CN118406456A - Preparation process of modified epoxy resin conductive adhesive - Google Patents
Preparation process of modified epoxy resin conductive adhesive Download PDFInfo
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- CN118406456A CN118406456A CN202410874553.3A CN202410874553A CN118406456A CN 118406456 A CN118406456 A CN 118406456A CN 202410874553 A CN202410874553 A CN 202410874553A CN 118406456 A CN118406456 A CN 118406456A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 53
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 53
- 239000000853 adhesive Substances 0.000 title claims abstract description 48
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000003756 stirring Methods 0.000 claims abstract description 56
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 47
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims abstract description 22
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 11
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- -1 amino graphene Chemical compound 0.000 claims abstract description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 4
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 25
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- 229920000767 polyaniline Polymers 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000010025 steaming Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000006683 Mannich reaction Methods 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 description 32
- 239000000463 material Substances 0.000 description 12
- 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 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical group C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002042 Silver nanowire Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of conductive adhesive and discloses a preparation process of modified epoxy resin conductive adhesive, which comprises the steps of obtaining amino graphene by substitution reaction by using aminopropyl triethoxy silane, graphene oxide and the like as raw materials, preparing an intermediate 1 by using 4-aminophenol, DOPO, formaldehyde and the like as raw materials through a one-pot method, obtaining a DOPO-containing graphene intermediate by using formaldehyde, amino graphene, intermediate 1 and the like as raw materials through a Mannich reaction, and finally adding DOPO-containing graphene intermediate and triethanolamine into epoxy resin, and uniformly stirring to obtain the modified epoxy resin conductive adhesive. The epoxy resin conductive adhesive prepared by the invention has better conductive performance, heat resistance and flame retardance.
Description
Technical Field
The invention relates to the technical field of conductive adhesive, in particular to a preparation process of modified epoxy resin conductive adhesive.
Background
Along with the gradual transition of electronic products to miniaturization and portability, the development of the conductive adhesive industry is rapidly promoted. The conductive adhesive is a special adhesive, is a composite material which is formed by taking a polymer as a matrix and adding conductive filler and has bonding property and conductivity, is a better electronic packaging connecting material, but still has the defects of low conductivity, poor stability and the like, and limits the wide application of the conductive adhesive.
The epoxy resin conductive adhesive is composed of an epoxy resin matrix, conductive filler and the like, and has good bonding performance, but has poor flame retardant performance and heat resistance, so that the epoxy resin conductive adhesive needs to be modified to improve the application field of the epoxy resin conductive adhesive. Graphene is a two-dimensional carbon-based structural material, has relatively excellent electrical conductivity, thermal conductivity and other properties, and is widely applied to various fields.
For example, patent with publication number CN103614098B discloses a functionalized graphene doped epoxy resin conductive adhesive and a preparation method thereof, the invention takes epoxy resin, graphene, silver nanowire and the like as raw materials, and the prepared adhesive has good conductivity and bonding strength and wide application prospect, but the heat resistance and flame retardance of the epoxy resin conductive adhesive are not improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation process of the modified epoxy resin conductive adhesive, and the prepared epoxy resin conductive adhesive has better conductive performance, heat resistance and flame retardance.
The preparation process of the modified epoxy resin conductive adhesive comprises the following steps:
(1) Adding graphene oxide into 80% tetrahydrofuran aqueous solution by mass fraction, stirring and dispersing, adding aminopropyl triethoxysilane and 0.1-0.2mol/L hydrochloric acid into the mixture at 70-80 ℃, stirring and reacting for 10-24h, and after the reaction is finished, carrying out suction filtration, washing with tetrahydrofuran and drying to obtain the amino graphene;
(2) Adding 4-aminophenol, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and formaldehyde into an N, N-dimethylformamide solvent, stirring and dispersing, heating to 60-80 ℃, reacting for 5-10h, precipitating methanol after the reaction is finished, filtering, washing with methanol, and drying to obtain an intermediate 1;
(3) Adding formaldehyde into chloroform solvent, stirring and dispersing, adding aminated graphene into the chloroform solvent at 60-65 ℃, stirring and dispersing, heating to 70-80 ℃, adding intermediate 1 into the chloroform solvent, stirring and reacting for 1-3h, cooling to room temperature after the reaction is finished, filtering, and steaming in a rotating way to obtain DOPO-containing graphene intermediate;
(4) Adding the epoxy resin E-44 into acetonitrile solvent, stirring and dispersing, adding the DOPO-containing graphene intermediate, triethanolamine and polyaniline into the mixture, fully and uniformly stirring, uniformly coating the mixture on a glass sheet, and placing the glass sheet in an oven for curing to obtain the modified epoxy resin conductive adhesive.
Preferably, in the step (1), the dosage ratio of graphene oxide to aminopropyl triethoxysilane is 1mg: (0.2-0.5) mL.
Preferably, in the step (2), the dosage ratio of 4-aminophenol, DOPO and formaldehyde is 1g: (3.5-5) g: (0.55-0.65) g.
Preferably, in the step (3), the dosage ratio of formaldehyde, the aminated graphene and the intermediate 1 is (0.12-0.4) g: (0.5-2) g:1g.
Preferably, in the step (4), the dosage ratio of the epoxy resin to the DOPO-containing graphene intermediate to the triethanolamine to the polyaniline is 1g: (0.1-0.5) g: (0.1-0.2) g: (0.1-0.3) g.
Preferably, in the step (4), the curing process is 120 ℃/2h,150 ℃/1h.
Reaction mechanism: according to the invention, aminopropyl triethoxysilane, graphene oxide and the like are used as raw materials, amino graphene is obtained through substitution reaction, 4-aminophenol, DOPO, formaldehyde and the like are used as raw materials, a one-pot method is used for preparing an intermediate 1, formaldehyde, amino graphene, the intermediate 1 and the like are used as raw materials, a mannich reaction is carried out for obtaining a DOPO-containing graphene intermediate, finally the DOPO-containing graphene intermediate and triethanolamine are added into epoxy resin, and the epoxy resin is stirred uniformly to obtain the modified epoxy resin conductive adhesive.
The beneficial effects are that: the modified epoxy resin conductive adhesive prepared by the invention contains graphene, the graphene has better conductivity, but the graphene has larger specific surface area and is easy to agglomerate.
The modified epoxy resin conductive adhesive prepared by the invention contains more rigid structures, such as benzene rings and six-membered rings, and the introduction of the rigid structures increases the molecular stacking density of the material, so that the heat resistance of the epoxy resin conductive adhesive is improved. In addition, the modified epoxy resin conductive adhesive prepared by the invention contains DOPO structures, and the DOPO structures generate strong dehydration substances such as phosphoric acid, metaphosphoric acid and the like when heated, so that the dehydration and the carbonization of the material are promoted, a compact carbon layer is formed on the surface of the material, and the flame retardant property of the material is further improved. The epoxy conductive adhesive prepared by the invention has better conductivity, flame retardance and heat resistance.
Drawings
FIG. 1 is a preparation route diagram of DOPO-containing graphene intermediates of the present invention.
Detailed Description
The following description will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation method of the graphene oxide comprises the following steps: adding 5g of graphite flake into 100mL of 98% concentrated sulfuric acid at 0 ℃, adding 15g of potassium permanganate and 2.5g of sodium nitrate into the mixture, reacting for 1h, heating to 35 ℃, continuously stirring and reacting for 2h, adding 250mL of deionized water into the mixture after the reaction is finished, heating to 95 ℃, stirring and reacting for 1h, adding 50mL of 30% hydrogen peroxide into the mixture after the reaction is finished, stirring and reacting for 1h, washing the mixture with hydrochloric acid and deionized water in sequence after the reaction is finished, and drying to obtain graphene oxide.
Example 1: the preparation process of the modified epoxy resin conductive adhesive comprises the following steps:
(1) Adding 200mg of graphene oxide into 200mL of 80% tetrahydrofuran aqueous solution, stirring and dispersing, adding 100mL of aminopropyl triethoxysilane and 0.4mL of 0.15mol/L hydrochloric acid into the mixture at 75 ℃, stirring and reacting for 24 hours, and after the reaction is finished, filtering, washing with tetrahydrofuran and drying to obtain the aminated graphene;
(2) Adding 10g of 4-aminophenol, 45g of DOPO and 6.5g of formaldehyde into 200mL of N, N-dimethylformamide solvent, stirring and dispersing, heating to 75 ℃, reacting for 8 hours, precipitating methanol after the reaction is finished, filtering, washing with methanol, and drying to obtain an intermediate 1;
(3) Adding 2g of formaldehyde into 200mL of chloroform solvent, stirring and dispersing, adding 15g of aminated graphene into the chloroform solvent at 60 ℃, stirring and dispersing, heating to 75 ℃, adding 10g of intermediate 1 into the chloroform solvent, stirring and reacting for 2 hours, cooling to room temperature after the reaction is finished, filtering, and steaming in a rotary way to obtain a DOPO-containing graphene intermediate;
(4) Adding 20g of epoxy resin into 100mL of acetonitrile solvent, stirring and dispersing, adding 2g of DOPO-containing graphene intermediate, 3g of triethanolamine and 2g of polyaniline into the mixture, fully and uniformly stirring, uniformly coating the mixture on a glass sheet, and placing the glass sheet into an oven for curing, wherein the curing process is 120 ℃/2h,150 ℃/1h, thus obtaining the modified epoxy resin conductive adhesive.
Example 2: the preparation process of the modified epoxy resin conductive adhesive comprises the following steps:
(1) Adding 200mg of graphene oxide into 200mL of tetrahydrofuran aqueous solution with the mass fraction of 80%, stirring and dispersing, adding 80mL of aminopropyl triethoxysilane and 0.4mL of hydrochloric acid with the concentration of 0.2mol/L into the mixture at 70 ℃, stirring and reacting for 12h, and after the reaction is finished, filtering, washing with tetrahydrofuran and drying to obtain the aminated graphene;
(2) Adding 10g of 4-aminophenol, 40g of DOPO and 6g of formaldehyde into 200mL of N, N-dimethylformamide solvent, stirring and dispersing, heating to 80 ℃, reacting for 6 hours, precipitating methanol after the reaction is finished, filtering, washing with methanol, and drying to obtain an intermediate 1;
(3) Adding 3g of formaldehyde into 200mL of chloroform solvent, stirring and dispersing, adding 16g of aminated graphene into the chloroform solvent at 60 ℃, stirring and dispersing, heating to 75 ℃, adding 10g of intermediate 1 into the chloroform solvent, stirring and reacting for 2 hours, cooling to room temperature after the reaction is finished, filtering, and steaming in a rotary way to obtain a DOPO-containing graphene intermediate;
(4) Adding 20g of epoxy resin into 100mL of acetonitrile solvent, stirring and dispersing, adding 4g of DOPO-containing graphene intermediate, 4g of triethanolamine and 6g of polyaniline into the mixture, fully and uniformly stirring, uniformly coating the mixture on a glass sheet, and placing the glass sheet into an oven for curing, wherein the curing process is 120 ℃/2h,150 ℃/1h, thus obtaining the modified epoxy resin conductive adhesive.
Example 3: the preparation process of the modified epoxy resin conductive adhesive comprises the following steps:
(1) Adding 200mg of graphene oxide into 200mL of tetrahydrofuran aqueous solution with the mass fraction of 80%, stirring and dispersing, adding 40mL of aminopropyl triethoxysilane and 0.4mL of hydrochloric acid with the concentration of 0.1mol/L into the mixture, stirring and reacting for 10h, and after the reaction is finished, filtering, washing with tetrahydrofuran and drying to obtain the aminated graphene;
(2) Adding 10g of 4-aminophenol, 50g of DOPO and 6.5g of formaldehyde into 200mL of N, N-dimethylformamide solvent, stirring and dispersing, heating to 70 ℃, reacting for 6 hours, precipitating methanol after the reaction is finished, filtering, washing with methanol, and drying to obtain an intermediate 1;
(3) Adding 2g of formaldehyde into 200mL of chloroform solvent, stirring and dispersing, adding 5g of aminated graphene into the chloroform solvent at 60 ℃, stirring and dispersing, heating to 70 ℃, adding 10g of intermediate 1 into the chloroform solvent, stirring and reacting for 1h, cooling to room temperature after the reaction is finished, filtering, and steaming in a rotary way to obtain a DOPO-containing graphene intermediate;
(4) Adding 20g of epoxy resin into 100mL of acetonitrile solvent, stirring and dispersing, adding 6g of DOPO-containing graphene intermediate, 2g of triethanolamine and 4g of polyaniline into the mixture, fully and uniformly stirring, uniformly coating the mixture on a glass sheet, and placing the glass sheet into an oven for curing, wherein the curing process is 120 ℃/2h,150 ℃/1h, thus obtaining the modified epoxy resin conductive adhesive.
Example 4: the preparation process of the modified epoxy resin conductive adhesive comprises the following steps:
(1) 200mg of graphene oxide is added into 200mL of tetrahydrofuran aqueous solution with the mass fraction of 80%, stirred and dispersed, 50mL of aminopropyl triethoxysilane and 0.4mL of hydrochloric acid with the concentration of 0.2mol/L are added into the mixture at the temperature of 75 ℃, the mixture is stirred and reacted for 12 hours, and after the reaction is finished, suction filtration, tetrahydrofuran washing and drying are carried out to obtain the aminated graphene;
(2) Adding 10g of 4-aminophenol, 40g of DOPO and 6g of formaldehyde into 200mL of N, N-dimethylformamide solvent, stirring and dispersing, heating to 80 ℃, reacting for 10 hours, precipitating methanol after the reaction is finished, filtering, washing with methanol, and drying to obtain an intermediate 1;
(3) Adding 1.2g of formaldehyde into 200mL of chloroform solvent, stirring and dispersing, adding 20g of aminated graphene into the chloroform solvent at 60 ℃, stirring and dispersing, heating to 80 ℃, adding 10g of intermediate 1 into the chloroform solvent, stirring and reacting for 3 hours, cooling to room temperature after the reaction is finished, filtering, and steaming to obtain DOPO-containing graphene intermediate;
(4) Adding 20g of epoxy resin into 100mL of acetonitrile solvent, stirring and dispersing, adding 8g of DOPO-containing graphene intermediate, 3g of triethanolamine and 4g of polyaniline into the mixture, fully and uniformly stirring, uniformly coating the mixture on a glass sheet, and placing the glass sheet into an oven for curing, wherein the curing process is 120 ℃/2h,150 ℃/1h, thus obtaining the modified epoxy resin conductive adhesive.
Example 5: the preparation process of the modified epoxy resin conductive adhesive comprises the following steps:
(1) 200mg of graphene oxide is added into 200mL of tetrahydrofuran aqueous solution with the mass fraction of 80%, stirred and dispersed, 60mL of aminopropyl triethoxysilane and 0.4mL of hydrochloric acid with the concentration of 0.14mol/L are added into the mixture at the temperature of 75 ℃, the mixture is stirred and reacted for 12 hours, and after the reaction is finished, suction filtration, tetrahydrofuran washing and drying are carried out to obtain the aminated graphene;
(2) Adding 10g of 4-aminophenol, 35g of DOPO and 5.5g of formaldehyde into 200mL of N, N-dimethylformamide solvent, stirring and dispersing, heating to 60 ℃, reacting for 5 hours, precipitating methanol after the reaction is finished, filtering, washing with methanol, and drying to obtain an intermediate 1;
(3) Adding 4g of formaldehyde into 200mL of chloroform solvent, stirring and dispersing, adding 10g of aminated graphene into the chloroform solvent at 65 ℃, stirring and dispersing, heating to 80 ℃, adding 10g of intermediate 1 into the mixture, stirring and reacting for 2 hours, cooling to room temperature after the reaction is finished, filtering, and steaming in a rotary way to obtain a DOPO-containing graphene intermediate;
(4) Adding 20g of epoxy resin into 100mL of acetonitrile solvent, stirring and dispersing, adding 10g of DOPO-containing graphene intermediate, 2g of triethanolamine and 5g of polyaniline into the mixture, fully and uniformly stirring, uniformly coating the mixture on a glass sheet, and placing the glass sheet into an oven for curing, wherein the curing process is 120 ℃/2h,150 ℃/1h, thus obtaining the modified epoxy resin conductive adhesive.
Comparative example 1: the present comparative example differs from the examples in that: the DOPO-containing graphene intermediate is not contained in the step (4).
And testing the heat resistance of the conductive adhesive by using a thermogravimetric analyzer, wherein the temperature rising rate is 10 ℃ under the condition of nitrogen, the testing temperature range is 40-550 ℃, and T 5% is the temperature at which the mass loss is 5%.
The flame retardant properties of the materials were tested using an oxygen index meter.
Table 1: results of the heat resistance and flame retardant property tests of examples and comparative examples
As is clear from Table 1, the heat resistance and flame retardance of examples 1 to 5 are better than those of comparative example 1, because examples 1 to 5 contain flame retardant DOPO structures, and heat resistant rigid benzene ring structures and benzoxazine structures. The DOPO structure generates strong dehydration substances such as phosphoric acid, metaphosphoric acid and the like when being heated, promotes the material to be dehydrated and carbonized, forms a compact carbon layer on the surface of the material, and further improves the flame retardant property of the material, wherein the introduction of the rigid structure increases the molecular stacking density of the material, thereby improving the heat resistance of the epoxy resin conductive adhesive, and the benzoxazine structure can be opened to generate a crosslinked network structure when being heated, so that the heat resistance of the material is further improved.
Referring to GB/T1410-2006, samples were prepared using glass slides with dimensions of 2.54cm×7.62cm, volume resistivity (Ω·cm) =volume resistance (Ω) ×glue line area (cm 2)/thickness of conductive glue (cm).
Table 2: results of the conductivity test of each of examples and comparative examples
As can be seen from Table 2, the epoxy resin conductive adhesive prepared by the invention has better conductive performance.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The preparation process of the modified epoxy resin conductive adhesive is characterized by comprising the following steps:
(1) Adding graphene oxide into 80% tetrahydrofuran aqueous solution by mass fraction, stirring and dispersing, adding aminopropyl triethoxysilane and 0.1-0.2mol/L hydrochloric acid into the mixture at 70-80 ℃, stirring and reacting for 10-24h, and after the reaction is finished, carrying out suction filtration, washing with tetrahydrofuran and drying to obtain the amino graphene;
(2) Adding 4-aminophenol, DOPO and formaldehyde into an N, N-dimethylformamide solvent, stirring and dispersing, heating to 60-80 ℃, reacting for 5-10 hours, precipitating methanol after the reaction is finished, filtering, washing with methanol, and drying to obtain an intermediate 1;
(3) Adding formaldehyde into chloroform solvent, stirring and dispersing, adding aminated graphene into the chloroform solvent at 60-65 ℃, stirring and dispersing, heating to 70-80 ℃, adding intermediate 1 into the chloroform solvent, stirring and reacting for 1-3h, cooling to room temperature after the reaction is finished, filtering, and steaming in a rotating way to obtain DOPO-containing graphene intermediate;
(4) Adding epoxy resin into acetonitrile solvent, stirring and dispersing, adding DOPO-containing graphene intermediate, triethanolamine and polyaniline into the mixture, fully and uniformly stirring, uniformly coating the mixture on a glass sheet, and placing the glass sheet into an oven for curing to obtain the modified epoxy resin conductive adhesive.
2. The process for preparing the modified epoxy resin conductive adhesive according to claim 1, wherein in the step (1), the dosage ratio of graphene oxide to aminopropyl triethoxysilane is 1mg: (0.2-0.5) mL.
3. The process for preparing the modified epoxy resin conductive adhesive according to claim 1, wherein in the step (2), the dosage ratio of 4-aminophenol, DOPO and formaldehyde is 1g: (3.5-5) g: (0.55-0.65) g.
4. The process for preparing the modified epoxy resin conductive adhesive according to claim 1, wherein in the step (3), the dosage ratio of formaldehyde, the aminated graphene and the intermediate 1 is (0.12-0.4) g: (0.5-2) g:1g.
5. The process for preparing the modified epoxy resin conductive adhesive according to claim 1, wherein in the step (4), the dosage ratio of the epoxy resin to the DOPO-containing graphene intermediate to the triethanolamine to the polyaniline is 1g: (0.1-0.5) g: (0.1-0.2) g: (0.1-0.3) g.
6. The process for preparing a modified epoxy resin conductive adhesive according to claim 1, wherein in the step (4), the curing process is 120 ℃/2h,150 ℃/1h.
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