CN117736411A - Preparation and degradation recovery method of high-performance degradable recovered epoxy resin - Google Patents
Preparation and degradation recovery method of high-performance degradable recovered epoxy resin Download PDFInfo
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- CN117736411A CN117736411A CN202410030610.XA CN202410030610A CN117736411A CN 117736411 A CN117736411 A CN 117736411A CN 202410030610 A CN202410030610 A CN 202410030610A CN 117736411 A CN117736411 A CN 117736411A
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- bisphenol
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 114
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 114
- 238000011084 recovery Methods 0.000 title claims abstract description 38
- 230000015556 catabolic process Effects 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims abstract description 56
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims abstract description 51
- 235000012141 vanillin Nutrition 0.000 claims abstract description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 21
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims abstract description 20
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 238000007731 hot pressing Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 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 claims description 24
- 239000000178 monomer Substances 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical group C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical group CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000003828 vacuum filtration Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000012264 purified product Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 2
- 238000007872 degassing Methods 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims 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 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 12
- 230000009477 glass transition Effects 0.000 abstract description 6
- 238000010292 electrical insulation Methods 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 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
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 235000013599 spices Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 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
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 241001093501 Rutaceae Species 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 229960002479 isosorbide Drugs 0.000 description 1
- 238000010983 kinetics study Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Epoxy Resins (AREA)
Abstract
The invention discloses a preparation method and a degradation recovery method of high-performance degradable recovered epoxy resin, and belongs to the technical field of epoxy resins. A high-performance degradable recycled epoxy resin is prepared from the following raw materials: para-aminophenol, vanillin, epichlorohydrin, bisphenol A epoxy resin, a curing agent, a catalyst, tetrabutylammonium bromide and sodium hydroxide solution. The high-performance degradable recycled vanillin-based epoxy resin provided by the invention has the advantages of strong reaction activity, low curing temperature and initial curing temperature lower than 100 ℃; the heat resistance is good, and the glass transition temperature is up to 159 ℃; the electrical insulation performance and the mechanical performance are excellent, the dielectric loss factor is only 0.34, and the maximum tensile strength can reach 76MPa; degradation can be realized in 25h at 100 ℃; the degraded solution and the crushed epoxy resin can be recycled by hot pressing, and the recovery rate of the electrical breakdown strength can reach 98% at maximum; has surface self-repairing ability, and can be maintained at 180deg.C for 60-180min to remove scratch.
Description
Technical Field
The invention relates to the technical field of epoxy resin, in particular to a preparation method and a degradation recovery method of high-performance degradable recovered epoxy resin.
Background
Epoxy Resin (EP) is a three-dimensionally crosslinked polymer material having excellent adhesive strength, thermal stability, mechanical properties, weather resistance and electrical insulation properties, and is widely used in the electrical application fields of composite insulation materials, electronic component packaging, dry reactors, dry transformers, and the like. At present, more than 90% of epoxy resins in the market are bisphenol A diglycidyl ether (DGEBA), which is a petroleum-based compound that consumes a large amount of petrochemical resources and causes large carbon emission and environmental pollution. With the aggravation of global energy crisis and the increasing worsening of the environment, the development of the bio-based epoxy resin which can replace or partially replace DGEBA by taking environment-friendly and renewable resources as raw materials becomes one of the important ways for realizing the environmental protection of the epoxy electrotechnical equipment
The bio-based epoxy resin is thermosetting epoxy resin prepared by taking renewable resources as raw materials through an epoxidation method, and researchers at home and abroad currently conduct extensive researches on the synthesis and application of the bio-based epoxy resin such as rosin, vanillin, itaconic acid, isosorbide and the like. The prepared part of bio-based epoxy resin is comparable with the traditional bisphenol A epoxy resin in thermal insulation performance and the like, however, the three-dimensional crosslinked network formed after the epoxy resin is solidified has the characteristics of insolubility and infusibility, high-efficiency degradation and recycling cannot be realized, the resource waste phenomenon of retired equipment is caused, and serious pollution is caused to the ecological environment.
Vanillin, also known as vanillin, is a chemical name 3-methoxy-4-hydroxybenzaldehyde, an organic compound extracted from the kidney bean of the family Rutaceae, is an important broad-spectrum high-grade spice, is one of the most global-yield spices by 2019, is one of the most commonly used food flavoring agents in the world at present, and has the reputation of "food spice king". Vanillin is white to yellowish crystal or crystalline powder, slightly sweet, soluble in hot water, glycerol and alcohol, not easily soluble in cold water and vegetable oil, easily oxidized in air, and easily discolored when meeting alkaline substances.
Disclosure of Invention
The invention aims to provide a preparation and degradation recovery method of high-performance degradable recycled epoxy resin, so as to provide a bio-based epoxy resin which has wide material sources and performance comparable to that of the traditional bisphenol A epoxy resin, but can be degraded and recycled, thereby reducing the resource waste and the environmental pollution caused by the traditional epoxy resin.
In order to achieve the above purpose, the invention provides a preparation and degradation recovery method of high-performance degradable recovered epoxy resin, which is prepared from the following raw materials:
para-aminophenol, vanillin, epichlorohydrin, bisphenol A epoxy resin, a curing agent, a catalyst, tetrabutylammonium bromide and sodium hydroxide solution.
Preferably, the catalyst is 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, the curing agent is 2-methyl hexahydrophthalic anhydride, the bisphenol A epoxy resin is E-51 bisphenol A epoxy resin, and the mass fraction of the sodium hydroxide solution is 20%.
Preferably, p-aminophenol: vanillin: the molar ratio of the epichlorohydrin is 1:1:10.
The preparation method of the high-performance degradable recycled epoxy resin comprises the following steps:
s1, respectively dissolving vanillin and para-aminophenol in deionized water and absolute ethyl alcohol, pouring the mixture into a round-bottom flask with a condensing device for reaction under certain conditions, performing vacuum filtration, washing the mixture with absolute ethyl alcohol for three times after the completion of vacuum filtration, and drying to obtain a purified product yellow powder which is vanillin-based diphenol monomer; the reaction formula is:
s2, placing a round-bottom flask with a condensing reflux and magnetic stirring device in an oil bath, then adding the vanillin diphenol monomer and epoxy chloropropane obtained in the step S1 into the round-bottom flask, starting stirring, adding tetrabutylammonium bromide after each component is dissolved, and then heating the system to a certain temperature and keeping for a certain time;
s3, slowly dropwise adding 20% sodium hydroxide in parts by weight into a reaction system, cooling the reaction system, reacting for a certain time after the reaction system is cooled to a required temperature, vacuum-filtering the obtained product, diluting with petroleum ether, adding distilled water for washing, extracting for three times, removing excessive epichlorohydrin and petroleum ether by using a rotary evaporator, and vacuum-drying overnight to obtain a white solid which is a vanillin-based epoxy monomer, wherein the reaction formula is as follows:
s4, uniformly mixing the E-51 bisphenol A epoxy resin and the vanillin-based epoxy monomer obtained in the step S3 at 110 ℃, then adding a curing agent, uniformly mixing the components in a melting way, adding a catalyst, uniformly mixing again, then placing the mixture in a vacuum oven for degassing, and curing according to a step curing mode of 100 ℃/2h+130 ℃/5 h.
Preferably, in the step S1, 1mol of vanillin is dissolved in 4L of deionized water, and 1mol of p-aminophenol is dissolved in 2L of absolute ethanol; reflux stirring for 2-3h at 50-60 ℃; drying in a vacuum drying oven at 50-65deg.C overnight.
Preferably, the amount of tetrabutylammonium bromide added in the step S2 is 10% of the mass of the vanillin diphenol monomer, the system is heated to a certain temperature and kept for a certain time, namely the system is heated to 80-90 ℃ and reacts for 1.5-3 hours; in the step S4, bisphenol a type epoxy resin: the molar ratio of the prepared vanillin epoxy resin is 1:1.
Preferably, in the step S3, 20% sodium hydroxide is slowly added dropwise in parts by weight, namely, the dropwise addition is completed within 0.5h, the amount of the 20% sodium hydroxide is 2 times of the mass of the vanillin diphenol monomer, the reaction is carried out for a certain time after the reaction is carried out at the required temperature, namely, the reaction is carried out for 3-5h after the reaction is carried out at room temperature; the addition amount of petroleum ether is 20 times of the mass of vanillin diphenol monomer; vacuum drying is carried out in a vacuum drying oven at 50-70 ℃ overnight.
The degradation method of the high-performance degradable recycled epoxy resin is realized by placing the epoxy resin in degradation liquid, wherein the degradation method comprises the following steps: the mass ratio of the degradation liquid is 1:20, and the degradation liquid is n-hexylamine.
The recovery method of the high-performance degradable recovered epoxy resin can be realized by a chemical recovery method or a physical recovery method, and the chemical recovery method comprises the following steps:
dissolving the prepared vanillin-based epoxy resin in degradation liquid, placing the system in a rotary evaporator, transferring the system into a mold when the solution is in a viscous state, heating in vacuum, continuously hot-pressing for 6 hours at 180 ℃ and 10MPa, naturally cooling, cooling to room temperature, and demolding to obtain the recovered vanillin-based epoxy resin;
the physical recovery method is as follows: crushing vanillin-based epoxy resin into particles with the diameter of 1-5mm by using a crusher, placing the particles into two steel plate molds coated with release oil, hot-pressing the steel plate molds for 4 hours at the temperature of 200 ℃ and the pressure of 20MPa on a plate vulcanizing machine, cooling the steel plate molds to room temperature for molding, and demolding to obtain recovered sample pieces.
Therefore, the preparation and degradation recovery method of the high-performance degradable recovered epoxy resin provided by the invention has the following specific technical effects:
(1) The high-performance degradable recycled vanillin-based epoxy resin provided by the invention has the advantages of strong reaction activity, low curing temperature and initial curing temperature lower than 100 ℃; the heat resistance is good, and the glass transition temperature can reach 159 ℃; the electrical insulation performance and the mechanical performance are excellent, the dielectric loss factor is only 0.34, and the maximum tensile strength can reach 76MPa;
(2) The high-performance degradable recycled vanillin-based epoxy resin provided by the invention can be degraded at 100 ℃ within 25 hours; the degraded solution and the crushed epoxy resin can be recycled by hot pressing, and the recovery rate of the electrical breakdown strength can reach 98% at maximum;
(3) The high-performance degradable recycled vanillin-based epoxy resin provided by the invention has the advantages that the vanillin-based vitrified epoxy resin with intrinsic imine bonds is prepared, so that the vanillin-based epoxy resin has the surface self-repairing capability, the vanillin-based epoxy resin is kept at 180 ℃ for 3 hours, scratches disappear, and the scratches can disappear in 60 minutes at best.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments of the present invention will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process for synthesizing an epoxy resin of the present invention;
FIG. 2 shows the curing temperature curves of epoxy resin and commercial bisphenol A epoxy resin prepared by the present invention, wherein (a) is a curing temperature curve of Van-0, (b) is a curing temperature curve of Van-0.25, (c) is a curing temperature curve of Van-0.5, (d) is a curing temperature curve of Van-0.75, (f) is a curing temperature curve of Van-1, ti is an initial curing temperature, tp is a peak curing temperature, te is a final curing temperature;
FIG. 3 is a DMA curve of an epoxy resin prepared according to the present invention with a commercially available bisphenol A type epoxy resin;
FIG. 4 is a graph showing the mechanical properties of the epoxy resin made in accordance with the present invention and a commercially available bisphenol A type epoxy resin;
FIG. 5 is a TGA curve of an epoxy resin made in accordance with the present invention versus a commercially available bisphenol A type epoxy resin;
FIG. 6 is a graph showing the electrical properties of an epoxy resin made in accordance with the present invention and a commercially available bisphenol A type epoxy resin;
FIG. 7 is a degradation image of an epoxy resin prepared in accordance with the present invention and a commercial bisphenol A type epoxy resin, wherein part A is a photograph of the epoxy resin just added to n-hexylamine and part B is a photograph of the epoxy resin degraded for 25 hours;
FIG. 8 is a graph showing the degradation of epoxy resins prepared in accordance with the present invention and commercial bisphenol A type epoxy resins;
FIG. 9 is a graph showing the recovery performance of the epoxy resin made in accordance with the present invention versus a commercially available bisphenol A type epoxy resin;
FIG. 10 shows a self-repairing process of an epoxy resin and a commercial bisphenol A epoxy resin, wherein (a) is a scratch photo of Van-0 at different times, (b) is a scratch photo of Van-0.25 at different times, (c) is a scratch photo of Van-0.5 at different times, (d) is a scratch photo of Van-0.75 at different times, and (e) is a scratch photo of Van-1 at different times.
Detailed Description
The technical scheme of the invention is further described below through the attached drawings and the embodiments.
In order to make the objects, technical solutions and advantages of the present application more clear, thorough and complete, the technical solutions of the present invention will be clearly and completely described below through the accompanying drawings and examples. The following detailed description is of embodiments, and is intended to provide further details of the invention. Unless defined otherwise, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
The instrumentation and reagent materials used in the examples are commercially available.
Example 1
The steps of the synthesis of vanillin epoxy monomer are as follows:
(1) 15.2g of vanillin (0.1 mol) and 10.9g of para-aminophenol (0.1 mol) were dissolved in 400mL of deionized water and 200mL of absolute ethanol, respectively, and poured into a round bottom flask equipped with a condensing device. The mixed solution is refluxed and stirred for 2 hours at 50 ℃, filtered under vacuum at room temperature and finally washed with absolute ethyl alcohol three times. Drying overnight in a vacuum oven at 60deg.C gave a yellow powder of the purified product as vanillin-based diphenol monomer (DV). According to the formula: yield = mass of product actually obtained/mass of product to be obtained by complete reaction x 100%, calculated as 90%.
(2) A500 mL round bottom flask with a condensing reflux and magnetic stirring device was placed in an oil bath, 24.3g DV (0.1 mol) and 92g (1 mol) epichlorohydrin were added, after stirring and dissolution, 2.43g tetrabutylammonium bromide (10% of DV mass) was added, the reaction temperature was gradually raised from room temperature to 85℃and stirring was maintained, and the reaction was continued for 2 hours. Subsequently, 50g of 20% sodium hydroxide solution was added dropwise to the mixture over 0.5h, stirring was maintained, and the reaction was continued with stirring for 4h after the temperature of the reaction system was lowered to room temperature. The resulting product was vacuum filtered, diluted with 480g of petroleum ether, washed with distilled water, extracted three times, excess epichlorohydrin and petroleum ether were removed by rotary evaporator, and finally the product was vacuum dried overnight at 60 ℃ to give a white solid as vanillin-based epoxy monomer (EDV). According to the formula: yield = mass of product actually obtained/mass of product to be obtained by complete reaction x 100%, calculated yield 60%.
Example two
A cured epoxy resin (Van-1) having 100% degradable recycled vanillin groups was prepared as follows:
after 10g of EDV and 4.5g of 2-methyl hexahydrophthalic anhydride (MHHPA) are melted and mixed uniformly at 110 ℃, 0.29g of 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole is added, mixed and stirred uniformly to obtain a prepolymer, and the prepolymer is poured into a mould (the specification is 10mm multiplied by 1 mm) conventionally, and is solidified by adopting a process of 100 ℃/2h+130 ℃/5h, and after solidification, the mixture is naturally cooled to room temperature, so that the solidified epoxy resin Van-1 with 100% of degradable recovered vanillin groups is obtained.
Example III
A cured epoxy resin (Van-0.75) having a degradable recovery vanillin group content of 75% was prepared as follows:
stirring, mixing 9g of EDV, 2.8g E-51 bisphenol A epoxy resin (DGEBA) and 5.4g MHHPA,0.35g 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole at 110 ℃ and stirring uniformly to obtain a prepolymer, conventionally pouring the prepolymer into a mould (specification is 10mm multiplied by 1 mm), solidifying at 100 ℃/2h+130 ℃/5h, and naturally cooling to room temperature after solidification is finished to obtain the solidified epoxy resin Van-0.75 with the degradable recovery vanillin group content of 75%, wherein the preparation reaction formula is shown in figure 1.
Example IV
A cured epoxy resin (Van-0.5) having a degradable recovery vanillin group content of 50% was prepared as follows:
7g of EDV, 6.6g of DGEBA and 6.3g MHHPA,0.4g 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole are mixed and stirred uniformly at 110 ℃ to obtain a prepolymer, the prepolymer is poured into a mould (the specification is 10mm multiplied by 1 mm) conventionally, and the mixture is solidified by adopting a process of 100 ℃/2h+130 ℃/5h, and is naturally cooled to room temperature after solidification is finished, so that the solidified epoxy resin Van-0.5 with the degradable recovery vanillin group content of 50% is obtained.
Example five
A cured epoxy resin (Van-0.25) having a degradable recovery vanillin radical content of 25% was prepared as follows:
3g of EDV, 8.5g of DGEBA and 5.4g MHHPA,0.33g 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole are mixed and stirred uniformly at 110 ℃ to obtain a prepolymer, the prepolymer is poured into a mould (the specification is 10mm multiplied by 1 mm) conventionally, and the mixture is solidified by adopting a process of 100 ℃/2h+130 ℃/5h, and is naturally cooled to room temperature after solidification, so that the solidified epoxy resin Van-0.25 with the degradable recovery vanillin group content of 25% is obtained.
Comparative example one
The preparation of the conventional bisphenol A type epoxy resin (Van-0) is as follows:
at 110 ℃,10 g DGEBA and 4.7g MHHPA,0.3g 2,4,6-tris (dimethylaminomethyl) phenol are mixed and stirred uniformly to obtain a prepolymer, and then the prepolymer is poured into a mould conventionally, and is solidified by adopting a process of 100 ℃/2h+130 ℃/5h, and after solidification, the prepolymer is naturally cooled to room temperature to obtain the commercial bisphenol A type epoxy resin Van-0.
Effect example 1
The epoxy resins prepared in examples one to five and comparative example one were examined for curing kinetics, thermal stability, dynamic mechanical properties, electrical properties, self-healing properties by the following method:
DSC test: the cure kinetics study was performed using DSC3500, 5mg of the sample was placed in an aluminum crucible with a nitrogen flow rate of 20mL/min, an initial temperature of 25℃and a termination temperature of 250 ℃. In order to determine the optimal curing process of different blending systems, the heating rate is set to be 5K/min,10K/min,15K/min and 20K/min in sequence, heating curing curves under different proportions of resin blending systems are recorded, curing dynamics research is carried out, the curing temperature curves are shown in figure 2, wherein (a) part is a curing temperature curve of Van-0, (b) part is a curing temperature curve of Van-0.25, (c) part is a curing temperature curve of Van-0.5, (d) part is a curing temperature curve of Van-0.75, (f) part is a curing temperature curve of Van-1, ti is an initial curing temperature, tp is a peak curing temperature, and Te is a termination curing temperature.
Thermogravimetric analysis (TGA): the thermal stability of the samples was measured by placing a 2mm diameter wafer specimen in an aluminum crucible using TGA4000 and testing the specimen in a nitrogen atmosphere at a temperature rising rate of 10K/min at a temperature ranging from 30 to 800℃and the results are shown in FIG. 5.
Dynamic Mechanical Analysis (DMA): a dynamic thermo-mechanical analyzer (TA Q800, USA) is adopted, a single cantilever mode is set, the heating rate is 5 ℃/min, the testing temperature range is 30-250 ℃, and the frequency is 10Hz. The results are shown in FIG. 3.
Mechanical property test: the tensile bending test is carried out by adopting a universal tensile testing machine and setting the loading rates of the load to be 5mm/min and 2mm/min respectively, and the result is shown in figure 4
Electrical performance test: (1) And carrying out power frequency breakdown voltage test by adopting a power frequency test transformer, carrying out boosting test by adopting a spherical electrode to clamp a square sample with the size of 15mm x 1mm in dimethyl silicone oil, wherein the boosting rate is constant at 2kV/s. The results are shown in FIG. 6.
(2) The leakage current test is carried out on an MS2621VS tester, 5 cylindrical samples with the diameter of 50mm and the height of 30mm are prepared, each surface is polished smoothly and flatly, immersed in 0.1wt% NaCl solution, boiled in 100 ℃ for 100 hours plus or minus 0.5 hours, the test voltage is 12kV, the heating rate is 2kV/s, and the withstand voltage time is 1min. The results are shown in FIG. 6.
(3) Dielectric loss factor test was performed on a YG9100 full-automatic anti-interference precision dielectric loss tester with test voltage of 1.5-3kV, and the result is shown in FIG. 6.
Self-repair test: the sample was gently scratched with a knife having a scratch width of about 30-40 μm, and the sample was placed in a dry box at 180℃for 3 hours and observed for scratch change every 30 minutes with an optical microscope, as shown in FIG. 10, wherein (a) part was a photograph of scratches of Van-0 different times, (b) part was a photograph of scratches of Van-0.25 different times, (c) part was a photograph of scratches of Van-0.5 different times, (d) part was a photograph of scratches of Van-0.75 different times, and (e) part was a photograph of scratches of Van-1 different times.
Effect example two
The degradation properties of the epoxy resins prepared in examples two to five and comparative example one were examined as follows:
2g of epoxy resin was taken, 40g of n-hexylamine was added, 3 repetitions were performed as observed at 25h of adding n-hexylamine, and the results are shown in FIG. 7, wherein part A is a photograph of the epoxy resin just added to n-hexylamine, and part B is a photograph of degradation for 25 h.
Taking out the epoxy resin added with n-hexylamine every 0.5h, sucking the surface liquid by using filter paper, weighing, and according to the formula: residual mass percent = mass of epoxy resin obtained/2 g x 100%, calculated as residual mass percent plotted against time after addition of n-hexylamine, results are shown in fig. 8.
Effect example three
The recovery properties of the epoxy resins prepared in examples two to five were examined as follows:
the recovery effect is expressed in terms of electrical breakdown strength, and the initial breakdown strength is measured first, after physical/chemical recovery, the breakdown strength after recovery is measured, and the recovery rate is characterized by the breakdown after recovery compared with the initial breakdown strength. The results are shown in FIG. 9.
Analysis of results
As can be seen from FIG. 2, the epoxy resins prepared in the second to fifth embodiments of the present invention have a curing initiation temperature lower than 100℃and a peak curing temperature and a final curing temperature lower than those of the conventional epoxy resin (comparative example I), and have high reactivity. Taken together, van-1 requires the lowest temperature for the curing process, with a final cure temperature of only 115 ℃.
As can be seen from fig. 3, all epoxy resins in the examples of the present invention have a glass transition temperature higher than 110 ℃ and exhibit a certain heat resistance at high temperature, which exhibits good inclusion for their application under high temperature conditions. The glass transition temperatures of the epoxy resins obtained in example IV (Van-0.5) and example V (Van-0.25) are higher than those of the conventional bisphenol A type epoxy resin (comparative example I).
As can be seen from fig. 4, the mechanical properties of the epoxy resins prepared in the second to fifth embodiments of the present invention are comparable to those of the conventional bisphenol a type epoxy resin (comparative example one), which indicates that the epoxy resins prepared in the second to fifth embodiments of the present invention have better mechanical properties. Among them, van-0.25 is the best and Van-0.75 and Van-1 are relatively poor.
As can be seen from FIG. 5, the heat resistance of the epoxy resins prepared in the second to fifth embodiments of the present invention is equivalent to that of the conventional bisphenol A epoxy resin, and the epoxy resins have good heat resistance, a certain high temperature resistance, van-0.25 shows the highest heat resistance, van-1 has the worst heat resistance, and thermal degradation is started first. The residual carbon content of the epoxy resin prepared in the second to fifth embodiments of the present invention is higher than that of the conventional bisphenol A epoxy resin, which indicates that the epoxy resin prepared in the second to fifth embodiments of the present invention has a certain flame retardant effect.
As can be seen from FIG. 6, the breakdown strength of the epoxy resin prepared by the embodiment of the invention increases with the reduction of the vanillin radical content, wherein Van-0.25 has the highest breakdown strength, which is close to that of the traditional bisphenol A epoxy resin, the dielectric dissipation factors Van-0.25 and Van-0.5 are superior to those of the traditional bisphenol A epoxy resin, and Van-0.75 and Van-1 are inferior to those of the traditional bisphenol A epoxy resin. The leakage current is equivalent to that of the traditional bisphenol A epoxy resin, and the electrical performance is excellent with only minor difference.
As can be seen from FIGS. 7 and 8, the epoxy resin prepared in the second to fourth embodiments of the present invention can be completely degraded after 25 hours, wherein Van-0.75 is degraded at the fastest rate, van-0.25 is degraded after 10 hours, and the epoxy resin can be degraded after 25 hours, and the epoxy resin in the fifth embodiment is partially degraded but not completely degraded with the conventional bisphenol A epoxy resin.
As can be seen from the recovery performance curves of the epoxy resin and the traditional bisphenol A type epoxy resin in FIG. 9, the chemical recovery effect of the epoxy resin prepared by the method is generally better than the physical recovery effect, the Van-1 recovery effect is best, and the recovery efficiency is 98%. Van-0.25 has the worst physical recycling effect.
As can be seen from FIG. 10, the epoxy resins prepared in the second to fifth embodiments of the present invention all completed self-repairing at 180 ℃/3h, wherein Van-1 has the best self-repairing performance, and Van-0.75 can complete repairing within 60min, and then repairing can complete repairing within 120min, while the conventional bisphenol A epoxy resin still has no self-repairing phenomenon within 180 min.
In conclusion, van-0.25 has the best thermoelectric performance, heat resistance and mechanical performance and the highest glass transition temperature; van-1 recovery and self-healing performance are best, van-0.5 comprehensive performance is best.
Therefore, the high-performance degradable recycled vanillin-based epoxy resin provided by the invention has strong reactivity, low curing temperature and initial curing temperature lower than 100 ℃; the heat resistance is good, and the glass transition temperature can reach 159 ℃; the electrical insulation performance and the mechanical performance are excellent, the dielectric loss factor is only 0.34, and the maximum tensile strength can reach 76MPa; degradation can be realized in 25h at 100 ℃; the degraded solution and the crushed epoxy resin can be recycled by hot pressing, and the recovery rate of the electrical breakdown strength can reach 98% at maximum; has surface self-repairing capability, and can be maintained at 180deg.C for 3 hr, and the scratch can disappear, preferably 60 min.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (9)
1. The high-performance degradable recycled epoxy resin is characterized by being prepared from the following raw materials:
para-aminophenol, vanillin, epichlorohydrin, bisphenol A epoxy resin, a curing agent, a catalyst, tetrabutylammonium bromide and sodium hydroxide solution.
2. A high performance degradable recycled epoxy resin according to claim 1, wherein: the catalyst is 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, the curing agent is 2-methyl hexahydrophthalic anhydride, the bisphenol A type epoxy resin is E-51 type bisphenol A epoxy resin, and the mass fraction of the sodium hydroxide solution is 20%.
3. A high performance degradable recycled vanillin based epoxy resin of claim 1, characterized in that: para-aminophenol: vanillin: the molar ratio of the epichlorohydrin is 1:1:10.
4. A process for the preparation of a high performance degradable recycled epoxy resin as claimed in any one of claims 1 to 3, characterized by the steps of:
s1, respectively dissolving vanillin and para-aminophenol in deionized water and absolute ethyl alcohol, pouring the mixture into a round-bottom flask with a condensing device for reaction under certain conditions, performing vacuum filtration, washing the mixture with absolute ethyl alcohol for three times after the completion of vacuum filtration, and drying to obtain a purified product yellow powder which is vanillin-based diphenol monomer; the reaction formula is:
s2, placing a round-bottom flask with a condensing reflux and magnetic stirring device in an oil bath, then adding the vanillin diphenol monomer and epoxy chloropropane obtained in the step S1 into the round-bottom flask, starting stirring, adding tetrabutylammonium bromide after each component is dissolved, and then heating the system to a certain temperature and keeping for a certain time;
s3, slowly dropwise adding 20% sodium hydroxide in parts by weight into a reaction system, cooling the reaction system, reacting for a certain time after the reaction system is cooled to a required temperature, vacuum-filtering the obtained product, diluting with petroleum ether, adding distilled water for washing, extracting for three times, removing excessive epichlorohydrin and petroleum ether by using a rotary evaporator, and vacuum-drying overnight to obtain a white solid which is a vanillin-based epoxy monomer, wherein the reaction formula is as follows:
s4, uniformly mixing the E-51 bisphenol A epoxy resin and the vanillin-based epoxy monomer obtained in the step S3 at 110 ℃, then adding a curing agent, uniformly mixing the components in a melting way, adding a catalyst, uniformly mixing again, then placing the mixture in a vacuum oven for degassing, and curing according to a step curing mode of 100 ℃/2h+130 ℃/5 h.
5. The method for preparing the high-performance degradable recycled epoxy resin, which is characterized in that: in the step S1, 1mol of vanillin is dissolved in 4L of deionized water, and 1mol of p-aminophenol is dissolved in 2L of absolute ethyl alcohol; reflux stirring for 2-3h at 50-60 ℃; drying in a vacuum drying oven at 50-65deg.C overnight.
6. The method for preparing the high-performance degradable recycled epoxy resin, which is characterized in that: the amount of tetrabutylammonium bromide added in the step S2 is 10% of the mass of the vanillin diphenol monomer; raising the temperature of the system to a certain temperature and keeping for a certain time, namely raising the temperature of the system to 80-90 ℃ and reacting for 1.5-3h; in the step S4, bisphenol a type epoxy resin: the molar ratio of the prepared vanillin epoxy resin is 1:1.
7. The method for preparing the high-performance degradable recycled epoxy resin, which is characterized in that: slowly dropwise adding 20% sodium hydroxide in part by mass in the step S3, namely finishing dropwise adding within 0.5h, wherein the amount of the 20% sodium hydroxide is 2 times of the mass of the vanillin diphenol monomer; cooling to the required temperature for reacting for a certain time, namely cooling to room temperature, and reacting for 3-5 hours; the addition amount of petroleum ether is 20 times of the mass of vanillin diphenol monomer; vacuum drying is carried out in a vacuum drying oven at 50-70 ℃ overnight.
8. A method of degrading a high performance degradable recycled epoxy resin according to any one of claims 1 to 3, wherein: by placing the epoxy resin in the degradation liquid, the epoxy resin: the mass ratio of the degradation liquid is 1:20, and the degradation liquid is n-hexylamine.
9. A method of recycling a high performance degradable recycled epoxy resin according to any one of claims 1 to 3, characterized in that: the chemical recovery method can be used, and also can be used by a physical recovery method, and the chemical recovery method comprises the following steps:
dissolving the prepared vanillin-based epoxy resin in degradation liquid, placing the system in a rotary evaporator, transferring the system into a mold when the solution is in a viscous state, heating in vacuum, continuously hot-pressing for 6 hours at 180 ℃ and 10MPa, naturally cooling, cooling to room temperature, and demolding to obtain the recovered vanillin-based epoxy resin;
the physical recovery method is as follows: crushing vanillin-based epoxy resin into particles with the diameter of 1-5mm by using a crusher, placing the particles into two steel plate molds coated with release oil, hot-pressing the steel plate molds for 4 hours at the temperature of 200 ℃ and the pressure of 20MPa on a plate vulcanizing machine, cooling the steel plate molds to room temperature for molding, and demolding to obtain recovered sample pieces.
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