CN114163780A - Epoxy resin composition and preparation method and application thereof - Google Patents
Epoxy resin composition and preparation method and application thereof Download PDFInfo
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- CN114163780A CN114163780A CN202111536075.8A CN202111536075A CN114163780A CN 114163780 A CN114163780 A CN 114163780A CN 202111536075 A CN202111536075 A CN 202111536075A CN 114163780 A CN114163780 A CN 114163780A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/025—Electric or magnetic properties
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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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B17/00—Insulators or insulating bodies characterised by their form
- H01B17/56—Insulating bodies
- H01B17/60—Composite insulating bodies
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B19/00—Apparatus or processes specially adapted for manufacturing insulators or insulating bodies
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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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
- C08K3/18—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
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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- Physics & Mathematics (AREA)
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- Epoxy Resins (AREA)
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Abstract
The invention provides an epoxy resin composition and a preparation method and application thereof. The epoxy resin composition comprises, by weight, 90-110 parts of epoxy resin, 100-120 parts of an inorganic flame retardant and 3-35 parts of a curing agent; the epoxy resin comprises a combination of bisphenol A type epoxy resin, triglycidyl type epoxy resin and tetraglycidyl amine type epoxy resin; the inorganic flame retardant includes a modified metal hydroxide flame retardant. The preparation method of the epoxy resin composition comprises the following steps: reacting the epoxy resin with a curing agent to obtain cured epoxy resin; and mixing the cured epoxy resin with an inorganic flame retardant, dispersing and grinding to obtain the epoxy resin composition. The epoxy resin composition selects the epoxy resin, the modified metal hydroxide flame retardant and the curing agent which are specially combined, so that the epoxy resin laminated board has excellent mechanical property, insulating property and flame retardant property.
Description
Technical Field
The invention belongs to the technical field of electrical materials, and particularly relates to an epoxy resin composition, and a preparation method and application thereof.
Background
The epoxy resin is a thermosetting resin, has large yield, various varieties and excellent physical and mechanical properties and electrical properties, and is widely applied to the fields of coatings, adhesives, electronic and electric appliances and the like; the use of epoxy impregnated fibers or fabrics is common, particularly in the field of electrical insulation. However, due to the particularity of electronics and electricity, and with the increasing awareness of safety and environmental protection, it is required that the material not only have excellent mechanical properties and insulating properties, but also have flame retardancy and low toxicity.
For example, CN106916416A discloses a phosphorus-containing nitrogen-containing halogen-free flame retardant epoxy resin adhesive, a prepreg and a high temperature resistant halogen-free flame retardant insulating structural member. The raw material formula of the epoxy resin adhesive comprises phosphorus-containing halogen-free epoxy resin, triallyl isocyanurate, 4' -bismaleimide diphenylmethane, a curing agent, a curing accelerator, a coloring agent and a solvent. The prepreg and the insulating structural member made of the epoxy resin adhesive have high temperature resistance (H level), and the flame retardance can reach the UL 94V-0 level flame retardance standard; the insulating structural member can further improve the flame retardant property of the H-level laminated plate. However, the mechanical properties of the material are deficient.
CN102407630A discloses a halogen-free flame-retardant phenolic epoxy glass cloth laminated board and a preparation method thereof. The laminate comprises an alkali-free glass cloth and a matrix resin; wherein, the matrix resin comprises the following components: epoxy resin, phenolic resin, aromatic amine curing agent and halogen-free phosphorus-containing nitrogen-containing flame retardant. The laminate can achieve the UL 94V-0 grade flame retardant standard in vertical combustion, has excellent flame retardant effect and better electrical and mechanical properties, can be used for printed circuit boards and other related electronic and electrical insulating materials or structural materials, but is not beneficial to environmental protection and health because the materials comprise phosphorus-containing flame retardants.
CN109735100A discloses an antimonide-free halogen-containing flame-retardant polyamide composite material and a preparation method thereof, wherein the composite material comprises, by weight, 20-80 parts of polyamide resin, 1-30 parts of a brominated flame retardant and 0.01-15 parts of condensed aluminum phosphate. The invention adopts condensed aluminum phosphate as a novel flame retardant, can achieve the flame retardant effect which is equal to that of a bromine-antimony flame retardant system on the premise of not introducing antimony white, and can endow bromine flame retardant polyamide with excellent electrical properties. However, bromine-containing resin generates many harmful substances including dioxin during combustion, and has high smoke concentration, thereby bringing great difficulty to rescue of fire and causing great damage to the environment.
Therefore, the development of a healthy and environment-friendly electric insulating material with good mechanical properties, high insulating property and good flame retardance is an urgent problem to be solved in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an epoxy resin composition, and a preparation method and application thereof. The epoxy resin composition enables the epoxy resin laminated board to have excellent mechanical property, insulating property and flame retardant property by synergistic use of epoxy resin, inorganic flame retardant and curing agent and selection of a combination of specific epoxy resin.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an epoxy resin composition, which comprises, by weight, 90-110 parts of an epoxy resin, 100-120 parts of an inorganic flame retardant and 3-35 parts of a curing agent; the epoxy resin comprises a combination of bisphenol A type epoxy resin, triglycidyl type epoxy resin and tetraglycidyl amine type epoxy resin; the inorganic flame retardant includes a modified metal hydroxide flame retardant.
In the present invention, the epoxy resin includes a combination of a bisphenol a type epoxy resin, a triglycidyl type epoxy resin, and a tetraglycidyl amine type epoxy resin, so that a material including the epoxy resin composition has excellent mechanical properties; by selecting the modified metal hydroxide flame retardant, the material comprising the epoxy resin composition has excellent flame retardant performance; by matching the epoxy resin, the modified metal hydroxide flame retardant and the curing agent, the mechanical property and the flame retardant property of the material comprising the epoxy resin composition are further improved, the smoke toxicity is low, and the high requirements of the field of electrical materials on the material are met.
Preferably, the epoxy resin composition comprises 90 to 110 parts by weight of epoxy resin, for example, 90 parts, 95 parts, 100 parts, 105 parts, 110 parts and the like.
Preferably, the epoxy resin composition comprises 100 to 120 parts by weight of an inorganic flame retardant, for example, 100 parts, 104 parts, 108 parts, 110 parts, 114 parts, 118 parts, 120 parts and the like.
In the invention, the halogen-free flame retardant can be realized by selecting the modified metal hydroxide as the flame retardant, and the excellent insulating property is ensured.
Preferably, the epoxy resin composition includes 3 to 35 parts by weight of the curing agent, and may be, for example, 3 parts, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, and the like.
In a preferred embodiment of the present invention, the triglycidyl-type epoxy resin includes triglycidyl-p-aminophenol epoxy resin.
Preferably, the tetraglycidyl amine type epoxy resin comprises 4,4' -diaminodiphenylmethane tetraglycidyl amine epoxy resin.
Preferably, the mass ratio of the bisphenol a type epoxy resin, the triglycidyl type epoxy resin and the tetraglycidyl amine type epoxy resin in the epoxy resin is 1: (0.2-0.5): (0.2 to 0.5), for example, it may be 1: 0.2: 0.2, 1: 0.2: 0.3, 1: 0.2: 0.5, 1: 0.3: 0.2, 1: 0.3: 0.5, 1: 0.5: 0.5, etc.
Preferably, the modified metal hydroxide flame retardant is a silane coupling agent modified metal hydroxide flame retardant.
Preferably, the particle size of the modified metal hydroxide flame retardant is 1 μm or less, and may be, for example, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1 μm or the like.
Preferably, the modified metal hydroxide flame retardant comprises a silane coupling agent and a metal hydroxide in a mass ratio of (0.01-0.02): 1, for example, may be 0.01: 1. 0.012 (b): 1. 0.014: 1. 0.016: 1. 0.018: 1. 0.02: 1, etc.
Preferably, the modified metal hydroxide flame retardant comprises a modified aluminum hydroxide and/or a modified magnesium hydroxide.
Preferably, the modified metal hydroxide flame retardant is prepared by a method comprising:
adding the metal hydroxide into a high-speed mixer, spraying a mixed solution of a silane coupling agent and a pH value regulator, and reacting to obtain the modified metal hydroxide flame retardant.
Preferably, the rotation speed of the high-speed mixer is 10000-20000 rpm, for example 10000rpm, 12000rpm, 15000rpm, 18000rpm, 20000rpm, etc.
Preferably, the reaction time is 20-30 min, for example, 20min, 22min, 24min, 26min, 28min, 30min, etc.
Preferably, the reaction temperature is 100-200 ℃, for example, can be 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃.
Preferably, the rotation speed of the reaction is 100 to 200rpm, and may be, for example, 100rpm, 120rpm, 150rpm, 180rpm, 200rpm, or the like.
Preferably, the curing agent comprises any one of dicyandiamide, dapsone or malondialdehyde, or a combination of at least two of them.
In a second aspect, the present invention provides a method for preparing the epoxy resin composition according to the first aspect, the method comprising the steps of:
reacting the epoxy resin with a curing agent to obtain cured epoxy resin; and mixing the cured epoxy resin with an inorganic flame retardant, dispersing and grinding to obtain the epoxy resin composition.
Preferably, the reaction time is 10-60 min, for example, 10min, 20min, 30min, 40min, 50min, 60min, etc.
In the invention, the gelation time of the cured epoxy resin at 160 ℃ is 3-5 min, for example, 3min, 4min, 5min and the like.
Preferably, the reaction temperature is 25-130 ℃, for example, can be 25 ℃, 50 ℃, 80 ℃, 100 ℃, 110 ℃, 120 ℃, 122 ℃, 124 ℃, 126 ℃, 128 ℃, 130 ℃ etc..
Preferably, the reaction also comprises a step of adding a solvent for dilution.
Preferably, the solvent comprises any one of toluene, xylene, methanol or N, N-dimethylformamide or a combination of at least two thereof.
Preferably, the solid content of the epoxy resin composition is 60 to 85%, for example, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 78%, 80%, 82%, 84%, and the like.
Preferably, the dispersing device is a disperser.
Preferably, the speed of rotation of the dispersion is 1000rpm or more, for example 1000rpm, 1200rpm, 1400rpm, 1600rpm, 1800rpm, 2000rpm, etc.
Preferably, the dispersing time is more than or equal to 1000min, such as 1000min, 1200min, 1400min, 1600min, 1800min, 2000min, etc.
Preferably, the grinding apparatus is a sand mill.
Preferably, the fineness of the grinding is 10 μm or less, and may be, for example, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, or the like.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
reacting epoxy resin and a curing agent for 10-60 min at 25-130 ℃, adding a solvent for dilution, adding an inorganic flame retardant, and dispersing and grinding by a dispersion machine and a sand mill to obtain the epoxy resin composition.
In a third aspect, the present invention provides an epoxy resin laminate comprising a reinforcing material and the epoxy resin composition of the first aspect adhered to the reinforcing material.
Preferably, the reinforcing material comprises glass fibre cloth.
In a fourth aspect, the present invention provides a method for producing an epoxy resin laminate according to the third aspect, the method comprising: and adhering the epoxy resin composition to a reinforcing material, drying, and performing compression molding to obtain the epoxy resin laminated board.
Preferably, the drying temperature is 150-170 ℃, for example, 150 ℃, 152 ℃, 154 ℃, 158 ℃, 160 ℃, 164 ℃, 168 ℃, 170 ℃.
Preferably, the drying time is 3-5 min, for example, 3min, 3.2min, 3.4min, 3.6min, 3.8min, 4min, 4.2min, 4.4min, 4.6min, 4.8min, 5min, etc.
Preferably, the temperature of the press molding is 150 to 200 ℃, for example, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 190 ℃ and the like.
Preferably, the time for the press forming is 0.5-3 h, for example, 0.5h, 1h, 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h and the like.
Preferably, the step of curing is further included after the press forming.
Preferably, the curing temperature is 180 to 200 ℃, for example, 180 ℃, 182 ℃, 184 ℃, 186 ℃, 190 ℃, 194 ℃, 198 ℃, 200 ℃ and the like.
Preferably, the curing time is 2-3 h, for example, 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, etc.
In a fourth aspect, the present invention provides an electrical insulating material comprising an epoxy resin composition according to the first aspect and/or an epoxy resin laminate according to the third aspect.
The recitation of numerical ranges herein includes not only the above-recited values, but also any values between any of the above-recited numerical ranges not recited, and for brevity and clarity, is not intended to be exhaustive of the specific values encompassed within the range.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides an epoxy resin composition, a preparation method and application thereof. The epoxy resin composition is used by matching specific polyfunctional epoxy resin with specific inorganic flame retardant and curing agent, so that the epoxy resin laminated board has excellent mechanical property, and the bending strength is not less than 789 MPa; the insulation property is good, and the tracking resistance index is more than or equal to 600V; the flame retardance is high, the oxygen index is more than 60, the smoke toxicity is low and is less than or equal to 0.15, the smoke density is less than or equal to 130.8, and the flame retardant is suitable for the field of insulation materials of ultra-high voltage power transmission systems.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The following examples and comparative examples do not indicate any particular technique or condition, and are carried out according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or apparatus used are conventional products commercially available from normal sources, not indicated by the manufacturer.
Preparation example 1
The preparation example provides modified aluminum hydroxide, and the specific preparation method comprises the following steps: 100 parts by weight of aluminum hydroxide (purity is more than or equal to 98 percent, D)90Less than or equal to 1 mu m) is added into a high-speed mixer with the rotating speed of 15000rpm, 1.5 parts by weight of silane coupling agent (KH560) and 0.05 part by weight of pH value regulator are dissolved in 25 parts by weight of water and slowly sprayed into the high-speed mixer, the temperature is raised to 110 ℃, the rotating speed is adjusted to 150rpm, and the mixture is stirred for 25min, thus obtaining the modified aluminum hydroxide.
Preparation example 2
The preparation example provides modified magnesium hydroxide, and the specific preparation method comprises the following steps: 100 parts by weight of magnesium hydroxide (purity is more than or equal to 98 percent, D)90Not more than 1 μm) is added into a high-speed mixer with the rotating speed of 15000rpm, 1.5 parts by weight of silane coupling agent (KH560) and 0.05 part by weight of pH value regulator (name, manufacturer, brand) are dissolved in 25 parts by weight of water and slowly sprayed into the high-speed mixer, the temperature is raised to 175 ℃, the rotating speed is adjusted to 150rpm, and the mixture is stirred for 25min, thus obtaining the modified magnesium hydroxide.
Preparation example 3
The preparation example provides modified aluminum hydroxide, and the specific preparation method comprises the following steps: 100 parts by weight of aluminum hydroxide (purity is more than or equal to 98 percent, D)90Less than or equal to 1 mu m) is added into a high-speed mixer with the rotating speed of 15000rpm, 5 weight parts of silane coupling agent (KH560) and 0.05 weight part of pH value regulator are dissolved in 25 weight parts of water and slowly sprayed into the high-speed mixer, the temperature is raised to 110 ℃, the rotating speed is adjusted to 150rpm, and the modified aluminum hydroxide is obtained after stirring for 25 min.
Preparation example 4
The preparation example provides modified magnesium hydroxide, and the specific preparation method comprises the following steps: 100 parts by weight of magnesium hydroxide (purity is more than or equal to 98 percent, D)90Not more than 1 μm) is added into a high-speed mixer with the rotating speed of 15000rpm, 1.5 parts by weight of silane coupling agent (KH560) is dissolved in 25 parts by weight of water and slowly sprayed into the high-speed mixer, the temperature is raised to 175 ℃, the rotating speed is adjusted to 150rpm, and the mixture is stirred for 25min, thus obtaining the modified magnesium hydroxide.
In the present invention, the materials used in all examples and comparative examples are as follows:
(1) bisphenol a type epoxy resin: available from Nantong star plastics, Inc., model E44;
(2) triglycidyl para-aminophenol epoxy resin: purchased from Guangzhou Tiangao high New technology, Inc., model AFG-90;
(3)4,4' -diaminodiphenylmethane tetraglycidyl amine epoxy resin: purchased from Guangzhou Tiangao high New technology Co., Ltd, model AG-80;
(4) glass fiber cloth: purchased from Shenzhen Spiran glass reinforced Plastic Ltd, model 7268.
Example 1
This example provides an epoxy resin composition comprising, in parts by weight, 100 parts of an epoxy resin, 50 parts of modified aluminum hydroxide (preparation example 1), 50 parts of modified magnesium hydroxide (preparation example 2), 3 parts of dicyandiamide, 40 parts of N, N-dimethylformamide, and 30 parts of methanol; in the epoxy resin, the mass ratio of bisphenol A type epoxy resin, triglycidyl para-aminophenol epoxy resin and 4,4' -diaminodiphenylmethane tetraglycidyl amine epoxy resin is 1: 0.3: 0.3.
the embodiment provides a preparation method of the epoxy resin composition, which comprises the following specific steps:
according to the formula amount, reacting epoxy resin and dicyandiamide in a reaction kettle at 120 ℃ for 10min, adding methanol and N, N-dimethylformamide for dilution, adding modified aluminum hydroxide and modified magnesium hydroxide, and dispersing and grinding by a high-speed dispersion machine and a sand mill to obtain the epoxy resin composition.
The embodiment provides an epoxy resin laminated board, and the specific preparation method comprises the following steps: impregnating glass fiber cloth with the epoxy resin composition, and drying for 4min at 160 ℃; and then pressing for 2.5h at the temperature of 155 ℃ to obtain the epoxy resin laminated plate.
Example 2
This example provides an epoxy resin composition comprising, in parts by weight, 100 parts of an epoxy resin, 110 parts of modified aluminum hydroxide (preparation example 1), 5 parts of dicyandiamide, 60 parts of N, N-dimethylformamide, and 50 parts of methanol; in the epoxy resin, the mass ratio of bisphenol A type epoxy resin, triglycidyl para-aminophenol epoxy resin and 4,4' -diaminodiphenylmethane tetraglycidyl amine epoxy resin is 1: 0.2: 0.5.
the embodiment provides a preparation method of the epoxy resin composition, which comprises the following specific steps:
according to the formula, epoxy resin and dicyandiamide react for 30min in a reaction kettle at the temperature of 25 ℃, methanol and N, N-dimethylformamide are added for dilution, modified aluminum hydroxide is added, and the epoxy resin composition is obtained by dispersing and grinding through a high-speed dispersing machine and a sand mill.
The embodiment provides an epoxy resin laminated board, and the specific preparation method comprises the following steps: impregnating glass fiber cloth with the epoxy resin composition, and drying for 5min at the temperature of 150 ℃; and then pressing for 3h at 160 ℃ to obtain the epoxy resin laminated plate.
Example 3
This example provides an epoxy resin composition comprising, in parts by weight, 100 parts of an epoxy resin, 120 parts of modified magnesium hydroxide (preparation example 2), 35 parts of dapsone, 30 parts of N, N-dimethylformamide, and 50 parts of toluene; in the epoxy resin, the mass ratio of bisphenol A type epoxy resin, triglycidyl para-aminophenol epoxy resin and 4,4' -diaminodiphenylmethane tetraglycidyl amine epoxy resin is 1: 0.5: 0.2.
the embodiment provides a preparation method of the epoxy resin composition, which comprises the following specific steps:
according to the formula amount, epoxy resin and dicyandiamide react for 60min in a reaction kettle at the temperature of 130 ℃, toluene and N, N-dimethylformamide are added for dilution, modified magnesium hydroxide is added, and the epoxy resin composition is obtained by dispersing and grinding through a high-speed dispersing machine and a sand mill.
The embodiment provides an epoxy resin laminated board, and the specific preparation method comprises the following steps: impregnating glass fiber cloth with the epoxy resin composition, and drying for 3min at the temperature of 170 ℃; and then pressing for 1h at 150 ℃, heating to 190 ℃, and curing for 2.5h to obtain the epoxy resin laminated board.
Example 4
This example provides an epoxy resin composition, which is different from example 1 only in that the modified aluminum hydroxide is the modified aluminum hydroxide obtained in preparation example 3, and other components and amounts are the same as those of example 1.
This example provides a method for preparing the epoxy resin composition, which includes the same steps as in example 1.
This example provides an epoxy resin laminate prepared in the same manner as in example 1.
Example 5
This example provides an epoxy resin composition, which is different from example 1 only in that the modified magnesium hydroxide is the modified magnesium hydroxide obtained in preparation example 4, and other components and amounts are the same as those of example 1.
This example provides a method for preparing the epoxy resin composition, which includes the same steps as in example 1.
This example provides an epoxy resin laminate prepared in the same manner as in example 1.
Example 6
This example provides an epoxy resin composition, which differs from example 1 only in that the epoxy resin contains a bisphenol a type epoxy resin, a triglycidyl p-aminophenol epoxy resin and a 4,4' -diaminodiphenylmethane tetraglycidyl amine epoxy resin in a mass ratio of 1: 0.1: 0.1, and the other components and the amounts are the same as in example 1.
This example provides a method for preparing the epoxy resin composition, which includes the same steps as in example 1.
This example provides an epoxy resin laminate prepared in the same manner as in example 1.
Example 7
This example provides an epoxy resin composition, which differs from example 1 only in that the epoxy resin contains a bisphenol a type epoxy resin, a triglycidyl p-aminophenol epoxy resin and a 4,4' -diaminodiphenylmethane tetraglycidyl amine epoxy resin in a mass ratio of 1: 1: 1, the other components and the amounts were the same as in example 1.
This example provides a method for preparing the epoxy resin composition, which includes the same steps as in example 1.
This example provides an epoxy resin laminate prepared in the same manner as in example 1.
Comparative example 1
This comparative example provides an epoxy resin composition which is different from example 1 only in that the epoxy resin composition includes 100 parts by weight of modified aluminum hydroxide (preparation example 1) and 100 parts by weight of modified magnesium hydroxide (preparation example 2), and the other components and amounts are the same as those of example 1.
The comparative example provides a preparation method of the epoxy resin composition, and the specific steps are the same as those of example 1.
This comparative example provides an epoxy laminate prepared in the same manner as in example 1.
Comparative example 2
This comparative example provides an epoxy resin composition which is different from example 1 only in that the epoxy resin composition includes 150 parts by weight of an epoxy resin, and other components and amounts are the same as example 1.
The comparative example provides a preparation method of the epoxy resin composition, and the specific steps are the same as those of example 1.
This comparative example provides an epoxy laminate prepared in the same manner as in example 1.
Comparative example 3
This comparative example provides an epoxy resin composition that differs from example 1 only in that the epoxy resin does not contain 4,4' -diaminodiphenylmethane tetraglycidyl amine epoxy resin, and the other components, amounts, and proportions are the same as in example 1.
The comparative example provides a preparation method of the epoxy resin composition, and the specific steps are the same as those of example 1.
This comparative example provides an epoxy laminate prepared in the same manner as in example 1.
Comparative example 4
This comparative example provides an epoxy resin composition which differs from example 1 only in that 4,4' -diaminodiphenylmethane tetraglycidyl amine epoxy resin is replaced with an equal mass of tetraglycidyl ether tetraphenylethane epoxy resin, and the other components, amounts and proportions are the same as in example 1.
The comparative example provides a preparation method of the epoxy resin composition, and the specific steps are the same as those of example 1.
This comparative example provides an epoxy laminate prepared in the same manner as in example 1.
Comparative example 5
This comparative example provides an epoxy resin composition which is different from example 1 only in that the triglycidyl p-aminophenol epoxy resin is replaced with an equal mass, and the other components, the amounts and the compounding ratios are the same as those of example 1.
The comparative example provides a preparation method of the epoxy resin composition, and the specific steps are the same as those of example 1.
This comparative example provides an epoxy laminate prepared in the same manner as in example 1.
Comparative example 6
This comparative example provides an epoxy resin composition which differs from example 1 only in that the epoxy resin does not contain a triglycidyl p-aminophenol epoxy resin, and the other components, amounts and proportions are the same as in example 1.
The comparative example provides a preparation method of the epoxy resin composition, and the specific steps are the same as those of example 1.
This comparative example provides an epoxy laminate prepared in the same manner as in example 1.
Performance testing
The epoxy resin laminates provided in all examples and comparative examples of the present invention were characterized as follows, and the results of the specific tests are shown in table 1.
(1) Bending strength: testing by adopting a GB/T1040-92 method;
(2) notched impact strength: testing by adopting a GB/T1043-;
(3) parallel layer shear strength: testing by adopting a GB/T1450.1-2005 method;
(4) tracking resistance index: the test is carried out by the method GB/T4207-2012;
(5) combustibility: testing by using a UL94 standard;
(6) oxygen index: the test is carried out by adopting the method GB/T2406-;
(7) smoke density: the GB/T8627-2007 method is adopted for testing;
(8) smoke toxicity: the test is carried out by adopting the GB/T20285-2006 method.
The specific test results are shown in table 1:
TABLE 1
As can be seen from the above table, the epoxy resin composition provided by the present invention enables the epoxy resin laminate to have excellent mechanical properties, insulation properties and flame retardancy by using the epoxy resin, the modified inorganic flame retardant and the curing agent in a specific combination. As is clear from examples 1 to 3, a preferable embodiment of the present invention is that the epoxy resin laminate has a flexural strength of 789 to 811MPa and a notched impact strength of 89.4 to 161KJ/m2(ii) a The tracking resistance index is more than or equal to 600V, and the insulativity is good; in addition, the flame retardant effect reaches UL 94V-0 grade standard, the smoke density after combustion is 117-130.8, and the smoke toxicity is 0.12-0.15.
From the comparison between example 1 and examples 4 and 5, it is understood that when the metal hydroxide is modified, the mass ratio of the silane coupling agent to the metal hydroxide is more than 0.02: 1 or when no pH regulator is added, the bending strength and impact strength of the epoxy resin laminated plate are reduced; as is clear from comparison of example 1 with examples 6 and 7, the epoxy resin in which the mass ratio of the bisphenol a type epoxy resin, the triglycidyl p-aminophenol epoxy resin and the 4,4' -diaminodiphenylmethane tetraglycidyl amine epoxy resin is not within a specific range, the mechanical properties of the epoxy resin laminate are deteriorated. As can be seen from comparison of example 1 with comparative examples 1 to 6, when the content of the inorganic flame retardant in the epoxy resin composition is not within a specific range or a specific combination of epoxy resins is not selected, the mechanical properties or flame retardancy of the epoxy resin laminate is deteriorated.
In conclusion, the epoxy resin composition provided by the invention is used by matching the epoxy resin, the modified inorganic flame retardant and the curing agent which are specially combined, so that the prepared epoxy resin laminated plate has excellent mechanical property, insulating property and flame retardance, is low in smoke density and smoke toxicity after combustion, is suitable for electric insulating materials, and is healthy and environment-friendly.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An epoxy resin composition is characterized by comprising 90-110 parts by weight of epoxy resin, 100-120 parts by weight of inorganic flame retardant and 3-35 parts by weight of curing agent;
the epoxy resin comprises a combination of bisphenol A type epoxy resin, triglycidyl type epoxy resin and tetraglycidyl amine type epoxy resin;
the inorganic flame retardant includes a modified metal hydroxide flame retardant.
2. The epoxy resin composition of claim 1, wherein the triglycidyl-type epoxy resin comprises triglycidyl p-aminophenol epoxy resin;
preferably, the tetraglycidyl amine type epoxy resin includes 4,4' -diaminodiphenylmethane tetraglycidyl amine epoxy resin;
preferably, the mass ratio of the bisphenol a type epoxy resin, the triglycidyl type epoxy resin and the tetraglycidyl amine type epoxy resin in the epoxy resin is 1: (0.2-0.5): (0.2-0.5).
3. The epoxy resin composition according to claim 1 or 2, wherein the modified metal hydroxide flame retardant is a silane coupling agent modified metal hydroxide flame retardant;
preferably, the particle size of the modified metal hydroxide flame retardant is less than or equal to 1 μm;
preferably, the modified metal hydroxide flame retardant comprises a silane coupling agent and a metal hydroxide in a mass ratio of (0.01-0.02): 1;
preferably, the modified metal hydroxide flame retardant comprises a modified aluminum hydroxide and/or a modified magnesium hydroxide;
preferably, the modified metal hydroxide flame retardant is prepared by a method comprising:
adding metal hydroxide into a high-speed mixer, spraying a mixed solution of a silane coupling agent and a pH value regulator, and reacting to obtain the modified metal hydroxide flame retardant;
preferably, the rotating speed of the high-speed mixer is 10000-20000 rpm;
preferably, the reaction time is 20-30 min;
preferably, the reaction temperature is 100-200 ℃;
preferably, the rotating speed of the reaction is 100-200 rpm.
4. The epoxy resin composition as claimed in any one of claims 1 to 3, wherein the curing agent comprises any one or a combination of at least two of dicyandiamide, dapsone or malondialdehyde.
5. A method for preparing the epoxy resin composition according to any one of claims 1 to 4, comprising the steps of:
reacting the epoxy resin with a curing agent to obtain cured epoxy resin; and mixing the cured epoxy resin with an inorganic flame retardant, dispersing and grinding to obtain the epoxy resin composition.
6. The preparation method according to claim 5, wherein the reaction time is 10-60 min;
preferably, the reaction temperature is 25-130 ℃;
preferably, the reaction also comprises a step of adding a solvent for dilution;
preferably, the solvent comprises any one of toluene, xylene, methanol or N, N-dimethylformamide or a combination of at least two thereof;
preferably, the solid content of the epoxy resin composition is 60-85%;
preferably, the dispersing equipment is a disperser;
preferably, the rotating speed of the dispersion is more than or equal to 1000 rpm;
preferably, the dispersing time is more than or equal to 1000 min;
preferably, the grinding apparatus is a sand mill;
preferably, the fineness of the grinding is less than or equal to 10 μm.
7. The method for preparing according to claim 5 or 6, characterized in that it comprises the following steps:
reacting epoxy resin and a curing agent for 10-60 min at 25-130 ℃, adding a solvent for dilution, adding an inorganic flame retardant, and dispersing and grinding by a dispersion machine and a sand mill to obtain the epoxy resin composition.
8. An epoxy resin laminate comprising a reinforcing material and the epoxy resin composition according to any one of claims 1 to 4 attached to the reinforcing material.
9. A method of manufacturing the epoxy laminate of claim 8, comprising: attaching the epoxy resin composition to a reinforcing material, drying, and performing compression molding to obtain the epoxy resin laminated board;
preferably, the drying temperature is 150-170 ℃;
preferably, the drying time is 3-5 min;
preferably, the temperature of the compression molding is 150-200 ℃;
preferably, the time for press forming is 0.5-3 h;
preferably, the step of curing is further included after the compression molding;
preferably, the curing temperature is 180-200 ℃;
preferably, the curing time is 2-3 h.
10. An electrical insulating material, characterized in that it comprises an epoxy resin composition according to any one of claims 1 to 4 and/or an epoxy resin laminate according to claim 8.
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