CN114806091A - POSS-CuPc-SiO 2 Preparation method of modified epoxy resin composite material - Google Patents
POSS-CuPc-SiO 2 Preparation method of modified epoxy resin composite material Download PDFInfo
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- CN114806091A CN114806091A CN202210546694.3A CN202210546694A CN114806091A CN 114806091 A CN114806091 A CN 114806091A CN 202210546694 A CN202210546694 A CN 202210546694A CN 114806091 A CN114806091 A CN 114806091A
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- 229910004298 SiO 2 Inorganic materials 0.000 title claims abstract description 66
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 43
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 60
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 22
- -1 3-chloropropyl Chemical group 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- XJGIDGNLXAJIOA-UHFFFAOYSA-N 2,11,20,29,37,38,39,40-octazanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1(36),2,4,6,8,10(40),11,13,15,17,19,21(38),22,24,26,28,30,32,34-nonadecaen-37-amine Chemical compound Nn1c2nc3nc(nc4[nH]c(nc5nc(nc1c1ccccc21)c1ccccc51)c1ccccc41)c1ccccc31 XJGIDGNLXAJIOA-UHFFFAOYSA-N 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 12
- 238000005266 casting Methods 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 239000000741 silica gel Substances 0.000 claims description 8
- 229910002027 silica gel Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000003989 dielectric material Substances 0.000 abstract description 6
- 239000000945 filler Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000006845 Michael addition reaction Methods 0.000 abstract description 2
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 239000002245 particle Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011370 conductive nanoparticle Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 229960001149 dopamine hydrochloride Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to the technical field of EP dielectric material synthesis, and discloses POSS-CuPc-SiO 2 The preparation method of the modified epoxy resin composite material comprises the following steps: by PDA-SiO 2 Phenyl functionality of hybrid monomers with copper (NH) amino phthalocyanine 2 -CuPc) to generate Michael addition reaction to obtain polyamino CuPc-SiO 2 A hybrid dielectric monomer; by polyaminoation of CuPc-SiO 2 The amino functional group of the hybrid dielectric monomer and the chlorine functional group of the monofunctional group 3-chloropropyl POSS are subjected to substitution reaction to obtain POSS-CuPc-SiO 2 A hybrid dielectric monomer; with POSS-CuPc-SiO 2 The hybrid dielectric monomer is used as a filler, and the E51 epoxy resin is used as a polymer matrix to prepare the POSS-CuPc-SiO with high dielectric constant and low dielectric loss 2 A modified epoxy resin composite material.
Description
Technical Field
The invention relates to the technical field of EP dielectric material synthesis, in particular to POSS-CuPc-SiO 2 A preparation method of a modified epoxy resin composite material.
Background
The electronics industry, which is developing at a high speed, greatly depends on the development of dielectric materials, and the conventional dielectric materials still have the problems of low dielectric constant, high dielectric loss, low energy storage density and the like, which cannot meet the requirements of miniaturization, integration, flexibility and high performance of electronic devices.
Of the two types of high dielectric composites currently under major research: the conductive nano particle/polymer composite material still has the problems of over-high dielectric loss, smaller percolation threshold, extremely poor breakdown strength and the like; the ceramic nano particle/polymer composite material also has the problems of overlarge filler concentration, poor filler compatibility, poor mechanical property of the composite material and the like. These problems severely limit their practical application in dielectric materials.
Nano SiO 2 The hybrid polymer material can retain nano SiO 2 The rigidity, the dimensional stability, the friction resistance and the high and low temperature resistance of the material can be maintained, and the plasticity of the polymer material can be maintained. The epoxy resin (EP) has good thermal stability, insulativity, cohesiveness and mechanical property, diversified forming process and high performance-price ratio, and is widely applied to the fields of aviation, aerospace, electricity, electronics and the like.
Phthalocyanines (Pcs) have a highly coplanar 18-electron large TT bond conjugated structure, which coordinates with a plurality of metal ions to form metal Phthalocyanines (MPcS), and MPcS are widely used in various research fields such as catalytic materials, conductive materials, dielectric materials, solar cells, optical materials, and the like due to their excellent chemical stability and photoelectric properties.
The following references are cited for the present invention: a doctor's scientific thesis in electronics university (research on Metal Phthalocyanine-Poly (arylene ether nitrile) functional composite) discloses copper (NH) phthalocyanine 2 -CuPc) structure and method of preparation;
the following references are cited for the present invention: the composite material bulletin at 2009, 12, 26, 6 th volume, preparation of POSS/PS composite material and thermal properties thereof, discloses a structure and a preparation method of monofunctional 3-chloropropyl POSS;
the invention tries to synthesize POSS-CuPc-SiO with high dielectric constant and low dielectric loss 2 A modified epoxy resin composite material.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation methodPOSS-CuPc-SiO with high dielectric constant and low dielectric loss 2 A method for modifying an epoxy resin composite.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme:
POSS-CuPc-SiO 2 The preparation method of the modified epoxy resin composite material comprises the following steps:
step S1, synthesizing polydopamine-silicon dioxide (PDA-SiO) 2 ) A hybrid monomer;
step S2, polyamino CuPc-SiO 2 Synthesis of hybrid dielectric monomer:
5-20 parts of PDA-SiO 2 Hybrid monomer and 10-35 parts of copper (NH) amino phthalocyanine 2 -CuPc) is added into a Tris-HCl solution, the solution is adjusted to be alkaline, the reaction temperature is controlled to be 30-40 ℃, the stirring reaction is carried out for 18-30h, and the polyamino CuPc-SiO is obtained 2 A hybrid dielectric monomer;
step S3, POSS-CuPc-SiO 2 Synthesis of hybrid dielectric monomer:
4-15 parts of polyamino CuPc-SiO 2 Adding a hybrid dielectric monomer and 15-40 parts of monofunctional 3-chloropropyl POSS into a three-neck flask, stirring, adding micron-sized silica gel serving as a catalyst, and heating and refluxing at 60-95 ℃ for 3-5h to obtain POSS-CuPc-SiO 2 A hybrid dielectric monomer;
step S4, POSS-CuPc-SiO 2 Synthesis of the modified epoxy resin composite material:
10 to 35 portions of POSS-CuPc-SiO 2 Adding a hybrid dielectric monomer into 100 parts of E51 epoxy resin, adding an ethyl acetate solvent, carrying out ultrasonic stirring, removing the ethyl acetate solvent, adding a curing agent polyetheramine (D230), stirring, casting the prepolymer into a polytetrafluoroethylene mold, and carrying out curing reaction in a forced air oven to obtain PEN-PAQR-SiO 2 A modified epoxy resin composite material.
Preferably, the step S2: pH 8-9.
Preferably, the step S3: the dosage of the silica gel is 0.2-2 parts, and the average grain diameter is 80 um.
It is preferable to useStep S4: casting the prepolymer into a polytetrafluoroethylene mold, carrying out curing reaction in a forced air oven, and controlling the reaction temperature rise program to be 60-90 ℃/2h, 90-110 ℃/2h and 110- 2 A modified epoxy resin composite material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the invention ensures that dopamine is in SiO with micron-sized particle diameter 2 The particle surface is subjected to polymerization reaction to obtain poly dopamine-silicon dioxide (PDA-SiO) 2 ) A hybrid monomer;
by PDA-SiO 2 Phenyl functionality of hybrid monomers with copper (NH) amino phthalocyanine 2 -CuPc) to generate Michael addition reaction to obtain polyamino CuPc-SiO 2 A hybrid dielectric monomer;
by polyaminoation of CuPc-SiO 2 The amino functional group of the hybrid dielectric monomer and the chlorine functional group of the monofunctional group 3-chloropropyl POSS are subjected to substitution reaction to obtain POSS-CuPc-SiO 2 A hybrid dielectric monomer;
with POSS-CuPc-SiO 2 The hybrid dielectric monomer is used as a filler, and the E51 epoxy resin is used as a polymer matrix to prepare POSS-CuPc-SiO 2 The relative dielectric constant epsilon r of the modified epoxy resin composite material reaches 21.0-28.8, and the dielectric loss tan delta is only 0.0024-0.0033;
in POSS-CuPc-SiO 2 In the modified epoxy resin composite material, SiO 2 CuPc-SiO with particles as rigid core and copper phthalocyanine coated on surface 2 The hybrid dielectric monomer serves as a dielectric core, POSS with low dielectric constant serves as a first coating layer, E51 epoxy resin serves as a second coating layer, and the structural design can promote charges in CuPc-SiO 2 The hybrid dielectric monomer and the POSS of the first coating layer are transferred in a short distance, which plays the technical roles of enhancing interface polarization and improving dielectric constant and can also prevent charges from being transferred in a CuPc-SiO 2 Hybrid dielectric monomer and adjacent CuPc-SiO 2 Migration over long distances between hybrid dielectric monomersThe leakage current is reduced, and the dielectric loss is reduced;
the whole POSS-CuPc-SiO is coated by E51 epoxy resin with low dielectric constant and good insulation 2 A hybrid dielectric monomer aimed at: in a POSS-CuPc-SiO 2 Hybrid dielectric monomer and adjacent POSS-CuPc-SiO 2 An insulating layer is formed between the hybridized dielectric monomers to block the charges from a POSS-CuPc-SiO 2 Migration of hybrid dielectric monomer to adjacent POSS-CuPc-SiO 2 The hybrid dielectric monomer has the technical effect of further reducing the leakage current.
Detailed Description
Example 1:
POSS-CuPc-SiO 2 The preparation method of the modified epoxy resin composite material comprises the following steps:
step S1, Polydopamine-silica (PDA-SiO) 2 ) And (3) synthesis of hybrid monomers:
20g of SiO having an average particle diameter of 1um 2 Dispersing the granules in 150mL Tris-HCl aqueous solution with the concentration of 10mM, adjusting the pH value to 8.5, carrying out ultrasonic treatment in ice bath for 1h, adding 10g dopamine hydrochloride, continuing ultrasonic treatment for 1h, carrying out centrifugal treatment, and dispersing by adopting ethanol to obtain PDA-TiO 2 A hybrid monomer;
step S2, polyamino CuPc-SiO 2 Synthesis of hybrid dielectric monomer:
10g of PDA-SiO 2 Hybrid monomer and 18g of copper (NH) amino phthalocyanine 2 -CuPc) is added into 100mL of Tris-HCl solution with the concentration of 10mmoL, the pH value is adjusted to 8.5, the reaction temperature is controlled to be 35 ℃, and the mixture is stirred and reacted for 24 hours under the condition of 300r/min, so that the polyamino CuPc-SiO is obtained 2 A hybrid dielectric monomer;
step S3, POSS-CuPc-SiO 2 Synthesis of hybrid dielectric monomer:
8g of polyamino CuPc-SiO 2 Adding a hybrid dielectric monomer and 30g of monofunctional 3-chloropropyl POSS into a three-neck flask, stirring, adding 0.8g of silica gel with the average particle size of 80 mu m as a catalyst, heating and refluxing at 80 ℃ for 4h, cooling to room temperature, filtering to obtain silica gel, dropping the filtrate into petroleum ether to separate outDissolving white precipitate in 200mL tetrahydrofuran, slowly adding 15g potassium hydroxide powder, stirring at room temperature for 3 hr, filtering to obtain filtrate, removing tetrahydrofuran from the filtrate with rotary evaporator, purifying with silica gel column chromatography, and purifying with ethyl acetate and petroleum ether (V) 1 ∶V 2 1: 10) as eluent, and drying the product in vacuum at 50 ℃ for 24h to obtain POSS-CuPc-SiO 2 A hybrid dielectric monomer;
step S4, POSS-CuPc-SiO 2 Synthesis of the modified epoxy resin composite material:
2g of POSS-CuPc-SiO 2 Adding a hybrid dielectric monomer into 10g E51 epoxy resin, adding 2g of ethyl acetate solvent, ultrasonically stirring for 1h, removing the ethyl acetate solvent at 80 ℃, adding curing agent polyetheramine (D230), stirring for 5min, casting the prepolymer into a polytetrafluoroethylene mold, carrying out curing reaction in a forced air oven, and controlling the reaction temperature rise program to be 90 ℃/2h, 110 ℃/2h and 140 ℃/2h to obtain PEN-PAQR-SiO 2 A modified epoxy resin composite material.
Example 2:
POSS-CuPc-SiO 2 The preparation method of the modified epoxy resin composite material comprises the following steps:
step S1, Polydopamine-silica (PDA-SiO) 2 ) Synthesis of hybrid monomer: the synthesis is described in example 1;
step S2, polyamino CuPc-SiO 2 Synthesis of hybrid dielectric monomer:
5g of PDA-SiO 2 Hybrid monomer and 10g of copper (NH) amino phthalocyanine 2 -CuPc) is added into 100mL of Tris-HCl solution with the concentration of 10mmoL, the pH value is adjusted to 8, the reaction temperature is controlled to be 30 ℃, and the mixture is stirred and reacted for 30 hours at the speed of 300r/min, so that the polyamino CuPc-SiO is obtained 2 A hybrid dielectric monomer;
step S3, POSS-CuPc-SiO 2 Synthesis of hybrid dielectric monomer:
4g of polyamino CuPc-SiO 2 The hybrid dielectric monomer and 15g of monofunctional 3-chloropropyl POSS were added to a three-necked flask and stirred with a magneton while adding 0.2g of the average particle diameter80um silica gel is used as a catalyst, heated and refluxed for 5h at the temperature of 60 ℃ to obtain POSS-CuPc-SiO 2 A hybrid dielectric monomer;
step S4, POSS-CuPc-SiO 2 Synthesis of the modified epoxy resin composite material:
1g of POSS-CuPc-SiO 2 Adding a hybrid dielectric monomer into 10g E51 epoxy resin, adding 2g of ethyl acetate solvent, ultrasonically stirring for 1h, removing the ethyl acetate solvent at 80 ℃, adding curing agent polyetheramine (D230), stirring for 5min, casting the prepolymer into a polytetrafluoroethylene mold, carrying out curing reaction in a forced air oven, and controlling the reaction temperature rise program to be 60 ℃/2h, 90 ℃/2h and 110 ℃/2h to obtain PEN-PAQR-SiO 2 A modified epoxy resin composite material.
Example 3:
POSS-CuPc-SiO 2 The preparation method of the modified epoxy resin composite material comprises the following steps:
step S1, Polydopamine-silica (PDA-SiO) 2 ) Synthesis of hybrid monomer: the synthesis is described in example 1;
step S2, polyamino CuPc-SiO 2 Synthesis of hybrid dielectric monomer:
20g of PDA-SiO 2 Hybrid monomer and 35g of copper (NH) amino phthalocyanine 2 -CuPc) is added into 100mL of Tris-HCl solution with the concentration of 10mmoL, the pH value is adjusted to 9, the reaction temperature is controlled to be 40 ℃, and the mixture is stirred and reacted for 18h under the condition of 300r/min, so that the polyamino CuPc-SiO is obtained 2 A hybrid dielectric monomer;
step S3, POSS-CuPc-SiO 2 Synthesis of hybrid dielectric monomer:
the 15g of polyamino CuPc-SiO 2 Adding a hybrid dielectric monomer and 40g of monofunctional 3-chloropropyl POSS into a three-neck flask, stirring by magnetons, simultaneously adding 2g of silica gel with the average particle size of 80 mu m as a catalyst, and heating and refluxing for 3h at 95 ℃ to obtain POSS-CuPc-SiO 2 A hybrid dielectric monomer;
step S4, POSS-CuPc-SiO 2 Synthesis of the modified epoxy resin composite material:
3.5g of POSS-CuPc-SiO 2 Hybrid dielectric monomer to 10g E51 epoxy resinAdding 2g of ethyl acetate solvent, ultrasonically stirring for 1h, removing the ethyl acetate solvent at 80 ℃, adding curing agent polyetheramine (D230), stirring for 5min, casting the prepolymer into a polytetrafluoroethylene mold, carrying out curing reaction in a forced air oven, and controlling the reaction temperature rise program to be 80 ℃/2h, 100 ℃/2h and 120 ℃/2h to obtain PEN-PAQR-SiO 2 A modified epoxy resin composite material.
Comparative example:
SiO (silicon dioxide) 2 The preparation method of the modified epoxy resin composite material comprises the following steps:
2g of SiO having an average particle diameter of 1um 2 Adding the particles into 10g E51 epoxy resin, adding 2g of ethyl acetate solvent, ultrasonically stirring for 1h, removing the ethyl acetate solvent at 80 ℃, adding curing agent polyether amine (D230), stirring for 5min, casting the prepolymer into a polytetrafluoroethylene mold, carrying out curing reaction in a forced air oven, and controlling the reaction temperature rise program to be 90 ℃/2h, 110 ℃/2h and 140 ℃/2h to obtain SiO 2 A modified epoxy resin composite material.
And (3) performance measurement:
according to GB/T12636-1990, the dielectric property of the sample is tested by using an Agilent E8363A precision impedance analyzer, the test frequency is 10GHz, and the test result is shown in the following table 1;
TABLE 1
| Sample (I) | Relative dielectric constant ε r | Dielectric loss tan delta |
| Example 1 | 28.8 | 0.0033 |
| Example 2 | 16.3 | 0.0027 |
| Example 3 | 21.0 | 0.0024 |
| Comparative example 1 | 3.1 | 0.0030 |
Claims (4)
1. POSS-CuPc-SiO 2 The preparation method of the modified epoxy resin composite material is characterized by comprising the following steps:
step S1, synthesizing polydopamine-silicon dioxide (PDA-SiO) 2 ) A hybrid monomer;
step S2, polyamino CuPc-SiO 2 Synthesis of hybrid dielectric monomer:
5-20 parts of PDA-SiO 2 Hybrid monomer and 10-35 parts of copper (NH) amino phthalocyanine 2 -CuPc) is added into a Tris-HCl solution, the solution is adjusted to be alkaline, the reaction temperature is controlled to be 30-40 ℃, the stirring reaction is carried out for 18-30h, and the polyamino CuPc-SiO is obtained 2 A hybrid dielectric monomer;
step S3, POSS-CuPc-SiO 2 Synthesis of hybrid dielectric monomer:
4-15 parts of polyamino CuPc-SiO 2 Adding a hybrid dielectric monomer and 15-40 parts of monofunctional 3-chloropropyl POSS into a three-neck flask, stirring, adding micron-sized silica gel serving as a catalyst, and heating and refluxing at 60-95 ℃ for 3-5h to obtain POSS-CuPc-SiO 2 A hybrid dielectric monomer;
step S4, POSS-CuPc-SiO 2 Synthesis of the modified epoxy resin composite material:
10 to 35 portions of POSS-CuPc-SiO 2 Hybrid dielectric monomer incorporationAdding ethyl acetate solvent into 100 parts of E51 epoxy resin, carrying out ultrasonic stirring, removing the ethyl acetate solvent, adding curing agent polyetheramine (D230), stirring, casting the prepolymer into a polytetrafluoroethylene mold, and carrying out curing reaction in a forced air oven to obtain PEN-PAQR-SiO 2 A modified epoxy resin composite material.
2. The POSS-CuPc-SiO of claim 1 2 The preparation method of the modified epoxy resin composite material is characterized in that the step S2: pH 8-9.
3. The POSS-CuPc-SiO of claim 1 2 The preparation method of the modified epoxy resin composite material is characterized in that the step S3: the dosage of the silica gel is 0.2-2 parts, and the average grain diameter is 80 um.
4. The POSS-CuPc-SiO of claim 1 2 The preparation method of the modified epoxy resin composite material is characterized in that the step S4: casting the prepolymer into a polytetrafluoroethylene mold, carrying out curing reaction in a forced air oven, and controlling the reaction temperature rise program to be 60-90 ℃/2h, 90-110 ℃/2h and 110- 2 A modified epoxy resin composite material.
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| CN115216170A (en) * | 2022-08-16 | 2022-10-21 | 宏元(江门)化工科技有限公司 | Water-based epoxy resin anticorrosive paint and preparation method thereof |
| CN115948080A (en) * | 2022-12-27 | 2023-04-11 | 海南电网有限责任公司文昌供电局 | Insulating glove and preparation method thereof |
Citations (5)
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