CN114702646B - Fluorenyl-biphenyl type epoxy material with high insulating property and preparation method thereof - Google Patents
Fluorenyl-biphenyl type epoxy material with high insulating property and preparation method thereof Download PDFInfo
- Publication number
- CN114702646B CN114702646B CN202210416498.4A CN202210416498A CN114702646B CN 114702646 B CN114702646 B CN 114702646B CN 202210416498 A CN202210416498 A CN 202210416498A CN 114702646 B CN114702646 B CN 114702646B
- Authority
- CN
- China
- Prior art keywords
- fluorenyl
- curing agent
- molecular structure
- trifluoromethyl
- epoxy material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004593 Epoxy Substances 0.000 title claims abstract description 93
- 239000000463 material Substances 0.000 title claims abstract description 87
- 239000004305 biphenyl Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 110
- 239000003822 epoxy resin Substances 0.000 claims abstract description 43
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims abstract description 43
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 43
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 17
- 150000001412 amines Chemical class 0.000 claims abstract description 12
- 125000005843 halogen group Chemical group 0.000 claims abstract description 9
- ZPSUIVIDQHHIFH-UHFFFAOYSA-N 3-(trifluoromethyl)-4-[2-(trifluoromethyl)phenyl]benzene-1,2-diamine Chemical group FC(F)(F)C1=C(N)C(N)=CC=C1C1=CC=CC=C1C(F)(F)F ZPSUIVIDQHHIFH-UHFFFAOYSA-N 0.000 claims description 20
- FWOLORXQTIGHFX-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluoroaniline Chemical group FC1=C(F)C(N)=C(F)C(F)=C1C1=C(F)C(F)=C(N)C(F)=C1F FWOLORXQTIGHFX-UHFFFAOYSA-N 0.000 claims description 20
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 15
- PQFRTJPVZSPBFI-UHFFFAOYSA-N 3-(trifluoromethyl)benzene-1,2-diamine Chemical group NC1=CC=CC(C(F)(F)F)=C1N PQFRTJPVZSPBFI-UHFFFAOYSA-N 0.000 claims description 14
- 238000009413 insulation Methods 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 claims description 10
- KZSXRDLXTFEHJM-UHFFFAOYSA-N 5-(trifluoromethyl)benzene-1,3-diamine Chemical compound NC1=CC(N)=CC(C(F)(F)F)=C1 KZSXRDLXTFEHJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- OVGAPUVMLZWQQF-UHFFFAOYSA-N 3-bromo-5-(trifluoromethyl)benzene-1,2-diamine Chemical compound NC1=CC(C(F)(F)F)=CC(Br)=C1N OVGAPUVMLZWQQF-UHFFFAOYSA-N 0.000 claims description 6
- RQWJHUJJBYMJMN-UHFFFAOYSA-N 4-(trifluoromethyl)benzene-1,2-diamine Chemical compound NC1=CC=C(C(F)(F)F)C=C1N RQWJHUJJBYMJMN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- ZQQOGBKIFPCFMJ-UHFFFAOYSA-N 2-(trifluoromethyl)benzene-1,4-diamine Chemical compound NC1=CC=C(N)C(C(F)(F)F)=C1 ZQQOGBKIFPCFMJ-UHFFFAOYSA-N 0.000 claims description 4
- BRLIJPMFMGTIAW-UHFFFAOYSA-N 3,5-bis(trifluoromethyl)benzene-1,2-diamine Chemical compound NC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1N BRLIJPMFMGTIAW-UHFFFAOYSA-N 0.000 claims description 4
- VCINLTLIJKUOQC-UHFFFAOYSA-N 3-bromo-5-fluorobenzene-1,2-diamine Chemical compound NC1=CC(F)=CC(Br)=C1N VCINLTLIJKUOQC-UHFFFAOYSA-N 0.000 claims description 4
- VWYTZNPMXYCBPK-UHFFFAOYSA-N 3-bromobenzene-1,2-diamine Chemical compound NC1=CC=CC(Br)=C1N VWYTZNPMXYCBPK-UHFFFAOYSA-N 0.000 claims description 4
- NVNLHLRVSHJKBN-UHFFFAOYSA-N 3-chloro-5-(trifluoromethyl)benzene-1,2-diamine Chemical compound NC1=CC(C(F)(F)F)=CC(Cl)=C1N NVNLHLRVSHJKBN-UHFFFAOYSA-N 0.000 claims description 4
- TTXGKCVKGXHPRI-UHFFFAOYSA-N 4,5-dibromobenzene-1,2-diamine Chemical compound NC1=CC(Br)=C(Br)C=C1N TTXGKCVKGXHPRI-UHFFFAOYSA-N 0.000 claims description 4
- ZWUBBMDHSZDNTA-UHFFFAOYSA-N 4-Chloro-meta-phenylenediamine Chemical compound NC1=CC=C(Cl)C(N)=C1 ZWUBBMDHSZDNTA-UHFFFAOYSA-N 0.000 claims description 4
- ZTSHEADNOHWIMO-UHFFFAOYSA-N 4-bromo-3-fluorobenzene-1,2-diamine Chemical compound NC1=CC=C(Br)C(F)=C1N ZTSHEADNOHWIMO-UHFFFAOYSA-N 0.000 claims description 4
- WIHHVKUARKTSBU-UHFFFAOYSA-N 4-bromobenzene-1,2-diamine Chemical compound NC1=CC=C(Br)C=C1N WIHHVKUARKTSBU-UHFFFAOYSA-N 0.000 claims description 4
- WMKGEQCSIZQIEK-UHFFFAOYSA-N 4-fluoro-5-(trifluoromethyl)benzene-1,2-diamine Chemical compound NC1=CC(F)=C(C(F)(F)F)C=C1N WMKGEQCSIZQIEK-UHFFFAOYSA-N 0.000 claims description 4
- KWEWNOOZQVJONF-UHFFFAOYSA-N 4-fluorobenzene-1,2-diamine Chemical compound NC1=CC=C(F)C=C1N KWEWNOOZQVJONF-UHFFFAOYSA-N 0.000 claims description 4
- QNDFYLBDUWCFJO-UHFFFAOYSA-N 4-fluorobenzene-1,3-diamine Chemical compound NC1=CC=C(F)C(N)=C1 QNDFYLBDUWCFJO-UHFFFAOYSA-N 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 8
- BXIXXXYDDJVHDL-UHFFFAOYSA-N 4-Chloro-ortho-phenylenediamine Chemical compound NC1=CC=C(Cl)C=C1N BXIXXXYDDJVHDL-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 32
- 230000006698 induction Effects 0.000 abstract description 19
- 238000004132 cross linking Methods 0.000 abstract description 4
- 239000011810 insulating material Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000011259 mixed solution Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 6
- 229920006779 EP-CF Polymers 0.000 description 4
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- IWFHBRFJOHTIPU-UHFFFAOYSA-N 4,5-dichlorobenzene-1,2-diamine Chemical compound NC1=CC(Cl)=C(Cl)C=C1N IWFHBRFJOHTIPU-UHFFFAOYSA-N 0.000 description 1
- MZUGVHBCNYNIHR-UHFFFAOYSA-N 4-(4-aminophenyl)aniline;benzene Chemical group C1=CC=CC=C1.C1=CC(N)=CC=C1C1=CC=C(N)C=C1 MZUGVHBCNYNIHR-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920005547 polycyclic aromatic hydrocarbon Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the technical field of insulating materials, and particularly relates to a fluorenyl-biphenyl epoxy material with high insulating performance and a preparation method thereof. The epoxy material comprises a fluorenyl epoxy resin molecular structure and an amine curing agent molecular structure, wherein a benzene ring of the amine curing agent molecular structure carries a halogen atom or a-CF 3 group. The invention uses the curing agent A and the curing agent B with electron induction effect in the molecular structure and the fluorenyl epoxy resin to construct a fluorenyl-biphenyl type epoxy crosslinking network with electron induction effect, thus obtaining the fluorenyl-biphenyl type epoxy material with high insulating property.
Description
The application claims the priority of 'a fluorenyl-biphenyl epoxy material with high insulating property and a preparation method thereof' of which the application number is 202210396879.0 in 4/15 of 2022, and the original acceptance mechanism is China.
Technical Field
The invention belongs to the field of insulating materials, and particularly relates to a fluorenyl-biphenyl type epoxy material with high insulating performance and a preparation method thereof.
Background
With the development of large-scale integrated circuits, new energy power equipment, energy storage devices and the like toward high power density and high integration density, this puts higher demands on the insulation performance and heat resistance of the packaging material. The third generation power device represented by SiC has higher operating temperature and higher bearing voltage, and the heat resistance and the insulativity of the packaging material directly influence the service life of the device. The polyaromatic polymer has good heat resistance, especially fluorenyl epoxy resin, has high aromatic ring content, has 'Cardo' ring with larger steric hindrance in a molecular structure, can be connected with a curing agent at two ends of the molecule to form a three-dimensional network structure, has excellent high-temperature stability, and has good application prospect in the fields of electrical equipment, power devices, microelectronics and the like. In order to ensure that the epoxy crosslinking network has higher heat resistance, a curing agent with a multi-aromatic ring structure is generally selected, and the aromatic ring ratio of the biphenyl amine curing agent is high, so that the epoxy crosslinking network has good application potential in high heat resistance epoxy materials.
However, the "Cardo" ring in the molecular structure of the fluorenyl epoxy resin can form a local conjugated pi bond, and charges are easily freely shared on the structure, thereby reducing the insulating property of the epoxy material. In addition, the biphenyl amine curing agent also has conjugated pi bonds on two adjacent benzene rings, so that the proportion of the conjugated pi bonds in the fluorenyl-biphenyl epoxy material is higher, the insulating property of the biphenyl amine curing agent is poorer than that of a common epoxy material, and the insulating property requirement under the operating condition of high electric field strength can not be met, so that the method for improving the insulating property of the fluorenyl-biphenyl epoxy material without reducing the heat resistance of the fluorenyl-biphenyl epoxy material has important significance.
Disclosure of Invention
To overcome the above-mentioned drawbacks of the prior art, it is therefore an object of the present invention to provide a fluorenyl-biphenyl type epoxy material having high insulation properties, which has high insulation properties and high heat resistance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the epoxy material comprises a fluorenyl epoxy resin molecular structure and an amine curing agent molecular structure, wherein a benzene ring of the amine curing agent molecular structure carries a halogen atom or a-CF 3 group.
Preferably, the molecular structure of the epoxy material comprises a crosslinked network molecular structure 1, and the structural formula of the crosslinked network molecular structure 1 is as follows:
the crosslinked network molecular structure 1 comprises X, wherein the structural formula of X is as follows:
the-CH 2 in the structural formula of X is connected with the N atom of the crosslinked network molecular structure 1.
Preferably, the molecular structure of the epoxy material comprises a crosslinked network molecular structure 2, and the structural formula of the crosslinked network molecular structure 2 is as follows:
the crosslinked network molecular structure 2 comprises X, wherein the structural formula of X is as follows:
and-CH 2 in the structural formula of X is connected with N atoms of the cross-linked network molecular structure 2.
Preferably, the molecular structure of the epoxy material comprises a crosslinked network molecular structure 1 and a crosslinked network molecular structure 2, and the structural formula of the crosslinked network molecular structure 1 is as follows:
the structural formula of the crosslinked network molecular structure 2 is as follows:
the cross-linked network molecular structure 1 and the cross-linked network molecular structure 2 both comprise X, and the structural formula of X is as follows:
the-CH 2 in the structural formula of X is connected with the N atom of the cross-linked network molecular structure 1 or the N atom of the cross-linked network molecular structure 2.
Preferably, the amine curing agent has a molecular structure of one of a trifluoromethyl diaminobiphenyl structure, a trifluoromethyl diaminobenzene structure, a trifluoromethyl halogenated diaminobenzene structure, a diamino halogenated biphenyl structure and a diamino halogenated benzene structure.
Preferably, the amine curing agent has two or more of trifluoromethyl diaminobiphenyl structure, trifluoromethyl diaminobenzene structure, trifluoromethyl halogenated diaminobenzene structure, diamino halogenated biphenyl structure and diamino halogenated benzene structure.
The second object of the present invention is to provide a method for preparing the above fluorenyl-biphenyl epoxy material with high insulation performance, which comprises the following steps:
S1, heating and melting fluorenyl epoxy resin, and respectively and independently melting or mixing a curing agent A and a curing agent B and then heating and melting, wherein the structure of the curing agent A contains one or more than two of a trifluoromethyl diaminobiphenyl structure, a trifluoromethyl diaminobenzene structure and a trifluoromethyl halogenated diaminobenzene structure, and the structure of the curing agent B contains one or more than two of a diamino halogenated biphenyl structure and a diamino halogenated benzene structure;
S2, uniformly mixing and curing the melt of the fluorenyl epoxy resin, the curing agent A and the curing agent B to obtain the fluorenyl-biphenyl epoxy material with high insulating property.
Preferably, the curing agent A is one of 2,2' -bis (trifluoromethyl) diaminobiphenyl, 3, 5-diaminobenzotrifluoride, 4-trifluoromethyl-o-phenylenediamine, 2, 3-diaminobenzotrifluoride, 2- (trifluoromethyl) -1, 4-phenylenediamine, 3-bromo-4, 5-diaminobenzotrifluoride, 4-fluoro-5- (trifluoromethyl) benzene-1, 2-diamine, 3-chloro-4, 5-diaminobenzotrifluoride, 3, 5-bis (trifluoromethyl) -1, 2-phenylenediamine.
Preferably, the curing agent A is two or more of 2,2' -bis (trifluoromethyl) diaminobiphenyl, 3, 5-diaminobenzotrifluoride, 4-trifluoromethyl-o-phenylenediamine, 2, 3-diaminobenzotrifluoride, 2- (trifluoromethyl) -1, 4-phenylenediamine, 3-bromo-4, 5-diaminobenzotrifluoride, 4-fluoro-5- (trifluoromethyl) benzene-1, 2-diamine, 3-chloro-4, 5-diaminobenzotrifluoride, 3, 5-bis (trifluoromethyl) -1, 2-phenylenediamine.
Preferably, the curing agent B is one of 4,4' -diaminooctafluorobiphenyl, 3-dichlorobenzidine, 2', 5' -tetrachlorobenzidine, 4-fluoro-1, 3-diaminobenzene, 3-bromo-1, 2-diaminobenzene, 6-bromo-2, 3-diaminofluorobenzene, 4, 5-dibromo-1, 2-phenylenediamine, 3-bromo-1, 2-diamino-5-fluorobenzene, 4-fluoro-1, 2-phenylenediamine, 4-bromo-1, 2-phenylenediamine, 4, 5-dichlorophthalenediamine, 4-chlorophthalidomide, 4-chloro-1, 3-phenylenediamine.
Preferably, the curing agent B is two or more of 4,4' -diaminooctafluorobiphenyl, 3-dichlorobenzidine, 2', 5' -tetrachlorobenzidine, 4-fluoro-1, 3-diaminobenzene, 3-bromo-1, 2-diaminobenzene, 6-bromo-2, 3-diaminofluorobenzene, 4, 5-dibromo-1, 2-phenylenediamine, 3-bromo-1, 2-diamino-5-fluorobenzene, 4-fluoro-1, 2-phenylenediamine, 4-bromo-1, 2-phenylenediamine, 4, 5-dichlorophthalenediamine, 4-chlorophthalidomide, 4-chloro-1, 3-phenylenediamine.
Preferably, the fluorenyl epoxy resin has an epoxy value of 0.3 to 0.5mol/100g.
Preferably, the temperature of heating and melting the fluorenyl epoxy resin, the curing agent A and the curing agent B is 150-220 ℃.
Preferably, the melt solutions of the fluorenyl epoxy resin, the curing agent A and the curing agent B are uniformly mixed under vacuum stirring, wherein the vacuum stirring temperature is 150-220 ℃ and the time is 1-20min.
Preferably, the three melts are uniformly mixed and then are subjected to vacuum defoamation and then are solidified.
Preferably, the temperature of vacuum deaeration is 150-200deg.C, and the time is 10-30min.
Preferably, the number of curing is one or more.
Preferably, the number of times of curing is one, the curing temperature is 150-220 ℃ and the curing time is 2-8 hours.
Preferably, when the number of curing is two, the primary curing temperature is 150-180 ℃, the curing time is 1-3h, the secondary curing temperature is 180-220 ℃, and the curing time is 2-5h.
Preferably, the mass ratio of the fluorenyl epoxy resin to the curing agent A to the curing agent B is (180-240): 40-90): 0-20.
The invention has the advantages that:
(1) The fluorenyl-biphenyl type epoxy material contains a fluorenyl epoxy resin molecular structure and an amine curing agent molecular structure, wherein the amine curing agent molecular structure is one or more than two of a diamino halogenated biphenyl structure, a diamino halogenated benzene structure, a trifluoromethyl diamino biphenyl structure, a trifluoromethyl diamino benzene structure and a trifluoromethyl halogenated diamino benzene structure; the epoxy material has high insulating property and heat resistance, and the heat resistance is not reduced, because the benzene ring of the curing agent carries halogen atoms or-CF 3 groups, and because the electronegativity of the halogen atoms and-CF 3 groups is larger than that of the C atoms on the benzene ring, electron induction effect can be generated on the halogen atoms and-CF 3 groups, electrons on the benzene ring are deviated to the halogen atoms and-CF 3 groups, thereby inhibiting free sharing of electrons of conjugated pi bonds on the benzene ring and realizing improvement of the insulating property of the epoxy material. In addition, since the molecular skeleton of the fluorenyl-biphenyl epoxy material is not changed by the method, the heat resistance thereof is not reduced.
(2) The curing agent A and the curing agent B selected by the invention have stronger electron induction effect in the molecular structure; compared with biphenyl amine curing agents, the molecular structures of the two curing agents have C-F bonds with larger electronegativity, electrons can be induced to deviate from the biphenyl structure through the C-F bonds and are bound around F atoms, free sharing of electrons on the biphenyl structure is inhibited, and therefore the insulating property of the fluorenyl-biphenyl epoxy material is improved; the two curing agents have good high-temperature stability, and can improve the heat resistance of the fluorenyl-biphenyl epoxy material while improving the insulating property of the fluorenyl-biphenyl epoxy material. Meanwhile, the chemical reaction process of the three raw materials is carried out in the curing stage, and the insulation performance of the fluorenyl-biphenyl epoxy material can be improved by reasonably proportioning the raw materials, so that the process is simple, and the industrial production is easy to realize.
(3) The mass ratio of the fluorenyl epoxy resin to the curing agent A to the curing agent B is (180-240): (40-90): (0-20), and the purpose of the invention is to crosslink and cure the curing agent A and the curing agent B with the fluorenyl epoxy resin to obtain the epoxy material with the electron induction effect.
The structure of the curing agent A contains one or more than two of trifluoromethyl diaminobiphenyl structure, trifluoromethyl diaminobenzene structure and trifluoromethyl halogenated diaminobenzene structure, the structure of the curing agent B contains one or more than two of diamino halogenated biphenyl structure and diamino halogenated benzene structure, and an electron induction effect is introduced into an epoxy crosslinking network through the curing agent A and the curing agent B.
The fluorenyl epoxy resin with the epoxy value of 0.3-0.5mol/100g is preferably used as the raw material, so that the use amount of the curing agent A and the curing agent B can be conveniently determined according to the epoxy value.
The temperature of heating and melting the three raw materials is 150-220 ℃; the melting points of the curing agent A and the curing agent B are close to the melting point (150-170 ℃) of the fluorenyl epoxy resin, the mixed solution reacts mildly, and the melting temperature of 150-220 ℃ is set to well control the progress of the sample curing reaction. The three melts are fully and uniformly mixed under vacuum, then vacuum defoamation and resolidification are carried out, and the vacuum mixing and the defoamation facilitate removing gas in the solidified matters and reduce defects in the solidified and molded samples.
The number of curing is one or more, which is favorable for obtaining the sample with the best performance.
Drawings
FIG. 1 is a cross-linked network molecular structure diagram of a fluorenyl-biphenyl epoxy material incorporating an electron-induced effect.
Fig. 2 is a graph showing breakdown strength of the fluorenyl-biphenyl type epoxy material having an electron-induced effect prepared in example 1 and the fluorenyl-biphenyl type epoxy material having no electron-induced effect prepared in comparative example.
Fig. 3 is a volume resistivity of the fluorenyl-biphenyl type epoxy material having an electron-induced effect prepared in example 1 and the fluorenyl-biphenyl type epoxy material having no electron-induced effect prepared in comparative example.
Fig. 4 is a graph showing glass transition temperatures of the fluorenyl-biphenyl type epoxy material having an electron-induced effect prepared in example 1 and the fluorenyl-biphenyl type epoxy material having no electron-induced effect prepared in comparative example.
Detailed Description
The present invention will be further described in detail with reference to the following examples, in order to make the objects, technical solutions and advantages of the present invention more apparent, and all other examples obtained by those skilled in the art without making any inventive effort are within the scope of the present invention based on the examples in the present invention.
In the present invention, the following is described. The trifluoromethyl diaminobiphenyl structure is also a trifluoromethyl diaminobiphenyl structure; the trifluoromethyl diaminobenzene structure is also a trifluoromethyl diaminobenzene structure; the trifluoromethyl halogenated diaminobenzene structure is also a fluoromethyl halogenated diaminobenzene structure; the diamino halogenated biphenyl structure is also a diamine halogenated biphenyl structure; the diamino halogenobenzene structure is also a diamine halogenobenzene structure; wherein the diamine or the diammine is the same group, namely-NH 2.
Example 1
S1, 200g of fluorenyl epoxy resin, 60.8g of curing agent A (2, 2 '-bis (trifluoromethyl) diaminobiphenyl) and 3.2g of curing agent B (4, 4' -diaminooctafluorobiphenyl) are taken and placed in a container, and heated and melted at 190 ℃;
S2, pouring the melted fluorenyl epoxy resin, a curing agent A (2, 2 '-bis (trifluoromethyl) diaminobiphenyl) and a curing agent B (4, 4' -diaminooctafluorobiphenyl) into a container, and stirring in vacuum at the temperature of 190 ℃ for 2min to obtain a uniform mixed solution;
S3, pouring the mixed solution into a mold, reducing the temperature to 185 ℃ for vacuum defoaming for 20min, and then raising the temperature of the mold to 190 ℃ for high-temperature curing reaction for 2h; and finally, raising the temperature of the die to 210 ℃ for high-temperature curing reaction for 3 hours to prepare a fluorenyl-biphenyl type epoxy material sample with an electron induction effect in a crosslinked network, wherein the diameter of the sample is 10cm, and the thickness of the sample is 1mm.
Example 2
S1, 200g of fluorenyl epoxy resin, 53.2g of curing agent A (2, 2 '-bis (trifluoromethyl) diaminobiphenyl) and 10.8g of curing agent B (4, 4' -diaminooctafluorobiphenyl) are taken and placed in a container, and the materials are heated and melted at 185 ℃;
S2, pouring the melted fluorenyl epoxy resin, a curing agent A (2, 2 '-bis (trifluoromethyl) diaminobiphenyl) and a curing agent B (4, 4' -diaminooctafluorobiphenyl) into a container, and stirring in vacuum for 5min at 185 ℃ to obtain a uniform mixed solution;
S3, pouring the mixed solution into a die, and reducing the temperature to 180 ℃ for vacuum defoaming for 15min; then the temperature of the die is increased to 185 ℃ to carry out high-temperature curing reaction for 3 hours; and finally, raising the temperature of the die to 195 ℃ for high-temperature curing reaction for 5 hours, and preparing a fluorenyl-biphenyl type epoxy material sample with an electron induction effect in a crosslinked network, wherein the diameter of the sample is 10cm, and the thickness of the sample is 1mm.
Example 3
S1, 200g of fluorenyl epoxy resin, 46.7g of curing agent A (2, 2 '-bis (trifluoromethyl) diaminobiphenyl) and 17.3g of curing agent B (4, 4' -diaminooctafluorobiphenyl) are taken and placed in a container, and the materials are heated and melted at a constant temperature of 200 ℃;
S2, pouring the melted fluorenyl epoxy resin, a curing agent A (2, 2 '-bis (trifluoromethyl) diaminobiphenyl) and a curing agent B (4, 4' -diaminooctafluorobiphenyl) into a container, and stirring in vacuum for 1min at the temperature of 200 ℃ to obtain a uniform mixed solution;
s3, pouring the mixed solution into a die, and reducing the temperature to 190 ℃ for vacuum defoaming for 10min; then the temperature of the die is increased to 200 ℃ for high-temperature curing reaction for 1h; and finally, raising the temperature of the die to 210 ℃ for high-temperature curing reaction for 2 hours to prepare a fluorenyl-biphenyl type epoxy material sample with an electron induction effect in a crosslinked network, wherein the diameter of the sample is 10cm, and the thickness of the sample is 1mm.
Example 4
S1, 200g of fluorenyl epoxy resin, 60.8g of curing agent A (2, 2 '-bis (trifluoromethyl) diaminobiphenyl (58 g) and 3, 5-diaminobenzotrifluoride (2.8 g)) and 3.2g of curing agent B (4, 4' -diaminooctafluorobiphenyl) are taken and placed in a container, and heated and melted at 190 ℃;
S2, pouring the melted fluorenyl epoxy resin, a curing agent A (2, 2 '-bis (trifluoromethyl) diaminobiphenyl, 3, 5-diaminobenzotrifluoride) and a curing agent B (4, 4' -diaminooctafluorobiphenyl) into a container, and stirring in vacuum at the temperature of 190 ℃ for 2min to obtain a uniform mixed solution;
S3, pouring the mixed solution into a mold, reducing the temperature to 185 ℃ for vacuum defoaming for 20min, and then raising the temperature of the mold to 190 ℃ for high-temperature curing reaction for 2h; and finally, raising the temperature of the die to 210 ℃ for high-temperature curing reaction for 3 hours to prepare a fluorenyl-biphenyl type epoxy material sample with an electron induction effect in a crosslinked network, wherein the diameter of the sample is 10cm, and the thickness of the sample is 1mm.
Example 5
S1, 200g of fluorenyl epoxy resin, 60.8g of curing agent A (2, 2 '-bis (trifluoromethyl) diaminobiphenyl (58 g) and 4-trifluoromethyl o-phenylenediamine (2.8 g) and 3.2g of curing agent B (4, 4' -diaminooctafluorobiphenyl) are taken and placed in a container, and heated and melted at 190 ℃;
S2, pouring the melted fluorenyl epoxy resin, a curing agent A (2, 2 '-bis (trifluoromethyl) diaminobiphenyl and 4-trifluoromethyl o-phenylenediamine) and a curing agent B (4, 4' -diamino octafluorobiphenyl) into a container, and stirring in vacuum at the temperature of 190 ℃ for 2min to obtain a uniform mixed solution;
S3, pouring the mixed solution into a mold, reducing the temperature to 185 ℃ for vacuum defoaming for 20min, and then raising the temperature of the mold to 190 ℃ for high-temperature curing reaction for 2h; and finally, raising the temperature of the die to 210 ℃ for high-temperature curing reaction for 3 hours to prepare a fluorenyl-biphenyl type epoxy material sample with an electron induction effect in a crosslinked network, wherein the diameter of the sample is 10cm, and the thickness of the sample is 1mm.
Example 6
S1, 200g of fluorenyl epoxy resin, 60.8g of curing agent A (2, 2 '-bis (trifluoromethyl) diaminobiphenyl) and 3.2g of curing agent B (4, 4' -diaminooctafluorobiphenyl (2 g) and 2,2', 5' -tetrachlorobenzidine (1.2 g)) are taken and placed in a container, and heated and melted at 190 ℃;
S2, pouring the melted fluorenyl epoxy resin, a curing agent A (2, 2 '-bis (trifluoromethyl) diaminobiphenyl) and a curing agent B (4, 4' -diaminooctafluorobiphenyl and 2,2', 5' -tetrachlorobenzidine) into a container, and stirring in vacuum at the temperature of 190 ℃ for 2min to obtain a uniform mixed solution;
S3, pouring the mixed solution into a mold, reducing the temperature to 185 ℃ for vacuum defoaming for 20min, and then raising the temperature of the mold to 190 ℃ for high-temperature curing reaction for 2h; and finally, raising the temperature of the die to 210 ℃ for high-temperature curing reaction for 3 hours to prepare a fluorenyl-biphenyl type epoxy material sample with an electron induction effect in a crosslinked network, wherein the diameter of the sample is 10cm, and the thickness of the sample is 1mm.
Example 7
S1, 200g of fluorenyl epoxy resin, 60.8g of curing agent A (2, 2 '-bis (trifluoromethyl) diaminobiphenyl (58 g) and 3, 5-diaminobenzotrifluoride (2.8 g)) and 3.2g of curing agent B (4, 4' -diaminooctafluorobiphenyl (2 g) and 2,2', 5' -tetrachlorobenzidine (1.2 g)) are taken and placed in a container, and heated and melted at 190 ℃;
s2, pouring the melted fluorenyl epoxy resin, a curing agent A (2, 2 '-bis (trifluoromethyl) diaminobiphenyl, 3, 5-diaminobenzotrifluoride) and a curing agent B (4, 4' -diaminooctafluorobiphenyl, 2', 5' -tetrachlorobenzidine) into a container, and stirring in vacuum at 190 ℃ for 2min to obtain a uniform mixed solution;
S3, pouring the mixed solution into a mold, reducing the temperature to 185 ℃ for vacuum defoaming for 20min, and then raising the temperature of the mold to 190 ℃ for high-temperature curing reaction for 2h; and finally, raising the temperature of the die to 210 ℃ for high-temperature curing reaction for 3 hours to prepare a fluorenyl-biphenyl type epoxy material sample with an electron induction effect in a crosslinked network, wherein the diameter of the sample is 10cm, and the thickness of the sample is 1mm.
Example 8
S1, 200g of fluorenyl epoxy resin, 60.8g of curing agent A (2, 2 '-bis (trifluoromethyl) diaminobiphenyl (55 g), 3, 5-diaminobenzotrifluoride (2.8 g), 3-bromo-4, 5-diaminobenzotrifluoride) (3 g) and 3.2g of curing agent B (4, 4' -diaminooctafluorobiphenyl (1.6 g), 2', 5' -tetrachlorobenzidine (0.8 g) and 4, 5-dichlorophthalenediamine (0.8 g) are taken and placed in a container, and heated and melted at 190 ℃;
S2, pouring melted fluorenyl epoxy resin, a curing agent A (2, 2 '-bis (trifluoromethyl) diaminobiphenyl, 3, 5-diaminobenzotrifluoride, 3-bromo-4, 5-diaminobenzotrifluoride) and a curing agent B (4, 4' -diaminooctafluorobiphenyl, 2', 5' -tetrachlorobenzidine and 4, 5-dichloro o-phenylenediamine) into a container, and stirring in vacuum at 190 ℃ for 2min to obtain a uniform mixed solution;
S3, pouring the mixed solution into a mold, reducing the temperature to 185 ℃ for vacuum defoaming for 20min, and then raising the temperature of the mold to 190 ℃ for high-temperature curing reaction for 2h; and finally, raising the temperature of the die to 210 ℃ for high-temperature curing reaction for 3 hours to prepare a fluorenyl-biphenyl type epoxy material sample with an electron induction effect in a crosslinked network, wherein the diameter of the sample is 10cm, and the thickness of the sample is 1mm.
Comparative example 1
S1, respectively placing 200g of fluorenyl epoxy resin and 37g of benzidine in a container, and heating and melting at 160 ℃;
s2, pouring the melted fluorenyl epoxy resin and benzidine into a container, and stirring in vacuum for 1min at 155 ℃ to obtain uniform mixed solution;
S3, pouring the mixed solution into a die, and reducing the temperature to 150 ℃ for vacuum defoaming for 20min; then the temperature of the die is increased to 160 ℃ for high-temperature curing reaction for 2 hours; and finally, raising the temperature of the die to 180 ℃ for high-temperature curing reaction for 3 hours to prepare the fluorenyl-biphenyl epoxy material sample of the comparative example, wherein the diameter of the sample is 10cm, and the thickness of the sample is 1mm.
The sample of the fluorenyl-biphenyl type epoxy material with electron induction effect prepared in example 1 and the sample of the fluorenyl-biphenyl type epoxy material prepared in comparative example were respectively subjected to a breakdown strength test, a volume resistivity test and a glass transition temperature test, and analysis of test results is shown in fig. 2, 3 and 4. In the figure, EP-0F is a sample of comparative example, and EP-CF+F is a sample of example 1.
The test method for the performance of the test sample is as follows:
volume resistivity test: the volume resistivity of the test pieces was measured at a temperature of 23℃and a relative humidity of 50% using a ZC36 type high resistance meter.
Breakdown strength test: placing the sample in insulating oil, testing the breakdown strength of the sample by adopting a ball-ball electrode, applying an alternating voltage with a linear rise of 2kV/s between the electrodes until the breakdown appears in the experiment, recording the voltage value of the breakdown of the sample, testing 8 samples of the same type, processing the tested 8 groups of data by adopting Weibull distribution, and taking the voltage value with the probability of 63.2% as the final breakdown strength value of the sample.
Glass transition temperature test: the samples were placed in a high purity nitrogen vessel, the temperature was first raised from room temperature to 300 ℃, then lowered from 300 ℃ to room temperature, finally raised to 300 ℃ at a rate of 10 ℃/min, the exotherm of the samples was tested using DSC (Q2000), the glass transition temperature of the samples was analyzed using TA Universal Analysis software, 3 samples were each tested, and the average value was taken as the final glass transition temperature.
As can be seen from fig. 2, the breakdown strength of the sample of the fluorenyl-biphenyl type epoxy material (EP-cf+f) obtained by introducing the electron-induced effect in example 1 was 39.18kV/mm, while the breakdown strength of the sample of the fluorenyl-biphenyl type epoxy material (EP-0F) without introducing the electron-induced effect in the comparative example was only 33.16kV/mm, and the breakdown strength of the EP-cf+f sample was improved by 18.2% with respect to EP-0F; the insulating properties of the sample prepared in example 1 were superior to those of the sample of comparative example 1. Therefore, the H atoms on the benzene ring of the biphenyl structure are replaced by atoms or groups with large electronegativity, and the introduction of electron induction effect can improve the insulating performance of the fluorenyl-biphenyl epoxy material.
As can be seen from FIG. 3, it was found from the test of the volume resistivity of the sample that the volume resistivity of the sample of the fluorenyl-biphenyl type epoxy material (EP-CF+F) obtained by introducing the electron-induced effect was 20.64X10 16 Ω.cm, the volume resistivity of the sample of the fluorenyl-biphenyl type epoxy material (EP-0F) obtained by not introducing the electron-induced effect was 3.21X10 16 Ω.cm, and the volume resistivity of the EP-CF+F was nearly an order of magnitude higher than that of the EP-0F. Therefore, the volume resistivity of the fluorenyl-biphenyl epoxy material can be improved by introducing the electron induction effect, so that the conclusion that the insulating property of the fluorenyl-biphenyl epoxy material is improved by introducing the electron induction effect is verified.
As can be seen from FIG. 4, the glass transition temperature of the sample of the fluorenyl-biphenyl type epoxy material (EP-CF+F) obtained by introducing the electron-induced effect was 26℃higher than that of the sample of the fluorenyl-biphenyl type epoxy material (EP-0F) without introducing the electron-induced effect. Since the electronegativity of the halogen atom and the-CF 3 group in the curing agent of example 1 is greater than that of the H atom on the benzidine benzene ring of the comparative example, and the preparation method of the present invention does not damage the molecular skeleton of the fluorenyl-biphenyl type epoxy material, the heat resistance thereof does not decrease. In addition, the C-F on the curing agent A and the curing agent B introduced in the embodiment 1 have higher bond energy (530 kJ/mol), and F atoms on the molecular structure of the curing agent A (curing agent B) can form hydrogen bond action with-NH-on the molecular structure of the adjacent curing agent A (curing agent B), and F atoms on the molecular structure of the curing agent A (curing agent B) can also form hydrogen bond action with-OH groups on the molecular structure of the adjacent fluorenyl epoxy resin, so that the heat resistance of the fluorenyl-biphenyl epoxy material is improved. The test results indicated that: the introduction of electron induction effect on the molecular structure of the fluorenyl epoxy resin can not only improve the insulating property of the fluorenyl-biphenyl epoxy material, but also improve the heat resistance of the fluorenyl-biphenyl epoxy material, and the fluorenyl-biphenyl epoxy material with both high insulating property and high heat resistance can be prepared by using the method, so that the fluorenyl-biphenyl epoxy material is beneficial to the application of the fluorenyl-biphenyl epoxy material to the fields of high temperature and high electric field intensity.
The above embodiments are merely preferred embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of the present invention.
Claims (18)
1. The fluorenyl-biphenyl type epoxy material with high insulating property is characterized by comprising a fluorenyl epoxy resin molecular structure and an amine curing agent molecular structure, wherein a benzene ring of the amine curing agent molecular structure carries a halogen atom or a-CF 3 group, and the halogen atom is fluorine;
The molecular structure of the epoxy material comprises a crosslinked network molecular structure 1, wherein the crosslinked network molecular structure 1 has the structural formula:
the crosslinked network molecular structure 1 comprises X, wherein the structural formula of X is as follows: -CH 2 in the structural formula of X is connected to the N atom of the crosslinked network molecular structure 1;
The molecular structure of the epoxy material comprises a crosslinked network molecular structure 2, wherein the crosslinked network molecular structure 2 has the structural formula:
the crosslinked network molecular structure 2 comprises X, wherein the structural formula of X is as follows: and-CH 2 in the structural formula of X is connected with N atoms of the cross-linked network molecular structure 2.
2. The fluorenyl-biphenyl epoxy material with high insulation performance according to claim 1, wherein the molecular structure of the epoxy material comprises a crosslinked network molecular structure 1 and a crosslinked network molecular structure 2, and the crosslinked network molecular structure 1 has the structural formula:
the structural formula of the crosslinked network molecular structure 2 is as follows:
the cross-linked network molecular structure 1 and the cross-linked network molecular structure 2 both comprise X, and the structural formula of X is as follows: the-CH 2 in the structural formula of X is connected with the N atom of the cross-linked network molecular structure 1 or the N atom of the cross-linked network molecular structure 2.
3. The fluorenyl-biphenyl epoxy material with high insulating property according to claim 1, wherein the amine curing agent molecular structure is one of a trifluoromethyl diaminobiphenyl structure, a trifluoromethyl diaminobenzene structure, a trifluoromethyl halogenated diaminobenzene structure, a diamino halogenated biphenyl structure and a diamino halogenated benzene structure.
4. The fluorenyl-biphenyl epoxy material with high insulating property according to claim 1, wherein the amine curing agent has a molecular structure of two or more of a trifluoromethyl diaminobiphenyl structure, a trifluoromethyl diaminobenzene structure, a trifluoromethyl halogenated diaminobenzene structure, a diamino halogenated biphenyl structure and a diamino halogenated benzene structure.
5. A method for producing a fluorenyl-biphenyl epoxy material having high insulation properties according to any one of claims 1 to 4, comprising the steps of:
S1, heating and melting fluorenyl epoxy resin, and respectively and independently melting or mixing a curing agent A and a curing agent B and then heating and melting, wherein the structure of the curing agent A contains one or more than two of a trifluoromethyl diaminobiphenyl structure, a trifluoromethyl diaminobenzene structure and a trifluoromethyl halogenated diaminobenzene structure, and the structure of the curing agent B contains one or more than two of a diamino halogenated biphenyl structure and a diamino halogenated benzene structure;
S2, uniformly mixing and curing the melt of the fluorenyl epoxy resin, the curing agent A and the curing agent B to obtain the fluorenyl-biphenyl epoxy material with high insulating property.
6. The method for producing a fluorenyl-biphenyl epoxy material having high insulating properties according to claim 5, wherein the curing agent a is one of 2,2' -bis (trifluoromethyl) diaminobiphenyl, 3, 5-diaminobenzotrifluoride, 4-trifluoromethyl-o-phenylenediamine, 2, 3-diaminobenzotrifluoride, 2- (trifluoromethyl) -1, 4-phenylenediamine, 3-bromo-4, 5-diaminobenzotrifluoride, 4-fluoro-5- (trifluoromethyl) benzene-1, 2-diamine, 3-chloro-4, 5-diaminobenzotrifluoride, 3, 5-bis (trifluoromethyl) -1, 2-phenylenediamine.
7. The method for producing a fluorenyl-biphenyl epoxy material having high insulating properties according to claim 5, wherein the curing agent a is two or more of 2,2' -bis (trifluoromethyl) diaminobiphenyl, 3, 5-diaminobenzotrifluoride, 4-trifluoromethyl-o-phenylenediamine, 2, 3-diaminobenzotrifluoride, 2- (trifluoromethyl) -1, 4-phenylenediamine, 3-bromo-4, 5-diaminobenzotrifluoride, 4-fluoro-5- (trifluoromethyl) benzene-1, 2-diamine, 3-chloro-4, 5-diaminobenzotrifluoride, 3, 5-bis (trifluoromethyl) -1, 2-phenylenediamine.
8. The method for producing a fluorenyl-biphenyl epoxy material having high insulating properties according to claim 5, wherein the curing agent B is one of 4,4' -diaminooctafluorobiphenyl, 3-dichlorobenzidine, 2', 5' -tetrachlorobenzidine, 4-fluoro-1, 3-diaminobenzene, 3-bromo-1, 2-diaminobenzene, 6-bromo-2, 3-diaminofluorobenzene, 4, 5-dibromo-1, 2-phenylenediamine, 3-bromo-1, 2-diamino-5-fluorobenzene, 4-fluoro-1, 2-phenylenediamine, 4-bromo-1, 2-phenylenediamine, 4, 5-dichlorophthalenediamine, 4-chloro-o-phenylenediamine, 4-chloro-1, 3-phenylenediamine.
9. The method for producing a fluorenyl-biphenyl epoxy material having high insulating properties according to claim 5, wherein the curing agent B is two or more of 4,4' -diaminooctafluorobiphenyl, 3-dichlorobenzidine, 2', 5' -tetrachlorobenzidine, 4-fluoro-1, 3-diaminobenzene, 3-bromo-1, 2-diaminobenzene, 6-bromo-2, 3-diaminofluorobenzene, 4, 5-dibromo-1, 2-phenylenediamine, 3-bromo-1, 2-diamino-5-fluorobenzene, 4-fluoro-1, 2-phenylenediamine, 4-bromo-1, 2-phenylenediamine, 4, 5-dichlorophthalenediamine, 4-chlorophthaline diamine, 4-chloro-1, 3-phenylenediamine.
10. The method for producing a fluorenyl-biphenyl epoxy material having high insulation performance according to claim 5, wherein the fluorenyl epoxy resin has an epoxy value of 0.3 to 0.5mol/100g.
11. The method for preparing a fluorenyl-biphenyl epoxy material with high insulation performance according to claim 5, wherein the temperature of heating and melting of the fluorenyl epoxy resin, the curing agent A and the curing agent B is 150-220 ℃.
12. The method for preparing a fluorenyl-biphenyl epoxy material with high insulation performance according to claim 5, wherein the melt of fluorenyl epoxy resin, curing agent A and curing agent B is uniformly mixed under vacuum stirring, and the vacuum stirring temperature is 150-220 ℃ and the time is 1-20min.
13. The method for preparing a fluorenyl-biphenyl epoxy material with high insulating property according to claim 5, wherein the three melt solutions are uniformly mixed and then subjected to vacuum defoaming and then are solidified.
14. The method for preparing a fluorenyl-biphenyl epoxy material with high insulation performance according to claim 13, wherein the vacuum defoamation temperature is 150-200 ℃ and the time is 10-30min.
15. The method for producing a fluorenyl-biphenyl epoxy material having high insulating properties according to claim 5, wherein the number of curing is one or more.
16. The method for preparing a fluorenyl-biphenyl epoxy material having high insulation performance according to claim 15, wherein the curing time is 2-8 hours at 150-220 ℃ when the number of times of curing is one time.
17. The method for preparing a fluorenyl-biphenyl epoxy material having high insulation performance according to claim 15, wherein the number of times of curing is two, the primary curing temperature is 150-180 ℃, the curing time is 1-3h, the secondary curing temperature is 180-220 ℃, and the curing time is 2-5h.
18. The method for producing a fluorenyl-biphenyl epoxy material having high insulation performance according to claim 5, wherein the mass ratio of the fluorenyl epoxy resin, the curing agent a, and the curing agent B is (180-240): (40-90): (0-20).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2022103968790 | 2022-04-15 | ||
| CN202210396879 | 2022-04-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114702646A CN114702646A (en) | 2022-07-05 |
| CN114702646B true CN114702646B (en) | 2024-05-31 |
Family
ID=82175868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210416498.4A Active CN114702646B (en) | 2022-04-15 | 2022-04-20 | Fluorenyl-biphenyl type epoxy material with high insulating property and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114702646B (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108642A (en) * | 1985-12-23 | 1987-07-22 | 标准石油公司 | Fluoridize epoxy fluorocarbon coating compositions and preparation method thereof |
| US4684678A (en) * | 1985-05-30 | 1987-08-04 | Minnesota Mining And Manufacturing Company | Epoxy resin curing agent, process, and composition |
| CN1995255A (en) * | 2006-12-20 | 2007-07-11 | 哈尔滨工程大学 | Thermostable epoxy resin adhesive and its preparation method |
| CN101704989A (en) * | 2009-11-13 | 2010-05-12 | 东华大学 | Fluorine-containing imine matrix resin used for advanced composite material and preparation method thereof |
| CN102660023A (en) * | 2012-04-25 | 2012-09-12 | 哈尔滨工程大学 | Mixed diamine type copolyfluorene benzoxazine prepolymer and preparation method thereof |
| CN103146331A (en) * | 2013-03-11 | 2013-06-12 | 东华大学 | 4,4'-bis(2,4-diamidophenoxy)biphenyl high-temperature-resistant epoxy adhesive and preparation method thereof |
| KR20150101932A (en) * | 2014-02-27 | 2015-09-04 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Method for producing fluorene skeleton-containing epoxy resin, epoxy resin composition, and cured product thereof |
| CN109400848A (en) * | 2018-10-23 | 2019-03-01 | 福州大学 | A kind of synthesis of fluorenyl epoxy resin and its application in thermosetting resin |
| CN109942793A (en) * | 2019-03-22 | 2019-06-28 | 合肥工业大学 | A kind of Organic fluoride modified epoxy and its preparation method and application improving edge flashing voltage |
| CN110540644A (en) * | 2019-09-06 | 2019-12-06 | 株洲时代新材料科技股份有限公司 | Polyamide-imide-polyimide copolymer molding compound and preparation method thereof |
| CN111675882A (en) * | 2020-07-23 | 2020-09-18 | 上海雄润树脂有限公司 | Electrical high-glass transition temperature epoxy resin and preparation process thereof |
| CN114015019A (en) * | 2021-11-05 | 2022-02-08 | 合肥工业大学 | Method for improving surface flashover voltage of epoxy resin insulating material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201717639D0 (en) * | 2017-10-26 | 2017-12-13 | Cytec Ind Inc | Resin compositions and resin infusion process |
-
2022
- 2022-04-20 CN CN202210416498.4A patent/CN114702646B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4684678A (en) * | 1985-05-30 | 1987-08-04 | Minnesota Mining And Manufacturing Company | Epoxy resin curing agent, process, and composition |
| CN86108642A (en) * | 1985-12-23 | 1987-07-22 | 标准石油公司 | Fluoridize epoxy fluorocarbon coating compositions and preparation method thereof |
| CN1995255A (en) * | 2006-12-20 | 2007-07-11 | 哈尔滨工程大学 | Thermostable epoxy resin adhesive and its preparation method |
| CN101704989A (en) * | 2009-11-13 | 2010-05-12 | 东华大学 | Fluorine-containing imine matrix resin used for advanced composite material and preparation method thereof |
| CN102660023A (en) * | 2012-04-25 | 2012-09-12 | 哈尔滨工程大学 | Mixed diamine type copolyfluorene benzoxazine prepolymer and preparation method thereof |
| CN103146331A (en) * | 2013-03-11 | 2013-06-12 | 东华大学 | 4,4'-bis(2,4-diamidophenoxy)biphenyl high-temperature-resistant epoxy adhesive and preparation method thereof |
| KR20150101932A (en) * | 2014-02-27 | 2015-09-04 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Method for producing fluorene skeleton-containing epoxy resin, epoxy resin composition, and cured product thereof |
| CN109400848A (en) * | 2018-10-23 | 2019-03-01 | 福州大学 | A kind of synthesis of fluorenyl epoxy resin and its application in thermosetting resin |
| CN109942793A (en) * | 2019-03-22 | 2019-06-28 | 合肥工业大学 | A kind of Organic fluoride modified epoxy and its preparation method and application improving edge flashing voltage |
| CN110540644A (en) * | 2019-09-06 | 2019-12-06 | 株洲时代新材料科技股份有限公司 | Polyamide-imide-polyimide copolymer molding compound and preparation method thereof |
| CN111675882A (en) * | 2020-07-23 | 2020-09-18 | 上海雄润树脂有限公司 | Electrical high-glass transition temperature epoxy resin and preparation process thereof |
| CN114015019A (en) * | 2021-11-05 | 2022-02-08 | 合肥工业大学 | Method for improving surface flashover voltage of epoxy resin insulating material |
Non-Patent Citations (3)
| Title |
|---|
| Effect of methyl substituent on the curing of bisphenol-arylamine-based benzoxazines;Song, Yan et al.;《THERMOCHIMICA ACTA》;20180204;第662卷;第55-63页 * |
| Synthesis and Optical Properties of n-Type Polymers Containing Perylene Moieties;Ki-Soo Kim et al.;《Molecular Crystals and Liquid Crystals》;20101114;第29卷(第38期);第445-454页 * |
| 含芴结构环氧树脂的合成与性能;张炜, 申蕾, 王新庆, 黄鹏程;复合材料学报;20030830;第20卷(第04期);第81-87页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114702646A (en) | 2022-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Crosslinked epoxy materials exhibiting thermal remendablility and removability from multifunctional maleimide and furan compounds | |
| US3669930A (en) | Thermally stable thermosetting resin | |
| JP3359410B2 (en) | Epoxy resin composition for molding, molded product for high voltage equipment using the same, and method for producing the same | |
| EP2470583A1 (en) | Curable epoxy resin composition | |
| Kong et al. | Low k epoxy resin containing cycloaliphatic hydrocarbon with high crosslinking density | |
| CN115806685B (en) | Polyimide film and preparation method thereof | |
| CN112694685B (en) | Preparation method of poly 4-methylpentene nanosheet composite film | |
| Wang et al. | Synthesis and properties of phthalonitrile terminated polyaryl ether nitrile containing fluorene group | |
| CN114702646B (en) | Fluorenyl-biphenyl type epoxy material with high insulating property and preparation method thereof | |
| Dong et al. | Preparation of fluorinated epoxy‐phthalonitrile resins with excellent thermal stability and low dielectric constant | |
| Iqbal et al. | Development of sustainable polybenzoxazine-based organic–inorganic hybrid nanocomposites for high voltage insulator applications | |
| Zhang et al. | Naphthalene‐containing poly (arylene ether ketone) with low dielectric constant | |
| Liu et al. | Copolymerization modification: improving the processability and thermal properties of phthalonitrile resins with novel comonomers | |
| Teh et al. | DGEBA‐grafted polyaniline: Synthesis, characterization and thermal properties | |
| Wang et al. | An investigation of the relationship between the performance of polybenzoxazine and backbone structure of hyperbranched epoxy modifiers | |
| CN116589830A (en) | High-heat-conductivity insulating resin and preparation method thereof | |
| Huang et al. | Molding compounds based on aminophenoxyphthalonitrile/epoxy resin for high-temperature electronic packaging applications | |
| Chen et al. | Preparation and properties of novolac epoxy resins containing polycyclic aromatic hydrocarbons | |
| Durga et al. | Synthesis and characterization of diamide–diimide–diamines based on p‐amino benzoic acid and their curing and thermal behavior with epoxy blends containing phosphorus/silicon in the main chain | |
| CN110563926A (en) | Fluorine-containing epoxy resin curing agent and preparation method thereof, and epoxy resin material and preparation method thereof | |
| Li et al. | A molecular design strategy to develop all‐organic crosslinked polyetherimide film with high discharged energy density at 150° C | |
| CN109280062A (en) | A kind of compound of the benzoxazine of azine containing phospha, epoxide resin material and its preparation method and application | |
| Bao et al. | Characterization of Heat-Resistant Insulating Impregnating Varnish Based on Bismaleimide/Diamine Copolymer | |
| Cui et al. | Synthesis and properties of an electroactive alternating multi‐block copolymer of poly (ethylene oxide) and oligo‐aniline with high dielectric constant | |
| An et al. | Synthesis and characterization of soluble poly (ether imide) s containing fluorenyl cardo groups |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |