CN112375337A - Preparation method of epoxy resin with low dielectric loss - Google Patents
Preparation method of epoxy resin with low dielectric loss Download PDFInfo
- Publication number
- CN112375337A CN112375337A CN202011425858.4A CN202011425858A CN112375337A CN 112375337 A CN112375337 A CN 112375337A CN 202011425858 A CN202011425858 A CN 202011425858A CN 112375337 A CN112375337 A CN 112375337A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- dielectric loss
- mixture
- low dielectric
- steps
- 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.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 61
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 24
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 24
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000008117 stearic acid Substances 0.000 claims abstract description 24
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 239000012298 atmosphere Substances 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 7
- 239000002114 nanocomposite Substances 0.000 claims abstract description 6
- 238000004321 preservation Methods 0.000 claims abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 54
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- WNXNUPJZWYOKMW-UHFFFAOYSA-N 5-bromopentanoic acid Chemical compound OC(=O)CCCCBr WNXNUPJZWYOKMW-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 12
- 229910000278 bentonite Inorganic materials 0.000 claims description 12
- 239000000440 bentonite Substances 0.000 claims description 12
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 12
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 12
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 12
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000008096 xylene Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 12
- 230000000052 comparative effect Effects 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 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
- 238000012360 testing method Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000243 solution Substances 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
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Polyurethanes Or Polyureas (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of epoxy resin with low dielectric loss; mixing epoxy resin and a bridging agent, adding the mixture into a reaction kettle, heating the mixture to 135-140 ℃ under the protection of inert atmosphere, carrying out heat preservation and stirring reaction for 35-40min, adding a mixture of stearic acid and diisocyanate, continuously heating the mixture to 168-170 ℃, and carrying out heat preservation and stirring for 1-1.5 h to obtain an intermediate; dissolving the intermediate in an organic solvent, stirring and dissolving, adding a nano additive, adjusting the temperature to 120-130 ℃, performing ultrasonic dispersion treatment for 20-25min, and performing rotary evaporation to remove the organic solvent to obtain the nano-composite material; the epoxy resin prepared by the method has greatly changed performance parameters.
Description
Technical Field
The invention belongs to the technical field of epoxy resin, and particularly relates to a preparation method of epoxy resin with low dielectric loss.
Background
The epoxy resin is a high molecular polymer, has a molecular formula of (C11H12O3) n, and is a general name of a polymer containing more than two epoxy groups in a molecule. It is a polycondensation product of epichlorohydrin and bisphenol A or a polyol. Because of the chemical activity of the epoxy group, the epoxy group can be opened by a plurality of compounds containing active hydrogen, and the epoxy group is cured and crosslinked to form a network structure, so that the epoxy group is a thermosetting resin. The bisphenol A epoxy resin has the largest yield and the most complete variety, and the new modified variety is continuously increased and the quality is continuously improved.
The excellent physical mechanical and electrical insulation properties of epoxy resins, their adhesion to various materials, and their flexibility in the process of use are not available with other thermosets. Therefore, the material can be made into coating, composite materials, casting materials, adhesives, mould pressing materials and injection molding materials, and can be widely applied to various fields of national economy.
The epoxy resin prepared by the prior art has high dielectric loss, the dielectric medium has heating phenomenon inside under the action of an external electric field, which means that part of electric energy is converted into heat energy to be dissipated, and the energy consumed by the dielectric medium in unit time due to heating under the action of the electric field is called dielectric loss power or dielectric loss (dielectric loss) for short. Dielectric loss is one of the important quality indicators for dielectrics used in alternating electric fields. The dielectric loss not only consumes electric energy, but also causes the element to generate heat to influence the normal operation of the element. If the dielectric loss is large, it may even cause overheating of the medium to cause dielectric breakdown, so in this sense, the smaller the dielectric loss is, the better.
Disclosure of Invention
The invention aims to provide a preparation method of epoxy resin with low dielectric loss, which aims to solve the defects in the prior art.
The technical scheme adopted by the invention is as follows:
a preparation method of epoxy resin with low dielectric loss comprises the steps of mixing epoxy resin and bridging agent, adding the mixture into a reaction kettle, heating the mixture to the temperature of 135-;
dissolving the intermediate in an organic solvent, stirring and dissolving, adding a nano additive, adjusting the temperature to 120-130 ℃, performing ultrasonic dispersion treatment for 20-25min, and performing rotary evaporation to remove the organic solvent to obtain the nano-composite material.
The preparation method of the bridging agent comprises the following steps:
sequentially adding triphenylphosphine and acetonitrile into a reaction kettle, introducing nitrogen, discharging air in the reaction kettle, adding 5-bromovaleric acid, adjusting the temperature to 70-76 ℃, keeping the temperature, stirring and reacting for 2 hours, naturally cooling to room temperature, filtering, washing for 3 times by using diethyl ether, combining the three filtrates, and removing the acetonitrile by rotary evaporation to obtain the final product;
the mixing mass ratio of the epoxy resin to the bridging agent is 60-68: 1-1.5.
The molar ratio of the triphenylphosphine to the 5-bromovaleric acid is 1: 1;
the mixing ratio of triphenylphosphine to acetonitrile was 10 g: 200 mL.
The inert atmosphere is helium atmosphere.
The mass ratio of stearic acid to diisocyanate in the mixture of stearic acid and diisocyanate is 5: 1-2;
the mass ratio of the mixture of stearic acid and diisocyanate to the epoxy resin is 4-5: 50.
the organic solvent is xylene;
the mixing ratio of the xylene to the intermediate is 500 mL: 50-60 g.
The ultrasonic frequency is 35kHz, and the power is 800W.
The preparation method of the nano additive comprises the following steps: uniformly dispersing nano bentonite into deionized water, adding sodium carboxymethylcellulose and ethanol into the deionized water, stirring for 40min, performing suction filtration, washing, and drying to constant weight.
The mixing mass ratio of the nano bentonite, the deionized water, the sodium carboxymethylcellulose and the ethanol is 30-40:80-88:1-2: 15-20.
The curing agent adopts diethylenetriamine, and the mixing ratio of the curing agent to the epoxy resin is 5: 2.
Has the advantages that:
the performance parameters of the epoxy resin prepared by the method are greatly changed, so that the participation degree of the method in the modification treatment of the epoxy resin is higher, the dielectric loss of the epoxy resin prepared by the method is greatly reduced, and the dielectric property of the epoxy resin prepared by the method is greatly improved, and particularly, the performance of the epoxy resin can be greatly improved by introducing the bridging agent prepared by the method; according to the invention, by introducing the prepared bridging agent and combining the bridging agent with epoxy resin molecules, in the reaction process, epoxy groups with larger polarity are gradually reduced, and a cross-linking structure with stable structure is regenerated, so that the stability of the system is promoted to be greatly improved, the polarity of the polymer system can be reduced by the new structure, and the prepared epoxy resin can show excellent dielectric property after being cured, and the dielectric loss is greatly reduced.
Detailed Description
A preparation method of epoxy resin with low dielectric loss comprises the steps of mixing epoxy resin and bridging agent, adding the mixture into a reaction kettle, heating the mixture to the temperature of 135-;
dissolving the intermediate in an organic solvent, stirring and dissolving, adding a nano additive, adjusting the temperature to 120-130 ℃, performing ultrasonic dispersion treatment for 20-25min, and performing rotary evaporation to remove the organic solvent to obtain the nano-composite material.
The preparation method of the bridging agent comprises the following steps:
sequentially adding triphenylphosphine and acetonitrile into a reaction kettle, introducing nitrogen, discharging air in the reaction kettle, adding 5-bromovaleric acid, adjusting the temperature to 70-76 ℃, keeping the temperature, stirring and reacting for 2 hours, naturally cooling to room temperature, filtering, washing for 3 times by using diethyl ether, combining the three filtrates, and removing the acetonitrile by rotary evaporation to obtain the final product;
the mixing mass ratio of the epoxy resin to the bridging agent is 60-68: 1-1.5.
The molar ratio of the triphenylphosphine to the 5-bromovaleric acid is 1: 1;
the mixing ratio of triphenylphosphine to acetonitrile was 10 g: 200 mL.
The inert atmosphere is helium atmosphere.
The mass ratio of stearic acid to diisocyanate in the mixture of stearic acid and diisocyanate is 5: 1-2;
the mass ratio of the mixture of stearic acid and diisocyanate to the epoxy resin is 4-5: 50.
the organic solvent is xylene;
the mixing ratio of the xylene to the intermediate is 500 mL: 50-60 g.
The ultrasonic frequency is 35kHz, and the power is 800W.
The preparation method of the nano additive comprises the following steps: uniformly dispersing nano bentonite into deionized water, adding sodium carboxymethylcellulose and ethanol into the deionized water, stirring for 40min, performing suction filtration, washing, and drying to constant weight.
The mixing mass ratio of the nano bentonite, the deionized water, the sodium carboxymethylcellulose and the ethanol is 30-40:80-88:1-2: 15-20.
The curing agent adopts diethylenetriamine, and the mixing ratio of the curing agent to the epoxy resin is 5: 2.
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of epoxy resin with low dielectric loss comprises the steps of mixing epoxy resin and a bridging agent, adding the mixture into a reaction kettle, heating the mixture to 135 ℃ under the protection of inert atmosphere, keeping the temperature, stirring and reacting for 35min, adding a mixture of stearic acid and diisocyanate, continuously heating the mixture to 168 ℃, keeping the temperature, and stirring for 1 hour to obtain an intermediate; dissolving the intermediate in an organic solvent, stirring for dissolving, adding the nano additive, adjusting the temperature to 120 ℃, performing ultrasonic dispersion treatment for 20min, and performing rotary evaporation to remove the organic solvent to obtain the nano-composite material. The preparation method of the bridging agent comprises the following steps: sequentially adding triphenylphosphine and acetonitrile into a reaction kettle, introducing nitrogen, discharging air in the reaction kettle, adding 5-bromovaleric acid, adjusting the temperature to 70 ℃, keeping the temperature, stirring and reacting for 2 hours, naturally cooling to room temperature, filtering, washing for 3 times by using ether, combining three filtrates, and removing the acetonitrile by rotary evaporation to obtain the product; the mixing mass ratio of the epoxy resin to the bridging agent is 60: 1. The molar ratio of the triphenylphosphine to the 5-bromovaleric acid is 1: 1; the mixing ratio of triphenylphosphine to acetonitrile was 10 g: 200 mL. The inert atmosphere is helium atmosphere. The mass ratio of stearic acid to diisocyanate in the mixture of stearic acid and diisocyanate is 5: 1; the mass ratio of the mixture of stearic acid and diisocyanate to the epoxy resin is 4: 50. the organic solvent is xylene; the mixing ratio of the xylene to the intermediate is 500 mL: 50 g. The ultrasonic frequency is 35kHz, and the power is 800W. The preparation method of the nano additive comprises the following steps: uniformly dispersing nano bentonite into deionized water, adding sodium carboxymethylcellulose and ethanol into the deionized water, stirring for 40min, performing suction filtration, washing, and drying to constant weight. The mixing mass ratio of the nano bentonite, the deionized water, the sodium carboxymethylcellulose and the ethanol is 30:80:1: 15.
Example 2
A preparation method of epoxy resin with low dielectric loss comprises the steps of mixing epoxy resin and bridging agent, adding the mixture into a reaction kettle, heating the mixture to 140 ℃ under the protection of inert atmosphere, keeping the temperature, stirring and reacting for 40min, adding a mixture of stearic acid and diisocyanate, continuously heating the mixture to 170 ℃, keeping the temperature, and stirring for 1.5 hours to obtain an intermediate; dissolving the intermediate in an organic solvent, stirring for dissolving, adding the nano additive, adjusting the temperature to 130 ℃, performing ultrasonic dispersion treatment for 25min, and performing rotary evaporation to remove the organic solvent to obtain the nano-composite material. The preparation method of the bridging agent comprises the following steps: sequentially adding triphenylphosphine and acetonitrile into a reaction kettle, introducing nitrogen, discharging air in the reaction kettle, adding 5-bromovaleric acid, adjusting the temperature to 76 ℃, keeping the temperature, stirring and reacting for 2 hours, naturally cooling to room temperature, filtering, washing for 3 times by using ether, combining three filtrates, and removing the acetonitrile by rotary evaporation to obtain the product; the mixing mass ratio of the epoxy resin to the bridging agent is 68: 1.5. The molar ratio of the triphenylphosphine to the 5-bromovaleric acid is 1: 1; the mixing ratio of triphenylphosphine to acetonitrile was 10 g: 200 mL. The inert atmosphere is helium atmosphere. The mass ratio of stearic acid to diisocyanate in the mixture of stearic acid and diisocyanate is 5: 2;
the mass ratio of the mixture of stearic acid and diisocyanate to the epoxy resin is 5: 50. the organic solvent is xylene; the mixing ratio of the xylene to the intermediate is 500 mL: 60 g. The ultrasonic frequency is 35kHz, and the power is 800W. The preparation method of the nano additive comprises the following steps: uniformly dispersing nano bentonite into deionized water, adding sodium carboxymethylcellulose and ethanol into the deionized water, stirring for 40min, performing suction filtration, washing, and drying to constant weight. The mixing mass ratio of the nano bentonite, the deionized water, the sodium carboxymethylcellulose and the ethanol is 40:88:2: 20.
Example 3
A preparation method of epoxy resin with low dielectric loss comprises the steps of mixing epoxy resin and a bridging agent, adding the mixture into a reaction kettle, heating the mixture to 137 ℃ under the protection of inert atmosphere, carrying out heat preservation and stirring reaction for 38min, adding a mixture of stearic acid and diisocyanate, continuously heating the mixture to 169 ℃, carrying out heat preservation and stirring for 1.3 h, and obtaining an intermediate; dissolving the intermediate in organic solvent, stirring for dissolving, adding nanometer additive, adjusting temperature to 124 deg.C, performing ultrasonic dispersion treatment for 20-25min, and performing rotary evaporation to remove organic solvent. The preparation method of the bridging agent comprises the following steps: sequentially adding triphenylphosphine and acetonitrile into a reaction kettle, introducing nitrogen, discharging air in the reaction kettle, adding 5-bromovaleric acid, adjusting the temperature to 73 ℃, keeping the temperature, stirring and reacting for 2 hours, naturally cooling to room temperature, filtering, washing for 3 times by using ether, combining three filtrates, and removing the acetonitrile by rotary evaporation to obtain the product; the mixing mass ratio of the epoxy resin to the bridging agent is 65: 1.2. The molar ratio of the triphenylphosphine to the 5-bromovaleric acid is 1: 1; the mixing ratio of triphenylphosphine to acetonitrile was 10 g: 200 mL. The inert atmosphere is helium atmosphere. The mass ratio of stearic acid to diisocyanate in the mixture of stearic acid and diisocyanate is 5: 1.5; the mass ratio of the mixture of stearic acid and diisocyanate to the epoxy resin is 4.6: 50. the organic solvent is xylene; the mixing ratio of the xylene to the intermediate is 500 mL: 53 g. The ultrasonic frequency is 35kHz, and the power is 800W. The preparation method of the nano additive comprises the following steps: uniformly dispersing nano bentonite into deionized water, adding sodium carboxymethylcellulose and ethanol into the deionized water, stirring for 40min, performing suction filtration, washing, and drying to constant weight. The mixing mass ratio of the nano bentonite to the deionized water to the sodium carboxymethylcellulose to the ethanol is 34:82:1.5: 18.
Test of
The untreated epoxy resin and the epoxy resin of examples 1 to 3 were subjected to performance testing (the curing agent was diethylenetriamine, and the mixing ratio of the curing agent to the epoxy resin was 5: 2), and compared;
TABLE 1
| Epoxy equivalent g/eq | Viscosity mPa.s/25 DEG C | |
| Example 1 | 267 | 6150 |
| Example 2 | 270 | 5800 |
| Example 3 | 275 | 5500 |
| Comparative example 1 | 182 | 12500 |
Comparative example 1: an untreated epoxy resin;
as can be seen from Table 1, the epoxy resin prepared by the method of the present invention has greatly changed performance parameters, and thus, the method of the present invention has a high participation degree in the modification treatment of the epoxy resin.
Dielectric loss:
the dielectric loss (Df) at 1GHz was determined by the plate method according to IPC-TM-6502.5.5.9:
TABLE 2
| Dielectric loss (Df) | |
| Example 1 | 0.0063 |
| Example 2 | 0.0066 |
| Example 3 | 0.0062 |
| Comparative example 2 | 0.0122 |
| Comparative example 3 | 0.0087 |
Comparative example 2: the difference from example 3 is that no bridging agent is added;
comparative example 3: the difference from example 3 is that no stearic acid is added;
as can be seen from Table 2, the dielectric loss of the epoxy resin prepared by the method of the present invention is greatly reduced, which indicates that the dielectric property of the epoxy resin prepared by the method of the present invention is greatly improved, and particularly, the performance of the epoxy resin can be greatly improved by introducing the bridging agent prepared by the present invention.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention, and the present invention is not limited to the illustrated embodiments, and all the modifications and equivalents of the embodiments may be made without departing from the spirit of the present invention.
Claims (9)
1. A preparation method of epoxy resin with low dielectric loss is characterized in that epoxy resin and bridging agent are mixed and added into a reaction kettle, then the mixture is heated to 135-plus-140 ℃ under the protection of inert atmosphere, the mixture is stirred and reacted for 35-40min under heat preservation, then the mixture of stearic acid and diisocyanate is added, the temperature is continuously raised to 168-plus-170 ℃, the mixture is stirred and preserved for 1-1.5 h, and an intermediate is obtained;
dissolving the intermediate in an organic solvent, stirring and dissolving, adding a nano additive, adjusting the temperature to 120-130 ℃, performing ultrasonic dispersion treatment for 20-25min, and performing rotary evaporation to remove the organic solvent to obtain the nano-composite material.
2. The method for preparing the epoxy resin with low dielectric loss according to claim 1, wherein the method comprises the following steps: the preparation method of the bridging agent comprises the following steps: :
sequentially adding triphenylphosphine and acetonitrile into a reaction kettle, introducing nitrogen, discharging air in the reaction kettle, adding 5-bromovaleric acid, adjusting the temperature to 70-76 ℃, keeping the temperature, stirring and reacting for 2 hours, naturally cooling to room temperature, filtering, washing for 3 times by using diethyl ether, combining the three filtrates, and removing the acetonitrile by rotary evaporation to obtain the final product;
the mixing mass ratio of the epoxy resin to the bridging agent is 60-68: 1-1.5.
3. The method for preparing the epoxy resin with low dielectric loss according to claim 2, wherein the method comprises the following steps: the molar ratio of the triphenylphosphine to the 5-bromovaleric acid is 1: 1;
the mixing ratio of triphenylphosphine to acetonitrile was 10 g: 200 mL.
4. The method for preparing the epoxy resin with low dielectric loss according to claim 1, wherein the method comprises the following steps: the inert atmosphere is helium atmosphere.
5. The method for preparing the epoxy resin with low dielectric loss according to claim 1, wherein the method comprises the following steps: the mass ratio of stearic acid to diisocyanate in the mixture of stearic acid and diisocyanate is 5: 1-2;
the mass ratio of the mixture of stearic acid and diisocyanate to the epoxy resin is 4-5: 50.
6. the method for preparing the epoxy resin with low dielectric loss according to claim 1, wherein the method comprises the following steps: the organic solvent is xylene;
the mixing ratio of the xylene to the intermediate is 500 mL: 50-60 g.
7. The method for preparing the epoxy resin with low dielectric loss according to claim 1, wherein the method comprises the following steps: the ultrasonic frequency is 35kHz, and the power is 800W.
8. The method for preparing the epoxy resin with low dielectric loss according to claim 1, wherein the method comprises the following steps: the preparation method of the nano additive comprises the following steps: uniformly dispersing nano bentonite into deionized water, adding sodium carboxymethylcellulose and ethanol into the deionized water, stirring for 40min, performing suction filtration, washing, and drying to constant weight.
9. The method for preparing the epoxy resin with low dielectric loss according to claim 8, wherein: the mixing mass ratio of the nano bentonite, the deionized water, the sodium carboxymethylcellulose and the ethanol is 30-40:80-88:1-2: 15-20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011425858.4A CN112375337A (en) | 2020-12-09 | 2020-12-09 | Preparation method of epoxy resin with low dielectric loss |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011425858.4A CN112375337A (en) | 2020-12-09 | 2020-12-09 | Preparation method of epoxy resin with low dielectric loss |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112375337A true CN112375337A (en) | 2021-02-19 |
Family
ID=74590629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011425858.4A Pending CN112375337A (en) | 2020-12-09 | 2020-12-09 | Preparation method of epoxy resin with low dielectric loss |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112375337A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004217869A (en) * | 2003-01-17 | 2004-08-05 | Dainippon Ink & Chem Inc | Epoxy resin composition and epoxy resin curing agent |
| CN102532481A (en) * | 2010-12-09 | 2012-07-04 | 中国科学院金属研究所 | Carboxyl functional group containing epoxy resin capable of chemically bonding with steel base material and preparation method thereof |
| CN106317779A (en) * | 2016-08-17 | 2017-01-11 | 阮丽丽 | Low temperature resistant cable material and preparation method thereof |
-
2020
- 2020-12-09 CN CN202011425858.4A patent/CN112375337A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004217869A (en) * | 2003-01-17 | 2004-08-05 | Dainippon Ink & Chem Inc | Epoxy resin composition and epoxy resin curing agent |
| CN102532481A (en) * | 2010-12-09 | 2012-07-04 | 中国科学院金属研究所 | Carboxyl functional group containing epoxy resin capable of chemically bonding with steel base material and preparation method thereof |
| CN106317779A (en) * | 2016-08-17 | 2017-01-11 | 阮丽丽 | Low temperature resistant cable material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 吴登瑜等: ""季膦盐4-羧丁基三苯基溴化膦的合成"" * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109824892B (en) | Polyimide copolymer precursor, polyimide, and method for producing polyimide film | |
| CN105315454B (en) | The application of the organic-silicon-modified method for preparing siliceous double hydroxyl polyphenylene oxide and product | |
| WO2024174291A1 (en) | Biomass epoxy monomer, self-curing epoxy resin and preparation method therefor | |
| CN114736354B (en) | Preparation method and application of resveratrol-based all-bio-based epoxy resin | |
| CN112375337A (en) | Preparation method of epoxy resin with low dielectric loss | |
| CN115160540B (en) | High-modulus high-activity epoxy resin and synthetic method and application thereof | |
| CN114685476B (en) | Bio-based p-hydroxyacetophenone-furfuryl amine benzoxazine monomer, resin and preparation method thereof | |
| CN114437657B (en) | Preparation method of high-strength metal epoxy AB glue | |
| CN115073785B (en) | Phthalonitrile resin film and preparation method thereof | |
| CN115466372A (en) | Epoxy resin prepolymer containing aldehyde group, preparation method and application thereof | |
| CN103086911B (en) | Oligomer, polyimide film/fiber containing oligomer and preparation method of polyimide film/fiber containing oligomer | |
| CN115010705B (en) | Bio-based raspberry ketone-furfuryl amine type benzoxazine monomer, resin and preparation method thereof | |
| CN110563926A (en) | Fluorine-containing epoxy resin curing agent and preparation method thereof, and epoxy resin material and preparation method thereof | |
| CN114736408B (en) | Preparation method of high-dielectric PI/PVDF composite film | |
| CN118755054A (en) | Method for preparing epoxy imine solid-plastic material by solvent-free one-step method | |
| CN116218216B (en) | Polyimide-based composite material with high energy storage density and preparation method thereof | |
| KR20160033009A (en) | Preparation method for polyimide product and the polyimide product thereby | |
| CN110156992A (en) | A kind of preparation and its application of aqueous polyimides | |
| CN117801668B (en) | Insulating paint for electrodeposition coating and preparation method and application thereof | |
| Liu et al. | Preparation and properties of hybrid silane-crosslinked sulfonated poly (aryl ether ketone) s as proton exchange membranes | |
| CN113956618B (en) | Preparation method of three-dimensional porous barium titanate composite dielectric material | |
| CN117164817B (en) | Autocatalysis type cardanol-based self-repairing and recyclable polymer and preparation method thereof | |
| CN112759732B (en) | Composite modified water-based phenolic resin and preparation method thereof | |
| CN113372604B (en) | Method for preparing thermosetting epoxy resin microporous foam with assistance of ultrasound | |
| CN115651189A (en) | Benzoxazine-functionalized polyphenylene ether resin prepolymer, thermosetting resin and preparation method thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210219 |
|
| RJ01 | Rejection of invention patent application after publication |