GB2616136A - Dielectricity and thermal conductivity enhanced bio-based high-temperature-resistant epoxy resin, preparation method therefor, and application thereof - Google Patents
Dielectricity and thermal conductivity enhanced bio-based high-temperature-resistant epoxy resin, preparation method therefor, and application thereof Download PDFInfo
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- GB2616136A GB2616136A GB2306059.3A GB202306059A GB2616136A GB 2616136 A GB2616136 A GB 2616136A GB 202306059 A GB202306059 A GB 202306059A GB 2616136 A GB2616136 A GB 2616136A
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- epoxy resin
- preparation
- temperature
- curing agent
- dielectric
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 85
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- BYTORXDZJWWIKR-UHFFFAOYSA-N Hinokiol Natural products CC(C)c1cc2CCC3C(C)(CO)C(O)CCC3(C)c2cc1O BYTORXDZJWWIKR-UHFFFAOYSA-N 0.000 claims description 9
- FVYXIJYOAGAUQK-UHFFFAOYSA-N honokiol Chemical compound C1=C(CC=C)C(O)=CC=C1C1=CC(CC=C)=CC=C1O FVYXIJYOAGAUQK-UHFFFAOYSA-N 0.000 claims description 9
- VVOAZFWZEDHOOU-UHFFFAOYSA-N honokiol Natural products OC1=CC=C(CC=C)C=C1C1=CC(CC=C)=CC=C1O VVOAZFWZEDHOOU-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000003990 capacitor Substances 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 125000004427 diamine group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 239000002861 polymer material Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 description 15
- 239000002994 raw material Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 206010037660 Pyrexia Diseases 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004382 potting Methods 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 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 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 241000411851 herbal medicine Species 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000009466 transformation Effects 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
Disclosed in the present invention are a dielectricity and thermal conductivity enhanced bio-based high-temperature-resistant epoxy resin, a preparation method therefor, and an application thereof. The dielectric constant of the epoxy resin is 8.2-10. The present method is simple in operation process and shorter in curing time; the obtained bio-based epoxy resin polymer material is excellent in performance, and the dielectric constant is increased to 8.2-10; moreover, the epoxy resin has good thermal conductivity and heat capacity ratio (0.743 W/m·K, 5.364 J/g·K), and can meet the application of corresponding functionalized electronic products.
Description
DIELECTRICITY AND THERMAL CONDUCTIVITY ENHANCED BIO-BASED HIGH-TEMPERATURE-RESISTANT EPDXY RESIN, PREPARATION METHOD THEREFOR, AND APPLICATION THEREOF
TECHNICAL FIELD
The present invention belongs to the field of polymer synthesis, and particularly relates to a dielectric thermal-conduction enhanced bio-based hightemperature-resistant epoxy resin, and a preparation method and application thereof.
BACKGROUND
Epoxy resin polymer is usually formed by cross-linking polymerization of an epoxy resin monomer and a curing agent, and is widely used in coating adhesive and electronic and electrical industries, multi-component composite materials and CO 15 engineering technology research fields. However, at present, most commercial epoxy resins are prepared from petroleum raw materials, and a bisphenol A epoxy resin accounts for more than 90% of total epoxy resin output. Although epichlorohydrin, which is one of raw materials, may be prepared from glycerin, which is a biomass raw material, bisphenol A, which is another main raw material, can only be produced from the petroleum raw materials at present. Petroleum is a non-renewable resource, and has been consumed in large quantities at present, causing a series of problems such as shortage of petroleum resources, soaring price of petroleum and environmental pollution, which have forced people to focus on the field of sustainable development. In addition, the bisphenol A epoxy resin has high viscosity at room temperature, poor fluidity, and high requirements on a construction process, and the epoxy resin obtained by curing has poor flame retardance and electrical conductivity, so that an application of the epoxy resin in high-tech fields is limited.
In 2019, the patent CN110408003A disclosed a preparation method of a honokiol epoxy resin, and corresponding difunctional and tetrafunctional epoxy resins were prepared with a natural Mangnolia officinalis derivative as a raw material. The Mangnolia officinalis derivative may be used for preparing Chinese herbal medicines and cosmetics, and has been proved to be a safe and low toxic compound. The preparation of the epoxy resin from this raw material can reduce health hazards of the epoxy resin to a human body. Moreover, a preparation process of the bio-based epoxy resin is simple and efficient, and is beneficial for large-scale production. It is more noteworthy that the bio-based epoxy resin after curing has excellent thermal resistance, mechanical property and flame retardance. However, there is no literature report on researches of dielectric property and thermal conductivity of related materials.
In 2017, the patent CN107057289A disclosed a high-thermal-conductivity and high-temperature-resistant epoxy resin and a preparation method thereof, and a potting epoxy resin was used as a potting material and applied to high-thermal-conductivity and high-temperature-resistant potting of new energy power batteries and motors, and wind power generation stators and motors. Meanwhile, there are few literature reports on bio-based epoxy resin materials with high thermal conductivity, high temperature resistance and strong electrical conductivity. Therefore, through the in-depth development of bio-based compounds, the CO 15 preparation of dielectric thermal-conduction enhanced high-temperature-resistant bio-based epoxy resin materials has a good research and application value, and is also one of frontier directions of functional transformation and application research 0 of bio-based materials.
SUMMARY
Object of the invention: the technical problem to be solved by the present invention is to provide a dielectric thermal-conduction enhanced bio-based hightemperature-resistant epoxy resin aiming at the defects in the prior art.
The technical problem to be further solved by the present invention is to provide a preparation method of the dielectric thermal-conduction enhanced bio-based high-temperature-resistant epoxy resin above.
The technical problem to be finally solved by the present invention is to provide an application of the dielectric thermal-conduction enhanced bio-based hightemperature-resistant epoxy resin above in a dielectric capacitor material.
In order to solve the first technical problem above, the present invention discloses a dielectric thermal-conduction enhanced bio-based high-temperatureresistant epoxy resin, wherein a frequency range is 0 MHz to 3 MHz, a dielectric constant remains constant at 8.2 to 10 basically.
Further, a change of a dielectric loss of the epoxy resin with a frequency is no higher than 0.075.
Further, a thermal conductivity coefficient of the epoxy resin is no less than 0.43 W/m*K, and a specific heat capacity is no less than 2.3 J/g*K.
Preferably, the thermal conductivity coefficient of the epoxy resin is no less than 0.743 W/m*K, and the specific heat capacity is no less than 5.364 J/g.K. Further, an initial decomposition temperature of the epoxy resin is 405°C to 420°C, and a temperature corresponding to a maximum decomposition rate is 445°C to 455°C; and preferably, the initial decomposition temperature of the epoxy resin is 410°C, and the temperature corresponding to the maximum decomposition rate is 451°C.
Further, the epoxy resin is capable of being extinguished after burning for 60 seconds, and preferably for 25 seconds.
In order to solve the second technical problem above, the present invention CO 15 discloses a preparation method of the epoxy resin above, wherein an epoxy resin monomer used in a preparation process comprises a compound shown in formula N*** DBDBBB:
DBDBBB
The epoxy resin monomer may be the compound shown in formula DBDBBB itself, or a mixture of the compound shown in formula DBDBBB and other monomers, such as a mixture of the compound shown in formula DBDBBB and DGEBA o o
DGEBA
The compound shown in formula DBDBBB is prepared by a reaction of honokiol (a compound shown in formula C) and epichlorohydrin.
Specifically, the reaction comprises: uniformly mixing epichlorohydrin, tetrabutylammonium bromide and 50% w/w sodium hydroxide solution at room temperature for 30 minutes, dropwise adding honokiol dissolved with tetrahydrofurane, extracting the mixture with dichloromethane after complete reaction at 50°C, drying the extracted organic phase with anhydrous sodium sulfate, then concentrating the dried organic phase by rotary distillation, and separating the concentrated organic phase by a silica gel column (petroleum ether and ethyl acetate 30/1 to 6/1) to obtain the compound.
A weight ratio of the epichlorohydrin to the tetrabutylammonium bromide and the sodium hydroxide solution is (38 to 42): 1: (26 to 32).
A mass ratio of the honokiol to the epichlorohydrin is 1: (4 to 5); and a dosage Cr) ratio of the honokiol to the tetrahydrofuran is 0.2 g/mL to 0.3 g/mL.
According to the preparation method of the epoxy resin, epoxy DBDBBB and an amine curing agent are subjected to a solventless curing reaction to prepare a corresponding bio-based epoxy resin polymer material; and specifically, the preparation method comprises the following steps of: (1) introducing nitrogen into the epoxy resin monomer (the compound shown in formula DBDBBB) to obtain a deoxygenated epoxy resin monomer; (2) adding a curing agent into the deoxygenated epoxy resin monomer obtained in the step (1) at a certain temperature in a nitrogen atmosphere, melting the mixture at a high temperature, uniformly stirring, and pouring the mixture into a mold; and (3) curing the mold in the step (2) at a high temperature in the nitrogen atmosphere, cooling the mold in the nitrogen atmosphere, and demoulding to obtain the epoxy resin.
In the step (2), the curing agent is a diamine curing agent.
In the step (2), the diamine curing agent is any one or a combination two of 4,4'-diaminodiphenyl sulfone (44DD5) shown in formula A and 3,3'-diaminodiphenyl sulfone (33DDS) shown in formula B (1 mol of curing agent contains 4 mol of NH-): H2N NH2 II H 0 S NH,
II 0 0 H2N
A
In the step (2), an addition amount of the curing agent is controlled, so that a molar ratio of ethylene oxide group in the epoxy resin monomer to NH-in the curing agent is 1: 0.85 to 1: 1.2.
In the step (2), the melting at the high temperature is carried out at a temperature of 120°C to 195°C, and preferably at a temperature of 150°C to 170°C.
In the step (3), the curing at the high temperature is carried out at a temperature of 170°C to 215°C, and preferably at a temperature of 200°C to 215°C.
In the step (3), the curing at the high temperature lasts for 3 hours to 10 hours, and preferably for 4 hours to 6 hours.
In order to solve the third technical problem above, the present invention discloses an application of the dielectric thermal-conduction enhanced bio-based CO high-temperature-resistant epoxy resin above in a dielectric capacitor material.
This is because the bio-based epoxy resin material prepared by the DBDBBB/DDS system in the present invention not only has excellent thermal stability and flame retardance, but also has excellent dielectric property and thermal conductivity, for example, at a frequency of 1,000 Hz, dielectric parameters (9.74 and 0.026) of DBDBBB/44DDS are similar to dielectric parameters (10 and 0.04) of a fluorine-containing polyvinylidene fluoride (PVDF) dielectric material.
Beneficial effects compared with the prior art, the present invention has the following advantages: (1) According to the present invention, the bio-based raw material honokiol is prepared into a green environment-friendly non-petroleum-based epoxy resin material through simple conversion, the raw material is widely available, and the obtained product has strong substitutability for a petroleum-based product and high biological safety, so that biological resources are fully and efficiently utilized and a development requirement of green chemistry is met.
(2) A curing process of the epoxy resin is simple in operation and convenient in process, and has no solvent pollution and a high green level.
(3) According to the present invention, the polymer system composed of the raw material has certain flame retardance, without using a halogen or phosphorus flame retardant or an inorganic flame retardant, so that biological safety is high.
(4) A dielectric constant (a') of the obtained epoxy resin material is greater than 5, a dielectric constant of a traditional resin material is 2 to 4, and a dielectric constant of this system is increased to 8.2 to 10, so that there is obvious improvement compared with the traditional polymer material.
(5) In terms of thermal conductivity, low thermal conductivity of traditional polymer resin (-0.3 W/m*K) greatly limits an application thereof in electronic industry; and a thermal conductivity coefficient and a specific heat capacity of a common epoxy resin material are 0.2 W/m*K to 2.2 W/m*K and 0.8 J/g*K to 1.5 J/g.K respectively, while the epoxy resin material reported in this patent has good thermal conductivity coefficient and specific heat capacity (0.743 W/m*K and 5.364 J/g*K) at the same time, so that an application of a corresponding functional CO 15 electronic product can be realized.
(6) The decomposition temperature of the material obtained by the present invention reaches a maximum value (410°C) in current bio-based epoxy resin, and the temperature corresponding to the maximum decomposition rate also reaches a corresponding maximum value (451°C), so that excellent thermal stability is shown.
(7) The dielectric thermal-conduction enhanced high-temperature-resistant polymer material is synthesized based on the bio-based honokiol for the first time in the present invention, which may satisfy substitution of some related petroleum-based chemicals and lay a foundation for further functional research of bio-based materials.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is further described in detail hereinafter with reference to the drawings and specific embodiments, and the advantages of the above and/or other aspects of the present invention will be clearer.
FIG. 1 shows 1H-NMR of DBDBBB.
FIG. 2 is an infrared spectrogram of DBDBBB/44DDS and DBDBDBBB/33DD8 epoxy resins (Embodiments 4 and 5).
FIG. 3 is a TG spectrogram of the DBDBBB/44DDS and DBDBDBBB/33DDS epoxy resins (Embodiments 4 and 5).
FIG. 4 shows dielectric properties of the epoxy resins (Embodiments 4 and 5). FIG. 5 shows thermal conductivities of the epoxy resins at room temperature (Embodiments 4 and 5).
FIG. 6 shows flame retardance experiments of the DBDBBB/44DDS and 5 DBDBDBBB/33DDS epoxy resins (Embodiments 4 and 5).
DETAILED DESCRIPTION
A detection method in the following embodiments is as follows. Thermogravimetric test parameters: test instrument: Discovery TGA-550, temperature range: 40°C to 900°C, flow rate of nitrogen: 20 mL/min, and heating rate: 20 °C/min.
Dielectric test parameters: test instrument: Novocontrol Concept 80, temperature: 25°C, and test frequency: 0 Hz to 3 MHz.
Thermal conductivity test parameters: test instrument: NETZSCH LFA 427, Cr) 15 temperature range: 25°C, and flow rate of argon 80 mL/min.
Combustion experiments are carried out according to the national standard GB 2408-96.
Embodiment 1 Epichlorohydrin (64.75 g), tetrabutylammonium bromide (1.61 g) and 50% (w/w) sodium hydroxide solution (48 g) were successively added into a single-mouth reaction bottle, uniformly mixed at room temperature for 30 minutes, and dropwise added with honokiol (13.31 g) dissolved with tetrahydrofurane (60 mL), the mixture was extracted with dichloromethane after complete reaction at 50°C, and the extracted organic phase was dried with anhydrous sodium sulfate, then concentrated by rotary distillation, and separated by a silica gel column (petroleum ether and ethyl acetate 30/1 to 6/1) to obtain 15.4 g of colorless DBDBBB liquid, with a yield of 85%, and a H-nuclear magnetic resonance spectrum shown in FIG. 1.
Embodiment 2 The epoxy resin monomer DBDBBB (3.78 g) prepared in Embodiment 1 was added into a sample bottle, and introduced with nitrogen. After an oxygen component was removed, 4,41-diaminodiphenyl sulfone (compound A, 1.24 g) was added in a nitrogen atmosphere. Air was further removed, and the mixture was fully mixed and stirred, and heated to 165°C to melt and mix the two uniformly. The material was poured into a stainless steel mold plate at 170°C, then heated at 210°C, cured for 2 hours, and then naturally cooled in a nitrogen atmosphere to obtain a transparent epoxy resin polymer.
Embodiment 3 The epoxy resin monomer DBDBBB (3.78 g) prepared in Embodiment 1 was added into a sample bottle, and introduced with nitrogen. After an oxygen component was removed, 3,3-diaminodiphenyl sulfone (compound B, 1.24 g) was added in a nitrogen atmosphere. Air was further removed, and the mixture was fully mixed and stirred, and heated to 180°C to melt and mix the two uniformly. The material was poured into a stainless steel mold plate at 170°C, then heated at 210°C, cured for 2 hours, and then naturally cooled in a nitrogen atmosphere to obtain a faint yellow transparent epoxy resin polymer.
Embodiment 4 CO 15 The epoxy resin monomer DBDBBB (7.56 g) prepared in Embodiment 1 was added into a sample bottle, and introduced with nitrogen. After an oxygen component was removed, 4,41-diaminodiphenyl sulfone (compound A, 2.48 g) was added in a nitrogen atmosphere. Air was further removed, and the mixture was fully mixed and stirred, and heated to 150°C to melt and mix the two uniformly. The material was poured into a stainless steel mold plate at 170°C, then heated at 210°C, cured for 2 hours, and then naturally cooled in a nitrogen atmosphere to obtain a transparent epoxy resin polymer. A dielectric constant of the obtained epoxy resin polymer was 9.74, and a change of a dielectric loss with a frequency was 0.026.
Embodiment 5 The epoxy resin monomer DBDBBB (7.56 g) prepared in Embodiment 1 was added into a sample bottle, and introduced with nitrogen. After an oxygen component was removed, 3,31-diaminodiphenyl sulfone (compound B, 2.48 g) was added in a nitrogen atmosphere. Air was further removed, and the mixture was fully mixed and stirred, and heated to 170°C to melt and mix the two uniformly. The material was poured into a stainless steel mold plate at 170°C, then heated at 210°C, cured for 2 hours, and then naturally cooled in a nitrogen atmosphere to obtain a faint yellow transparent epoxy resin polymer. CO 15 N*** Ne*
Infrared spectra of the epoxy resin polymers prepared in Embodiment 4 and Embodiment 5 are shown in FIG. 2, TG spectra of the epoxy resin polymers are shown in FIG. 3, dielectric properties of the epoxy resin polymers are shown in FIG. 4, thermal conductivities of the epoxy resin polymers are shown in FIG. 5, and flame retardance experiments of the epoxy resin polymers are shown in FIG. 6. Comparative Example 1 Similar to Embodiment 4, the epoxy resin monomer was replaced by DGEBA from DBDBDBBB, melted at 180°C and then poured, and then cured at 215°C for 2 hours to obtain the epoxy resin material. A combustion experiment showed that the combustion lasted for 155 seconds and then was extinguished, which showed that the corresponding DBDBBB material system had better flame retardance. A dielectric test showed that, in a range of 0 MHz to 3 MHz, a charge of a dielectric loss of the DGEBA/44DDS polymer with a frequency (0.1 to 0.45) was great, which was obviously higher than that of the DBDBBB/DDS system (<0.075). Therefore, the DGEBA/DDS system was not suitable for being used as a dielectric material due to large energy consumption and a high calorific value. In addition, a thermal conductivity coefficient and a specific heat capacity of the DGEBA/44DDS were both small, which were 0.333 W/m*K and 1.96 J/g*K respectively, and were obviously smaller than those of the bio-based DBDBBB/DDS system. However, a thermal conductivity coefficient and a specific heat capacity of a common epoxy resin material were 0.2 W/rn*K to 2.2 W/m*K and 0.8 J/g*K to 1.5 J/g*K respectively. Therefore, the polymer system developed based on the bio-based DBDBBB not only had flame retardance, but also had obviously enhanced dielectric property and thermal conductivity. Tr°
DGEBA
The present invention provides an idea and a method for a dielectric thermal-conduction enhanced bio-based high-temperature-resistant epoxy resin and a preparation method thereof, with many methods and ways to realize the technical solution specifically. Those described above are merely the preferred embodiments of the present invention, and it should be pointed out that those of ordinary skills in the art may further make improvements and decorations without departing from the principle of the present invention, and these improvements and decorations should also be regarded as the scope of protection of the present invention. All the unspecified components in the embodiments can be realized by the prior art.
CO C \I
N-
N r
Claims (10)
- Claims 1. A dielectric thermal-conduction enhanced bio-based high-temperature-resistant epoxy resin, wherein a dielectric constant of the epoxy resin is 8.2 to 10.
- 2. The epoxy resin according to claim 1, wherein a thermal conductivity coefficient of the epoxy resin is no less than 0.43 W/m*K, and a specific heat capacity is no less than 2.3 J/g.K.
- 3. A preparation method of the epoxy resin according to claim 1 or 2, wherein an epoxy resin monomer used in a preparation process comprises a compound shown in formula DBDBBB:
- 4. The preparation method according to claim 3, wherein the compound shown in formula DBDBBB is prepared by a reaction of honokiol and epichlorohydrin.
- 5. The preparation method according to claim 3, comprising the following steps of: (1) introducing nitrogen into the epoxy resin monomer to obtain a deoxygenated epoxy resin monomer; (2) adding a curing agent into the deoxygenated epoxy resin monomer obtained in the step (1) in a nitrogen atmosphere, melting the mixture at a high temperature, uniformly stirring, and pouring the mixture into a mold; and (3) curing the mold in the step (2) at a high temperature in the nitrogen atmosphere, cooling the mold in the nitrogen atmosphere, and demoulding to obtain the epoxy resin.
- 6. The preparation method according to claim 5, wherein in the step (2), the curing agent is a diamine curing agent.
- 7. The preparation method according to claim 6, wherein in the step (2), the diamine curing agent is any one or a combination two of 4,4'-diaminodiphenyl sulfone shown in formula A and 3,31-diaminodiphenyl sulfone shown in formula B: H2N NH2 0 0 NH2 0 0A H2N
- 8. The preparation method according to claim 6, wherein in the step (2), an addition amount of the curing agent is controlled, so that a molar ratio of ethylene oxide group in the epoxy resin monomer to NH-in the curing agent is 1: 0.85 to 1: 1.2; and the melting at the high temperature is carried out at a temperature of 120°C to 195°C.
- 9. The preparation method according to claim 6, wherein in the step (3), the curing at the high temperature is carried out at a temperature of 170°C to 215°C, and lasts for 3 hours to 10 hours.
- 10. An application of the dielectric thermal-conduction enhanced bio-based high-temperature-resistant epoxy resin according to claim 1 or 2 in a dielectric capacitor material.
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| PCT/CN2021/087179 WO2022062370A1 (en) | 2020-09-27 | 2021-04-14 | Dielectricity and thermal conductivity enhanced bio-based high-temperature-resistant epoxy resin, preparation method therefor, and application thereof |
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| CN113896694B (en) * | 2021-11-16 | 2022-12-06 | 韦尔通(厦门)科技股份有限公司 | Polyfunctional group hybrid epoxy compound and photo-thermal dual-curing resin composition as well as preparation method and application thereof |
| CN114315814B (en) * | 2021-12-29 | 2022-10-21 | 南京工业大学 | Honokiol/glycosyl furan biobased epoxy resin monomer and preparation method and application thereof |
| CN114395110B (en) * | 2022-01-30 | 2023-04-07 | 南京工业大学 | All-bio-based cyano epoxy resin and green preparation method thereof |
| CN116178356A (en) * | 2022-11-02 | 2023-05-30 | 南京工业大学 | Magnolol/glycosyl furan bis-bio-based epoxy resin monomer, and preparation method and application thereof |
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