CN114163780B - 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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- CN114163780B CN114163780B CN202111536075.8A CN202111536075A CN114163780B CN 114163780 B CN114163780 B CN 114163780B CN 202111536075 A CN202111536075 A CN 202111536075A CN 114163780 B CN114163780 B CN 114163780B
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- epoxy resin
- resin composition
- flame retardant
- metal hydroxide
- parts
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 209
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 209
- 239000000203 mixture Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 239000003063 flame retardant Substances 0.000 claims abstract description 39
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 27
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 27
- 150000001412 amines Chemical class 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000012796 inorganic flame retardant Substances 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 47
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 20
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 15
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000004593 Epoxy Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012779 reinforcing material Substances 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000012772 electrical insulation material Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 3
- 229960000860 dapsone Drugs 0.000 claims description 3
- WSMYVTOQOOLQHP-UHFFFAOYSA-N Malondialdehyde Chemical compound O=CCC=O WSMYVTOQOOLQHP-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229940118019 malondialdehyde Drugs 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 28
- 238000012360 testing method Methods 0.000 description 11
- 239000000779 smoke Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000004744 fabric Substances 0.000 description 8
- 231100000419 toxicity Toxicity 0.000 description 5
- 230000001988 toxicity Effects 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- KGSFMPRFQVLGTJ-UHFFFAOYSA-N 1,1,2-triphenylethylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 KGSFMPRFQVLGTJ-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000168254 Siro Species 0.000 description 1
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention provides an epoxy resin composition, a preparation method and application thereof. The epoxy resin composition comprises 90-110 parts of epoxy resin, 100-120 parts of inorganic flame retardant and 3-35 parts of curing agent by weight; 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 enables the epoxy resin laminated board to have excellent mechanical property, insulating property and flame retardant property by selecting the epoxy resin, the modified metal hydroxide flame retardant and the curing agent in specific combination.
Description
Technical Field
The invention belongs to the technical field of electrical materials, and particularly relates to an epoxy resin composition, a preparation method and application thereof.
Background
The epoxy resin is a thermosetting resin, has high yield and full variety, has excellent physical and mechanical properties and electrical properties, and is widely applied to the fields of paint, adhesive, electronic appliances and the like; in particular in the field of electrical insulation, the use of epoxy-impregnated fibres or fabrics is common. However, due to the special properties of electronics and electricity, and with increasing awareness of safety and environmental protection, not only are materials required to have excellent mechanical properties and insulating properties, but also flame retardancy and low toxicity should be achieved.
For example, CN106916416a discloses a phosphorus-containing nitrogen-containing halogen-free flame retardant epoxy resin adhesive, prepreg and 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 colorant and a solvent. The prepreg and the insulating structural member prepared from the epoxy resin adhesive have high temperature resistance (H level), and the flame retardance can reach UL 94V-0 level flame retardance standard; the insulating structural member can further improve the flame retardant property of the H-level laminated board. However, the mechanical properties of the material are lacking.
CN102407630a discloses a halogen-free flame-retardant phenolic epoxy glass cloth laminated board and a preparation method thereof. The laminated board comprises alkali-free glass cloth and matrix resin; wherein, the components of the matrix resin include: epoxy resin, phenolic resin, aromatic amine curing agent and halogen-free phosphorus-containing nitrogen-containing flame retardant. The laminated board has the advantages of vertical combustion reaching UL 94V-0 level flame retardant standard, excellent flame retardant effect and good electrical and mechanical properties, can be used for printed circuit boards and other related electronic and electrical insulating materials or structural materials, but comprises phosphorus flame retardants, and is not beneficial to environmental protection and health.
CN109735100a discloses a halogen-containing flame retardant polyamide composite material without antimonide and a preparation method thereof, wherein the composite material comprises, by weight, 20-80 parts of polyamide resin, 1-30 parts of 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 same flame retardant effect as a bromine-antimony flame retardant system on the premise of not introducing antimony white, and can endow the brominated flame retardant polyamide with excellent electrical property. However, when the bromine-containing resin burns, a plurality of harmful substances including dioxin are generated, the smoke concentration is high, the difficulty is brought to the rescue of fire, and the environment is also damaged greatly.
Therefore, developing an electrical insulation material with good mechanical property, high insulation property and good flame retardance is a problem to be solved in the field.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide an epoxy resin composition, 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 through the synergistic use of the epoxy resin, the inorganic flame retardant and the curing agent and through the selection of the combination of specific epoxy resins.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an epoxy resin composition comprising, in parts by weight, 90 to 110 parts of an epoxy resin, 100 to 120 parts of an inorganic flame retardant, and 3 to 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 bisphenol a type epoxy resin, triglycidyl type epoxy resin, and tetraglycidyl amine type epoxy resin, so that a material including the epoxy resin composition has excellent mechanical properties; the modified metal hydroxide flame retardant is selected, so that the material comprising the epoxy resin composition has excellent flame retardant property; through the matching use of 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 electric material field on the material are met.
Preferably, the epoxy resin composition includes 90 to 110 parts by weight of epoxy resin, for example, 90 parts, 95 parts, 100 parts, 105 parts, 110 parts, etc.
Preferably, the epoxy resin composition includes 100 to 120 parts by weight of the inorganic flame retardant, for example, 100 parts, 104 parts, 108 parts, 110 parts, 114 parts, 118 parts, 120 parts, etc.
In the invention, the halogen-free flame retardance 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 a curing agent, for example, 3 parts, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, etc.
As a preferred embodiment of the present invention, the triglycidyl-type epoxy resin includes triglycidyl para-aminophenol epoxy resin.
Preferably, the tetraglycidyl amine type epoxy resin comprises 4,4' -diaminodiphenylmethane tetraglycidyl amine epoxy resin.
Preferably, the mass ratio of bisphenol a type epoxy resin, triglycidyl type epoxy resin and tetraglycidyl amine type epoxy resin in the epoxy resin is 1: (0.2-0.5): (0.2 to 0.5), for example, 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. Mu.m, for example, 0.1. Mu.m, 0.2. Mu.m, 0.3. Mu.m, 0.4. Mu.m, 0.5. Mu.m, 0.6. Mu.m, 0.7. Mu.m, 0.8. Mu.m, 0.9. Mu.m, 1. Mu.m, etc.
Preferably, the mass ratio of the silane coupling agent to the metal hydroxide in the modified metal hydroxide flame retardant is (0.01-0.02): 1, for example, may be 0.01: 1. 0.012: 1. 0.014: 1. 0.016: 1. 0.018: 1. 0.02:1, etc.
Preferably, the modified metal hydroxide flame retardant comprises modified aluminum hydroxide and/or modified magnesium hydroxide.
Preferably, the modified metal hydroxide flame retardant is prepared by a process 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 rotation speed of the high speed mixer is 10000 to 20000rpm, for example, 10000rpm, 12000rpm, 15000rpm, 18000rpm, 20000rpm, etc.
Preferably, the reaction time is 20 to 30 minutes, for example, 20 minutes, 22 minutes, 24 minutes, 26 minutes, 28 minutes, 30 minutes, and the like.
Preferably, the temperature of the reaction is 100 to 200 ℃, and for example, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃ and the like can be used.
Preferably, the rotational speed of the reaction is 100 to 200rpm, and for example, 100rpm, 120rpm, 150rpm, 180rpm, 200rpm, etc. may be used.
Preferably, the curing agent comprises any one or a combination of at least two of dicyandiamide, dapsone or malondialdehyde.
In a second aspect, the present invention provides a method for producing 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 to 60 minutes, for example, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 minutes, and the like.
In the present invention, the gelation time of the cured epoxy resin at 160℃is 3 to 5 minutes, and may be, for example, 3 minutes, 4 minutes, 5 minutes, or the like.
Preferably, the temperature of the reaction is 25 to 130 ℃, for example, 25 ℃, 50 ℃, 80 ℃, 100 ℃, 110 ℃, 120 ℃, 122 ℃, 124 ℃, 126 ℃, 128 ℃, 130 ℃ and the like can be used.
Preferably, the reaction further comprises the step of adding a solvent for dilution.
Preferably, the solvent comprises any one or a combination of at least two of toluene, xylene, methanol or N, N-dimethylformamide.
The epoxy resin composition preferably has a solid content of 60 to 85%, and may be 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 78%, 80%, 82%, 84%, or the like, for example.
Preferably, the dispersing device is a dispersing machine.
Preferably, the rotational speed of the dispersion is ≡1000rpm, for example, 1000rpm, 1200rpm, 1400rpm, 1600rpm, 1800rpm, 2000rpm, etc.
Preferably, the dispersing time is equal to or longer than 1000min, for example, 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 preferable 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 into the mixture, and dispersing and grinding the mixture by a dispersing machine and a sand mill to obtain the epoxy resin composition.
In a third aspect, the present invention provides an epoxy laminate comprising a reinforcing material and the epoxy resin composition of the first aspect attached to the reinforcing material.
Preferably, the reinforcing material comprises a glass cloth.
In a fourth aspect, the present invention provides a method for producing the epoxy resin laminate according to the third aspect, the method comprising: and (3) attaching the epoxy resin composition to a reinforcing material, drying and pressing to form the epoxy resin laminated board.
Preferably, the drying temperature is 150 to 170 ℃, and may be 150 ℃, 152 ℃, 154 ℃, 158 ℃, 160 ℃, 164 ℃, 168 ℃, 170 ℃, or the like, for example.
Preferably, the drying time is 3 to 5min, 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 ℃, and for example, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 190 ℃, and the like can be used.
Preferably, the time for the press molding is 0.5 to 3 hours, and may be, for example, 0.5 hours, 1 hour, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 3 hours, or the like.
Preferably, the press molding further comprises a curing step.
Preferably, the curing temperature is 180 to 200 ℃, and may be 180 ℃, 182 ℃, 184 ℃, 186 ℃, 190 ℃, 194 ℃, 198 ℃, 200 ℃, or the like, for example.
Preferably, the curing time is 2 to 3 hours, for example, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 3 hours, etc.
In a fourth aspect, the present invention provides an electrical insulation material comprising the epoxy resin composition according to the first aspect and/or the epoxy resin laminate according to the third aspect.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
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 the specific multifunctional epoxy resin with the specific inorganic flame retardant and the curing agent, so that the epoxy resin laminated board has excellent mechanical property, and the bending strength is more than or equal to 789MPa; the insulation property is good, and the tracking 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 retardance is suitable for the field of insulating materials of ultra-high voltage transmission systems.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The following examples and comparative examples do not identify specific techniques or conditions, which may be followed by those described in the literature in the field or by the product specifications. The reagents or apparatus used were conventional products commercially available through regular channels, with no manufacturer noted.
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%, D) 90 Less than or equal to 1 μm) is added into a high-speed mixer with the rotating speed of 15000rpm, 1.5 parts by weight of silane coupling agent (KH 560) and 0.05 part by weight of pH value regulator are dissolved in 25 parts by weight of water, the mixture is slowly sprayed into the high-speed mixer, the temperature is increased to 110 ℃, the rotating speed is adjusted to 150rpm, and the mixture is stirred for 25 minutes, so that the modified aluminum hydroxide is obtained.
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%, D) 90 1.5 parts by weight of a silane coupling agent (KH 560) and 0.05 part by weight of a pH regulator (name, manufacturer) were added to a high-speed mixer at a rotation speed of 15000rpmAnd the brand) is dissolved in 25 parts by weight of water, slowly sprayed into a high-speed mixer, the temperature is increased to 175 ℃, the rotating speed is adjusted to 150rpm, and the modified magnesium hydroxide is obtained after stirring for 25 minutes.
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%, D) 90 Less than or equal to 1 μm) is added into a high-speed mixer with the rotating speed of 15000rpm, 5 parts by weight of silane coupling agent (KH 560) and 0.05 part by weight of pH value regulator are dissolved in 25 parts by weight of water, the mixture is slowly sprayed into the high-speed mixer, the temperature is increased to 110 ℃, the rotating speed is adjusted to 150rpm, and the mixture is stirred for 25min, so that the modified aluminum hydroxide is obtained.
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%, D) 90 Less than or equal to 1 μm) is added into a high-speed mixer with the rotating speed of 15000rpm, 1.5 parts by weight of silane coupling agent (KH 560) is dissolved in 25 parts by weight of water, the mixture is slowly sprayed into the high-speed mixer, the temperature is increased to 175 ℃, the rotating speed is adjusted to 150rpm, and the mixture is stirred for 25min, so that the modified magnesium hydroxide is obtained.
In the present invention, all the materials used in the examples and comparative examples are as follows:
(1) Bisphenol a epoxy resin: purchased from Nantong star synthetic materials Co., ltd., model E44;
(2) Triglycidyl para-aminophenol epoxy resin: model AFG-90, available from Guangzhou Tiantai high technology Co., ltd;
(3) 4,4' -diaminodiphenylmethane tetraglycidyl amine epoxy resin: purchased from Guangzhou Tiantai high technology Co., ltd., model AG-80;
(4) Glass fiber cloth: purchased from Shenzhen Siro glass fiber reinforced plastic Co., 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; the mass ratio of bisphenol A epoxy resin to triglycidyl para-aminophenol epoxy resin to 4,4' -diaminodiphenyl methane tetraglycidyl amine epoxy resin in the 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, epoxy resin and dicyandiamide are reacted in a reaction kettle at 120 ℃ for 10min, methanol and N, N-dimethylformamide are added for dilution, modified aluminum hydroxide and modified magnesium hydroxide are added, and the epoxy resin composition is obtained through dispersion and grinding by 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 4min at 160 ℃; and then pressing at 155 ℃ for 2.5 hours to obtain the epoxy resin laminated board.
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; the mass ratio of bisphenol A epoxy resin to triglycidyl para-aminophenol epoxy resin to 4,4' -diaminodiphenyl methane tetraglycidyl amine epoxy resin in the 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 amount, epoxy resin and dicyandiamide are reacted in a reaction kettle at 25 ℃ for 30min, methanol and N, N-dimethylformamide are added for dilution, modified aluminum hydroxide is added, and the epoxy resin composition is obtained through dispersion and grinding by 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 150 ℃; and then pressing for 3 hours at 160 ℃ to obtain the epoxy resin laminated board.
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; the mass ratio of bisphenol A epoxy resin to triglycidyl para-aminophenol epoxy resin to 4,4' -diaminodiphenyl methane tetraglycidyl amine epoxy resin in the 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 are reacted in a reaction kettle at 130 ℃ for 60min, toluene and N, N-dimethylformamide are added for dilution, modified magnesium hydroxide is added, and the epoxy resin composition is obtained through dispersion and grinding by 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 at 170 ℃ for 3min; 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 differing from example 1 only in that the modified aluminum hydroxide is the modified aluminum hydroxide obtained in production example 3, and other components and amounts are the same as in example 1.
This example provides a method for preparing the epoxy resin composition, and the specific steps are the same as in example 1.
This example provides an epoxy laminate, and the specific preparation method is the same as in example 1.
Example 5
This example provides an epoxy resin composition which differs 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 in example 1.
This example provides a method for preparing the epoxy resin composition, and the specific steps are the same as in example 1.
This example provides an epoxy laminate, and the specific preparation method is the same as in example 1.
Example 6
This example provides an epoxy resin composition differing from example 1 only in that the mass ratio of bisphenol a type epoxy resin, triglycidyl para-aminophenol epoxy resin, and 4,4' -diaminodiphenylmethane tetraglycidyl amine epoxy resin in the epoxy resin is 1:0.1:0.1, other components and amounts were the same as in example 1.
This example provides a method for preparing the epoxy resin composition, and the specific steps are the same as in example 1.
This example provides an epoxy laminate, and the specific preparation method is the same as in example 1.
Example 7
This example provides an epoxy resin composition differing from example 1 only in that the mass ratio of bisphenol a type epoxy resin, triglycidyl para-aminophenol epoxy resin, and 4,4' -diaminodiphenylmethane tetraglycidyl amine epoxy resin in the epoxy resin is 1:1:1, other components and amounts were the same as in example 1.
This example provides a method for preparing the epoxy resin composition, and the specific steps are the same as in example 1.
This example provides an epoxy laminate, and the specific preparation method is the same as in example 1.
Comparative example 1
This comparative example provides an epoxy resin composition differing from example 1 only in that the epoxy resin composition comprises 100 parts by weight of modified aluminum hydroxide (preparation example 1) and 100 parts by weight of modified magnesium hydroxide (preparation example 2), and other components and amounts are the same as in example 1.
This comparative example provides a method for preparing the epoxy resin composition, and the specific procedure is the same as in example 1.
This comparative example provides an epoxy resin laminate, and the specific preparation method is the same as in example 1.
Comparative example 2
This comparative example provides an epoxy resin composition differing 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 those of example 1.
This comparative example provides a method for preparing the epoxy resin composition, and the specific procedure is the same as in example 1.
This comparative example provides an epoxy resin laminate, and the specific preparation method is the same as in example 1.
Comparative example 3
This comparative example provides an epoxy resin composition differing from example 1 only in that the epoxy resin is free of 4,4' -diaminodiphenylmethane tetraglycidyl amine epoxy resin, and the other components, amounts and proportions are the same as in example 1.
This comparative example provides a method for preparing the epoxy resin composition, and the specific procedure is the same as in example 1.
This comparative example provides an epoxy resin laminate, and the specific preparation method is the same as in example 1.
Comparative example 4
This comparative example provides an epoxy resin composition differing from example 1 only in that the epoxy resin was replaced with equal mass of tetraglycidyl ether tetraphenyl ethane epoxy resin in 4,4' -diaminodiphenyl methane tetraglycidyl amine epoxy resin, and the other components, amounts and proportions were the same as in example 1.
This comparative example provides a method for preparing the epoxy resin composition, and the specific procedure is the same as in example 1.
This comparative example provides an epoxy resin laminate, and the specific preparation method is the same as in example 1.
Comparative example 5
This comparative example provides an epoxy resin composition differing from example 1 only in that the triglycidyl para-aminophenol epoxy resin was replaced with an equal mass in the epoxy resin, and the other components, amounts and proportions were the same as in example 1.
This comparative example provides a method for preparing the epoxy resin composition, and the specific procedure is the same as in example 1.
This comparative example provides an epoxy resin laminate, and the specific preparation method is the same as in example 1.
Comparative example 6
This comparative example provides an epoxy resin composition differing from example 1 only in that the epoxy resin has no triglycidyl para-aminophenol epoxy resin therein, and the other components, amounts and proportions are the same as in example 1.
This comparative example provides a method for preparing the epoxy resin composition, and the specific procedure is the same as in example 1.
This comparative example provides an epoxy resin laminate, and the specific preparation method is the same 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 specific test results are shown in table 1.
(1) Flexural strength: testing by using a GB/T1040-92 method;
(2) Notched impact strength: testing by using a GB/T1043-2008 method;
(3) Parallel layer shear strength: testing by using a GB/T1450.1-2005 method;
(4) Tracking index: testing by using a GB/T4207-2012 method;
(5) Combustibility: testing by using UL94 standard;
(6) Oxygen index: testing by using a GB/T2406-1992 method;
(7) Smoke density: testing by using a GB/T8627-2007 method;
(8) Smoke toxicity: the test was performed using 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, through the cooperation of the epoxy resin, the modified inorganic flame retardant and the curing agent in specific combination, enables the epoxy resin laminate to have excellent mechanical properties, insulation and flame retardance. As is clear from examples 1 to 3, the epoxy resin laminate has a flexural strength of 789 to 811MPa and a notched impact strength of 89.4 to 161KJ/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The tracking index is more than or equal to 600V, and the insulation property is good; in addition, the flame retardant effect reaches the UL 94V-0 level standard, the smoke density after combustion is 117-130.8, and the smoke toxicity is 0.12-0.15.
As can be seen from comparison of example 1 with examples 4 and 5, when the metal hydroxide is modified, the mass ratio of the silane coupling agent to the metal hydroxide is greater than 0.02:1 or no pH adjuster is added, the flexural strength and impact strength of the epoxy resin laminate decrease; as is clear from a comparison of example 1 with examples 6 and 7, the mass ratio of bisphenol A type epoxy resin, triglycidyl para-aminophenol epoxy resin and 4,4' -diaminodiphenylmethane tetraglycidyl amine epoxy resin in the epoxy resin was not within a specific range, and the mechanical properties of the epoxy resin laminate were degraded. As is clear from a comparison of example 1 and 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 the epoxy resin is not selected from a specific combination, the mechanical properties or flame retardant properties of the epoxy resin laminate are lowered.
In summary, according to the epoxy resin composition provided by the invention, through the matched use of the epoxy resin, the modified inorganic flame retardant and the curing agent which are specifically combined, the prepared epoxy resin laminated board has excellent mechanical properties, insulativity and flame retardance, and low smoke density and smoke toxicity after combustion, is suitable for electrical insulation materials, and is healthy and environment-friendly.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (30)
1. The epoxy resin composition is characterized by comprising, by weight, 90-110 parts of epoxy resin, 100-120 parts of inorganic flame retardant and 3-35 parts 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 comprises a modified metal hydroxide flame retardant;
the mass ratio of bisphenol A type epoxy resin to triglycidyl type epoxy resin to tetraglycidyl amine type epoxy resin in the epoxy resin is 1: (0.2 to 0.5): (0.2 to 0.5);
the modified metal hydroxide flame retardant is a silane coupling agent modified metal hydroxide flame retardant;
the mass ratio of the silane coupling agent to the metal hydroxide in the modified metal hydroxide flame retardant is (0.01-0.02): 1, a step of;
the triglycidyl type epoxy resin is triglycidyl para-aminophenol epoxy resin;
the tetraglycidyl amine type epoxy resin is 4,4' -diaminodiphenyl methane tetraglycidyl amine type epoxy resin;
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.
2. The epoxy resin composition of claim 1, wherein the modified metal hydroxide flame retardant has a particle size of 1 μm or less.
3. The epoxy resin composition according to claim 1, wherein the modified metal hydroxide flame retardant comprises modified aluminum hydroxide and/or modified magnesium hydroxide.
4. The epoxy resin composition according to claim 1, wherein the rotational speed of the high-speed mixer is 10000 to 20000 rpm.
5. The epoxy resin composition according to claim 1, wherein the reaction time is 20 to 30 minutes.
6. The epoxy resin composition according to claim 1, wherein the reaction temperature is 100 to 200 ℃.
7. The epoxy resin composition according to claim 1, wherein the rotational speed of the reaction is 100 to 200 rpm.
8. The epoxy resin composition of claim 1, wherein the curing agent comprises any one or a combination of at least two of dicyandiamide, dapsone, or malondialdehyde.
9. A method of producing the epoxy resin composition according to any one of claims 1 to 8, characterized by 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.
10. The method according to claim 9, wherein the reaction time is 10 to 60 minutes.
11. The method according to claim 9, wherein the reaction temperature is 25 to 130 ℃.
12. The method of claim 9, further comprising the step of adding a solvent for dilution after the reaction.
13. The method of claim 12, wherein the solvent comprises toluene, xylene, methanol, or methanolN,N-any one or a combination of at least two of dimethylformamide.
14. The method of claim 12, wherein the epoxy resin composition has a solids content of 60 to 85%.
15. The method of claim 9, wherein the dispersing apparatus is a disperser.
16. The process according to claim 9, wherein the speed of dispersion is not less than 1000 rpm.
17. The method of claim 9, wherein the dispersing time is greater than or equal to 1000 minutes.
18. The method of claim 9, wherein the grinding apparatus is a sand mill.
19. The method according to claim 9, wherein the fineness of the grinding is 10 μm or less.
20. The preparation method according to claim 9, characterized in that the preparation method comprises the steps of:
and (3) reacting the epoxy resin with the curing agent for 10-60 min at the temperature of 25-130 ℃, adding a solvent for dilution, adding an inorganic flame retardant into the mixture, and dispersing and grinding the mixture by a dispersing machine and a sand mill to obtain the epoxy resin composition.
21. An epoxy laminate comprising a reinforcing material and the epoxy composition of any one of claims 1 to 8 attached to the reinforcing material.
22. A method of producing an epoxy resin laminate according to claim 21, comprising: and (3) attaching the epoxy resin composition to a reinforcing material, drying and pressing to form the epoxy resin laminated board.
23. The method of claim 22, wherein the drying temperature is 150-170 ℃.
24. The method of producing an epoxy resin laminate according to claim 22, wherein the drying time is 3 to 5 minutes.
25. The method of producing an epoxy resin laminate according to claim 22, wherein the press molding temperature is 150 to 200 ℃.
26. The method of producing an epoxy resin laminate according to claim 22, wherein the press molding time is 0.5 to 3 hours.
27. The method of manufacturing an epoxy laminate of claim 22, further comprising the step of curing after the compression molding.
28. The method of claim 27, wherein the curing temperature is 180-200 ℃.
29. The method of claim 27, wherein the curing time is 2 to 3 hours.
30. An electrical insulation material, characterized in that it comprises an epoxy resin composition according to any one of claims 1-8 and/or an epoxy resin laminate according to claim 21.
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| JP2002146118A (en) * | 2000-11-06 | 2002-05-22 | Sumitomo Wiring Syst Ltd | Flame-retardant resin composition and flame-retardant insulated wire using the same as coating material |
| JP2002265948A (en) * | 2001-03-06 | 2002-09-18 | Konoshima Chemical Co Ltd | Magnesium hydroxide flame retardant coated with silane coupling agent, its production method, and flame- retardant resin composition |
| JP2006291092A (en) * | 2005-04-13 | 2006-10-26 | Yokohama Rubber Co Ltd:The | Epoxy resin composition for fiber-reinforced composite material |
| JP2013095889A (en) * | 2011-11-04 | 2013-05-20 | Kyocera Chemical Corp | Epoxy resin composition for dip coating |
| CN105885358A (en) * | 2016-06-29 | 2016-08-24 | 西安超码复合材料有限公司 | Halogen-free high temperature resistant resin |
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