has been widely applied in various fields of national economy, relating to the high and new technology field, general technical field, national defense and military industry, civil industry, etc. However, due to the creep property of the polymer segment itself and the multiplicity of moving units, the gas barrier property of epoxy resin is poor, limiting its application in the fields of high-barrier packaging materials, fuel tanks, and the like.
At present, methods for enhancing the gas barrier property of polymer materials include a film coating method, a blending method, a compounding method and a filling method. The blending method and the compounding method are to blend or compound multiple polymers in multiple layers so as to improve the integral gas barrier property of the material, but usually at the cost of the loss of mechanical properties; the film coating method is to add a layer of gas isolation layer on the surface of the polymer through surface treatment, film coating and the like, and has the defects of high cost, complex process and easy falling of the isolation layer. The filling method is to add the layered inorganic nano material into the polymer matrix, and improve the diffusion path of gas molecules in the polymer by using the barrier of the nanosheet layer, so that the barrier property of the composite material is improved, and meanwhile, the layered inorganic nano material can also improve the mechanical property of the polymer-based composite material.
With the development of nanotechnology, researches on improving the barrier property, mechanical property and the like of epoxy resin by modifying the epoxy resin with a layered inorganic nanomaterial are also more and more extensive. The existing layered inorganic nano-filler mainly comprises montmorillonite, vermiculite, rectorite, sepiolite, attapulgite, muscovite, graphene oxide and the like. However, since the inorganic material and the organic polymer material have different structures and opposite properties, the compatibility of the layered inorganic filler with the polymer is poor; due to the binary composition of the epoxy resin (the epoxy resin and the curing agent), the compatibility between the organically modified montmorillonite and the matrix resin is more complex, the dispersion of the nanosheet layer in the epoxy resin is not facilitated, and the performance of the composite material is greatly influenced. Therefore, it is important to select a suitable organic modifier for organically modifying the layered inorganic filler while improving its compatibility with the epoxy resin and the curing agent.
For the layered inorganic nano-filler with positive charges between layers, the preparation of the modified inorganic material by adopting organic cations through cation exchange intercalation is an effective method. Commonly used organic cation intercalating agents include alkylamine salts, quaternary ammonium salts, polyether amine salts, and the like. The intercalation agent can effectively improve the lamella spacing of the lamellar inorganic nano-filler and the compatibility with a polymer matrix, but because the molecular structures of the modifier and the resin matrix are different, the dispersion state of the modified filler in the resin is still not ideal (mainly in an intercalation type), and the intercalation agent is not beneficial to competition of interlayer polymerization reaction and outer layer polymerization reaction. To solve this problem, gareas.a [ Applied Clay Science, 2010, 50: 469-475 reacting epoxy DGEBA with two monoamines (B100 and XTJ505) to obtain epoxy-monoamine adduct, protonating, intercalating montmorillonite, and mixing with epoxy and diamine curing agent to obtain montmorillonite/epoxy nanocomposite. The results show that: compared with the montmorillonite modified by long-chain quaternary ammonium salt, the montmorillonite modified by the epoxy-monoamine adduct not only has better compatibility with an epoxy resin matrix, but also can promote the polymerization reaction of interlayer epoxy and a curing agent by taking the cation of the epoxy-monoamine adduct in a montmorillonite crystal layer as a catalyst, thereby being more beneficial to obtaining the exfoliated epoxy/montmorillonite nanocomposite, and particularly being capable of obtaining the completely exfoliated epoxy/montmorillonite nanocomposite when an epoxy prepolymer used for synthesizing the adduct is taken as the matrix epoxy resin. However, no functional groups chemically bond to the epoxy resin matrix after acidification of the epoxy-monoamine intercalator, resulting in poor interfacial bonding between the modified inorganic filler and the resin matrix. For the layered inorganic filler/epoxy resin nano composite material, the improvement of the properties such as barrier property, mechanics and the like is limited by the existing inorganic/organic weak interfaces in large quantity.
From the above, it can be presumed that: the epoxy and curing agent which form the epoxy resin matrix are used as raw materials to synthesize the epoxy prepolymer with large molecular weight or the partially acidified prepolymer salt modified inorganic layered material, which is an ideal method for modifying the nano-filler applied to the modification of the epoxy resin and has the most application potential in developing the layered inorganic filler/epoxy resin nano-composite material with excellent barrier property and mechanical property. Similar studies have not been reported.
Disclosure of Invention
The invention aims to improve the interface between the inorganic filler and the epoxy resin by organically modifying the layered inorganic nano filler, thereby improving the barrier property and the mechanical property of the layered inorganic filler/epoxy resin nano composite material.
In order to achieve the above object, the present invention provides a layered inorganic filler/epoxy resin nanocomposite and a method for preparing the same.
The invention relates to a layered inorganic filler/epoxy resin nano composite material, which is prepared from epoxy resin, a curing agent and a layered inorganic nano filler modified by a prepolymer of the epoxy resin and the curing agent, wherein the ratio of each component is as follows: the equivalent ratio of the epoxy resin to the curing agent is 0.9-1.1, the prepolymer modified layered inorganic filler accounts for 0.01-80 wt% of the total amount of the nano composite material, and the prepolymer accounts for 1-90 wt% of the total amount of the prepolymer modified layered inorganic filler.
The layered inorganic filler/epoxy resin nanocomposite material is characterized in that the epoxy resin is one or a mixture of two or more of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy compound and linear aliphatic epoxy compound.
Specifically, the epoxy resin provided by the invention is epoxy E51 or TDE 85.
The invention relates to a layered inorganic filler/epoxy resin nano composite material, wherein a curing agent is one or a mixture of two or more of polyamine, acid anhydride and imidazole.
Specifically, the curing agent is one or a mixture of two or more of polyether amine (D400, D2000 and T5000), m-phenylenediamine, diaminodiphenyl sulfone, 2-ethyl-4-methylimidazole and 2-phenylimidazole.
The layered inorganic filler/epoxy resin nano composite material is one or a mixture of two or more of montmorillonite, vermiculite, rectorite, sepiolite, attapulgite, muscovite and graphene oxide.
The invention relates to a layered inorganic filler/epoxy resin nano composite material, which comprises the following preparation processes: (1) weighing epoxy resin and a curing agent with an equivalent ratio of 0.9-1.1, polymerizing at a temperature lower than the initial curing temperature, and controlling the reaction time to finish the reaction before gelation to obtain a prepolymer of the epoxy resin and the curing agent; (2) dissolving or melting the prepolymer, and adding a certain amount of hydrochloric acid to obtain prepolymer salt; (3) mixing the prepolymer or/and prepolymer salt and the layered inorganic nano-filler by stirring or/and ultrasonic or/and ball milling for 1-24 hours to obtain the prepolymer modified layered inorganic nano-filler; (4) adding the layered inorganic nano filler modified by the prepolymer into epoxy resin, and fully mixing by stirring or/and ball milling; (5) removing the solvent from the mixed system, and fully mixing by stirring or/and ball milling; (6) adding a curing agent according to the equivalent ratio of 0.9-1.1 to the epoxy resin, and fully mixing by mechanical stirring or/and ball milling; (7) vacuumizing to remove bubbles, pouring the mixed system into a mould, and heating, curing and molding.
The preparation method of the layered inorganic filler/epoxy resin nano composite material is characterized in that functional groups in the prepolymer are partially acidified by controlling the dosage of hydrochloric acid to prepare prepolymer salt; the acidified cations are subjected to cation exchange with cations between the layers of the layered inorganic filler, and the non-acidified functional groups are reacted with epoxy groups of the epoxy resin, thereby improving the interfacial bonding of the inorganic filler and the resin matrix.
Compared with the prior art, the layered inorganic filler/epoxy resin nano composite material and the preparation method thereof have the advantages that the prepolymer with the same structure as the matrix is adopted to modify the layered inorganic filler, so that the interface bonding of the inorganic sheet layer and the resin matrix is improved. The composite material and the fiber reinforced nano composite material compounded with the carbon fiber have excellent barrier property and mechanical property. For epoxy E51 and epoxy TDE85 resin systems, the barrier property of the nano composite material is 2-10 times of that of pure epoxy resin, the tensile strength and the bending strength are 1.1-3 times of those of the pure epoxy resin, and the tensile modulus and the bending modulus are 1.1-5 times of those of the pure epoxy resin, so that the nano composite material can be widely applied to the fields of high-barrier packaging materials, fuel storage tanks and the like.
Detailed Description
Example 1
Weighing 10.2g of bisphenol A epoxy resin (E51) and 6.0g of polyetheramine (D400), and mechanically stirring for 2 hours at 100 ℃ to prepare an E51-D400 prepolymer; adding a proper amount of acetone to dissolve the prepolymer, dripping an acetone solution of hydrochloric acid, wherein the amount and the concentration of substances of the hydrochloric acid are 0.5 times of the amount and the concentration of amino in the prepolymer solution, and magnetically stirring for 3 hours in an ice-water bath to obtain semi-ammonium salt of the E51-D400 prepolymer; 30g of montmorillonite (CEC is 100mmol/100g) aqueous solution is dropped into the half ammonium salt solution of the E51-D400 prepolymer, heated and stirred for 4h at 70 ℃ to obtain the E51-D400 prepolymer modified montmorillonite. Adding 3g of modified montmorillonite corresponding to the montmorillonite into 61g E51 resin, mechanically stirring for 30h, and ball-milling for 60 h; vacuumizing at room temperature to remove the solvent, and continuing ball milling for 30 hours; then, 36g of curing agent D400 is added, and ball milling is continued for 30-60min after mechanical stirring is carried out uniformly; and finally, vacuumizing to remove bubbles, pouring the mixed system into a mold, and curing at 75 ℃ for 2h, 115 ℃ for 2h and 150 ℃ for 2 h.
Example 2
Weighing 5.1g E51 and 3.0g D400, mixing, mechanically stirring for 2h at 100 ℃ to obtain E51-D400 prepolymer, and adding a proper amount of acetone to dissolve; and (3) dripping the E51-D400 prepolymer solution into 1g of graphene oxide aqueous solution, and stirring at room temperature for 2 hours to obtain the E51-D400 prepolymer modified graphene oxide. Adding 0.5g of modified graphene oxide corresponding to graphene oxide into 61g of E51 resin, mechanically stirring for 30h, and ball-milling for 60 h; vacuumizing at room temperature to remove the solvent, and continuing ball milling for 30 hours; then, 38g of curing agent D400 is added, and ball milling is continued for 30-60min after mechanical stirring is carried out uniformly; and finally, vacuumizing to remove bubbles, pouring the mixed system into a mold, and curing at 75 ℃ for 2h, 115 ℃ for 2h and 150 ℃ for 2 h.
Example 3
Weighing 1.8g of m-phenylenediamine (mPDA), heating to 115 ℃ for 15min, naturally cooling to 40 ℃, adding 10.0g of 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester resin (TDE85) with the temperature of 60 ℃, and mechanically stirring for 3h at 40 ℃ to prepare a TDE85-mPDA prepolymer; adding a proper amount of acetone to dissolve the prepolymer, dripping an acetone solution of hydrochloric acid, wherein the amount and the concentration of substances of the hydrochloric acid are 0.5 times of the amount and the concentration of amino in the prepolymer solution, and reacting for 3 hours under magnetic stirring in an ice water bath to obtain TDE85-mPDA prepolymer semi-ammonium salt; 30.0g of montmorillonite (CEC is 100mmol/100g) aqueous solution is dropped into TDE85-mPDA prepolymer half ammonium salt solution, heated and stirred for 4h at 60 ℃, and TDE85-mPDA prepolymer modified montmorillonite is obtained. Adding modified soil corresponding to 3.0g of montmorillonite into 82.2g of TDE85 resin, mechanically stirring for 30h, and ball-milling for 60 h; vacuumizing at room temperature to remove the solvent, and continuing ball milling for 30 hours; then, 14.8g of mPDA is added, and ball milling is continued for 30-60min after mechanical stirring is carried out uniformly; and finally, vacuumizing to remove bubbles, pouring the mixed system into a mold, and curing at 40 ℃ for 2h, at 80 ℃ for 2h and at 120 ℃ for 3 h.
Example 4
Weighing 0.9g of mPDA, heating to 115 ℃ for 15min, naturally cooling to 40 ℃, adding 5.0g of TDE85 resin with the temperature of 60 ℃, mechanically stirring for 3h at 40 ℃ to prepare a TDE85-mPDA prepolymer, and adding a proper amount of acetone for dissolving; and (3) dripping the TDE85-mPDA prepolymer solution into 1.0g of graphene oxide aqueous solution, and stirring at room temperature for 2 hours to obtain TDE85-mPDA prepolymer modified graphene oxide. Adding 0.5g of modified graphene oxide corresponding to graphene oxide into 83.9g of TDE85 resin, mechanically stirring for 30h, and ball-milling for 60 h; vacuumizing at room temperature to remove the solvent, and continuing ball milling for 30 hours; then, adding 15.1g of mPDA, mechanically stirring uniformly, and continuing ball milling for 30-60 min; and finally, vacuumizing to remove bubbles, pouring the mixed system into a mold, and curing at 40 ℃ for 2h, at 80 ℃ for 2h and at 120 ℃ for 3 h.
Mechanical and barrier property tests were performed on the E41/D400 and TDE85/mPDA resin matrices and the layered inorganic filler/epoxy nanocomposite prepared in examples 1 to 4. Testing the tensile and flexural properties of the resin matrix and nanocomposite according to the standards ASTM D638-10 and ASTM D790-10, respectively; the nitrogen transmission coefficient was measured according to the standard ASTM D1434-82. The test results are shown in Table 1.
TABLE 1 mechanical and Barrier Properties of the resin matrix and nanocomposite
Example 5
The nanocomposite material obtained in example 4 was compounded with T700 carbon fiber, and heated and cured to prepare a unidirectional carbon fiber reinforced resin-based nanocomposite material. According to standard GBThe tensile property and the bending property of the carbon fiber reinforced epoxy resin and the carbon fiber reinforced nano filler modified epoxy resin are tested by the aid of/T1447 and GB/T1449; the nitrogen permeability at the same thickness was tested according to the standard ASTM D1434-82 (gas permeability coefficient is only significant for homogeneous materials). The results show that the tensile strength and the modulus of the carbon fiber composite material are respectively improved from 930MPa and 46.8GPa to 945MPa and 51.2GPa by using the epoxy resin modified by the layered inorganic filler as the matrix of the carbon fiber composite material; the bending strength and the modulus are improved from 133MPa and 3.88GPa to 156MPa and 4.13 GPa; the nitrogen gas permeability is from 0.38cm3/m2The 24h0.1MPa is reduced to 0.24cm3/m224h0.1MPa。
In conclusion, the mechanical property and the gas barrier property of the layered inorganic filler/epoxy resin nanocomposite material and the carbon fiber composite material thereof prepared by the method are remarkably improved.
Claims (6)
1. The layered inorganic filler/epoxy resin nano composite material is characterized by being prepared from epoxy resin, a curing agent and a layered inorganic nano filler modified by a prepolymer of the epoxy resin and the curing agent, wherein the ratio of each component is as follows: the equivalent ratio of the epoxy resin to the curing agent is 0.9-1.1, the prepolymer modified layered inorganic filler accounts for 0.01-80 wt% of the total amount of the nano composite material, and the prepolymer accounts for 1-90 wt% of the total amount of the prepolymer modified layered inorganic filler; the curing agent is polyamine; when the epoxy resin-polyamine prepolymer modified layered inorganic nano filler is prepared, the equivalent ratio of the epoxy resin to the curing agent is 1.1, and the dosage of hydrochloric acid is controlled to ensure that the amino functional groups in the prepolymer are partially acidified to prepare prepolymer salt; after the prepolymer salt is used for modifying the layered inorganic nano filler, amino functional groups which are not acidified can still participate in the curing reaction in the epoxy resin matrix;
the epoxy resin is a mixture of more than one of glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy compound and linear aliphatic epoxy compound;
the curing agent is a mixture of more than one of polyether amine, m-phenylenediamine and diamino diphenyl sulfone.
2. The layered inorganic filler/epoxy nanocomposite as claimed in claim 1, wherein the layered inorganic nanofiller is a mixture of more than one of montmorillonite, vermiculite, rectorite, sepiolite, attapulgite, muscovite and graphene oxide.
3. The layered inorganic filler/epoxy nanocomposite as claimed in claim 1, wherein the epoxy resin is epoxy E51 or TDE 85.
4. The layered inorganic filler/epoxy nanocomposite as claimed in claim 1, wherein the curing agent is a mixture of one or more of D400, D2000, and T5000.
5. A process for the preparation of a layered inorganic filler/epoxy resin nanocomposite as claimed in any one of claims 1 to 4, which comprises: (1) weighing epoxy resin and a curing agent with an equivalent ratio of 1.1, polymerizing at a temperature lower than the initial curing temperature, and controlling the reaction time to finish the reaction before gelation to obtain a prepolymer of the epoxy resin and the curing agent; (2) dissolving or melting the prepolymer, and adding a certain amount of hydrochloric acid to obtain prepolymer salt, wherein the amount and the concentration of substances of the hydrochloric acid are 0.5 times of the amount and the concentration of amino in the prepolymer solution; (3) mixing the prepolymer or/and prepolymer salt and the layered inorganic nano-filler by stirring or/and ultrasonic or/and ball milling for 1-24 hours to obtain the prepolymer modified layered inorganic nano-filler; (4) adding the layered inorganic nano filler modified by the prepolymer into epoxy resin, and fully mixing by stirring or/and ball milling; (5) removing the solvent from the mixed system, and fully mixing by stirring or/and ball milling; (6) adding a curing agent according to the equivalent ratio of 0.9-1.1 to the epoxy resin, and fully mixing by mechanical stirring or/and ball milling; (7) vacuumizing to remove bubbles, pouring the mixed system into a mould, and heating, curing and molding.
6. The method of claim 5, wherein the tensile strength, tensile modulus, flexural strength and flexural modulus of the nanocomposite and the fiber-reinforced nanocomposite compounded with carbon fiber are increased and the nitrogen permeability coefficient is decreased compared to pure epoxy and carbon fiber/epoxy composite.
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