CN114479176A - Method for curing epoxy resin and composite material thereof by DES (data encryption standard) degradation of amine - Google Patents
Method for curing epoxy resin and composite material thereof by DES (data encryption standard) degradation of amine Download PDFInfo
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- CN114479176A CN114479176A CN202210154023.2A CN202210154023A CN114479176A CN 114479176 A CN114479176 A CN 114479176A CN 202210154023 A CN202210154023 A CN 202210154023A CN 114479176 A CN114479176 A CN 114479176A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 63
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 63
- 150000001412 amines Chemical class 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000015556 catabolic process Effects 0.000 title claims abstract description 26
- 238000013478 data encryption standard Methods 0.000 title claims description 46
- 239000002904 solvent Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000011084 recovery Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims abstract description 5
- 235000019743 Choline chloride Nutrition 0.000 claims abstract description 5
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229960003178 choline chloride Drugs 0.000 claims abstract description 5
- 230000000593 degrading effect Effects 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000004917 carbon fiber Substances 0.000 claims description 17
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 13
- 239000003365 glass fiber Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 150000004714 phosphonium salts Chemical group 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 5
- 239000002798 polar solvent Substances 0.000 claims description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- NHJVRSWLHSJWIN-UHFFFAOYSA-N 2,4,6-trinitrobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O NHJVRSWLHSJWIN-UHFFFAOYSA-N 0.000 claims description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- MFIUDWFSVDFDDY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 MFIUDWFSVDFDDY-UHFFFAOYSA-M 0.000 claims description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 2
- NJXBVBPTDHBAID-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 NJXBVBPTDHBAID-UHFFFAOYSA-M 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 7
- 150000007524 organic acids Chemical class 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000005496 eutectics Effects 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- 238000002144 chemical decomposition reaction Methods 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000007857 degradation product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/28—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic compounds containing nitrogen, sulfur or phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/26—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing carboxylic acid groups, their anhydrides or esters
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- 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
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Abstract
The invention discloses a method for degrading amine cured epoxy resin and a composite material thereof through DES, and belongs to the technical field of solid waste degradation and recovery. The invention provides a simple and feasible method for solving the problems of low resource utilization rate, large energy consumption in pyrolysis, easy volatilization of solvent in chemical degradation, difficult recovery, harsh reaction conditions, poor product quality and the like in the prior art due to a physical crushing technology. According to the preparation method, organic acid and choline chloride are heated and mixed to prepare a eutectic solvent (DES), and then the amine cured epoxy resin or the composite material is in full contact with the DES in a reaction kettle to react; after the reaction is finished, filtering out undissolved components in the composite material, washing and drying, adding water into filtrate for precipitation, centrifuging and drying to obtain a product; DES dissolved in water can be recycled by evaporating the water. The invention has the advantages of simple solvent preparation, small loss, mild reaction conditions, good product quality, recyclable solvent system and the like.
Description
Technical Field
The invention belongs to the technical field of solid waste recovery, and particularly relates to a method for degrading an amine cured epoxy resin composite material.
Background
Amine-cured epoxy resins are a class of resins in which an amine curing agent is attached to an epoxy resin by a C-N bond. Compared with unsaturated polyester resin which is widely applied at present, the thermosetting resin has better physical property, electrical insulation property, chemical corrosion resistance, heat resistance and adhesion property, and is often applied to wind power blades, aerospace, transportation and other aspects. With the continuous improvement of the preparation process and the curing technology of the epoxy resin, the price of the epoxy resin is reduced year by year, the yield is continuously increased, and if the waste material of the epoxy resin cannot be treated in time, the environment is seriously influenced. Epoxy resin composites are most commonly of the carbon or glass fiber reinforced type, which have superior mechanical properties. At present, the composite material with the fiber mass fraction accounting for more than 70 percent is easier to prepare, so that the recycling of the fiber in the composite material is very important.
Conventional physical comminution and pyrolysis treatments of amine cured epoxy resins and composites thereof do not maximize the value of utilizing these wastes, and the high degree of crosslinking of the epoxy resins makes other processes difficult. The chemical recovery is to degrade the three-dimensional resin macromolecules into oligomers or micromolecules by a chemical means, and the method can protect the fibers from being damaged to the maximum extent under the condition of separating the high value-added fibers. Patent CN1974641 discloses a method for decomposing thermosetting epoxy resin and a composite material thereof, wherein tetrahydronaphthalene or decahydronaphthalene is used as a solvent, metal powder is used as a catalyst, and the thermosetting epoxy resin is decomposed at 280-350 ℃. However, this method is too high in reaction temperature, expensive in catalyst, and easy in oxidation of the solvent in air. Patent CN105153461A discloses a process for recovering epoxy resin composite material, which uses ethanol and p-toluic acid as solvent, and adds imidazolium salt or pyridinium salt ionic liquid to degrade epoxy resin composite material. However, the ionic liquid used in the method has complex preparation process and high price. Patent CN 110105619B discloses a controllable degradation recovery method of polyurethane, which utilizes choline chloride and ethylene glycol or tetramethylammonium chloride and oxalic acid to prepare DES, and catalyzes the urethane bond of polyurethane to break so as to degrade the polyurethane. However, the DES cannot break the chemical bonds of the amine-cured epoxy resin, and thus has no degradation effect on the amine-cured epoxy resin. In summary, the methods for degrading amine cured epoxy resin and the composite material thereof still have the problems of complex preparation of solvent or catalyst, high price, overhigh reaction temperature, poor product quality, difficult solvent recovery and the like.
Disclosure of Invention
Aiming at the problems in the degradation and recovery of the amine cured epoxy resin and the composite material thereof, the invention provides a method for degrading the amine cured epoxy resin composite material, which has the advantages of simple preparation of a solvent system and mild conditions. The DES solvent system can be prepared by simple heating and mixing, and the DES can be used as a solvent, a catalyst and a reactant in the reaction process without an additional catalyst; the reaction conditions are mild, so that the obtained fiber product is clean and has little damage; the DES system is simple to recycle.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for curing epoxy resin and composite material thereof by DES degradation of amine comprises the following steps: heating organic strong acid or a mixed solution of the organic strong acid and water and a hydrogen bond acceptor to form a clear and transparent DES, and placing amine cured epoxy resin or a composite material of the amine cured epoxy resin in the DES for heating and degradation reaction; and after degradation is finished, separating and recovering the product, removing other components in the DES through rotary evaporation, and recycling the solvent.
Further, the organic strong acid is one or a mixture of more of trifluoromethanesulfonic acid, trifluoroacetic acid, trichloroacetic acid, mellitic acid, trinitrobenzenesulfonic acid, nitrothiofanic acid, methanesulfonic acid, p-toluenesulfonic acid and dodecylbenzenesulfonic acid in any proportion. The organic strong acid belongs to strong Lewis acid, has strong proton donating capability and can interact with N in epoxy resin, thereby breaking C-N bonds.
Further, the hydrogen bond acceptor is any one of quaternary ammonium salt and quaternary phosphonium salt or a mixture of two of the quaternary ammonium salt and the quaternary phosphonium salt in any proportion. The hydrogen bond acceptor is selected to be capable of forming stable DES with organic strong acid reagent easily.
Further, the quaternary ammonium salt substance comprises one or a mixture of several of choline chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium chloride and tetraethylammonium chloride; the quaternary phosphonium salt substance comprises one or a mixture of more than one of methyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium chloride, butyl triphenyl phosphonium chloride and tetrabutyl phosphonium bromide in any proportion. The hydrogen bond acceptor can form clear and transparent DES with strong organic acid or the mixture of the strong organic acid and water at a lower temperature and in a shorter time.
Further, the mass ratio of the organic strong acid to water is 1: 0.01-0.1. If the water content is too high, the acidity of the system becomes weak, which affects selective bond breaking of the resin by the strong organic acid.
Further, the composite material of the amine cured epoxy resin is any one of carbon fiber reinforced amine cured epoxy resin or glass fiber reinforced amine cured epoxy resin or a mixture of two of the carbon fiber reinforced amine cured epoxy resin and the glass fiber reinforced amine cured epoxy resin in any proportion. Fiber-reinforced epoxy resin composites are the most common, and the fibers have high recycling value.
Further, the mass ratio of the amine cured epoxy resin or the composite material of the amine cured epoxy resin to the DES is 1: 5-25; the temperature of the degradation reaction is 160-240 ℃, and the time is 1-24 h. The degradation reaction is carried out at the proportion, the temperature and the time, the degradation effect is good, and the surface damage to the fiber product is small. If the temperature or time is too low, the degradation effect is affected, and if the temperature is too high, the fiber surface is damaged and the resin degradation product is carbonized.
Further, the separation and recovery method comprises the steps of separating insoluble substances from DES, washing and drying to obtain a clean fiber product; the product dissolved in DES is obtained by adding the third component to precipitate, centrifuging, and drying. The fiber product recovered by the method has high quality; the DES is easy to recover and recycle.
Further, the third component is any one of water or a weakly polar solvent. The resin degradation products can be separated from DES better and more conveniently by selecting water or a weakly polar solvent, and then purified.
Further, the weak polar solvent is any one of petroleum ether and dichloromethane or a mixture of two of petroleum ether and dichloromethane in any proportion. Petroleum ether and dichloromethane have small polarity and low boiling point, and when the DES is recovered, the third component dissolved in the DES is better removed.
Compared with the prior art, the invention has the following advantages:
(1) the DES preparation process is simple, and clear and transparent DES can be obtained only by mixing and heating.
(2) No extra catalyst is needed in the degradation process, and the DES is used as a solvent, a catalyst and a reactant in the process.
(3) The reaction conditions are mild.
(4) The recycled carbon fiber or glass fiber product has excellent quality and has little difference with the tensile strength of the precursor.
(5) After the system is degraded and separated, the DES can be reused only by simple rotary evaporation.
Drawings
FIG. 1 is a diagram of a carbon fiber/glass fiber reinforced amine cured epoxy resin feedstock;
FIG. 2 is a diagram of a recycled fiber after degradation of a carbon/glass fiber reinforced amine cured epoxy resin;
FIG. 3 is an electron micrograph of recycled glass fibers after degradation of the glass fiber reinforced amine cured epoxy;
FIG. 4 resin degradation products after degradation of carbon fiber reinforced amine cured epoxy resin1H NMR chart.
Detailed Description
Example 1
2.5g of trifluoromethanesulfonic acid are mixed with 2.5g of choline chloride in an oil bath at 80 ℃ with stirring until a clear and transparent solution is formed. 1g of carbon fiber reinforced epoxy resin was added to the DES prepared above and reacted at 160 ℃ for 20 hours. And after the reaction is finished, cooling the system to room temperature, separating the fibers from the DES, washing with ethanol, and drying to obtain a clean carbon fiber product. The resin degradation rate was found to be 90% by calculation, and the tensile strength of the carbon fiber was found to be 2.812GPa (a decrease of 3.0% from the strength of the original carbon fiber). And adding a third group of water into the degradation product dissolved in the DES for precipitation, and centrifuging, washing and drying to obtain the epoxy resin degradation product. The DES can be recycled by rotary evaporation.
The following examples are the same as the procedure of example 1, and the different materials or conditions involved are given in the form of tabular data.
The carbon fiber reinforced epoxy resin raw material in example 4 and the glass fiber reinforced epoxy resin raw material in example 8 are shown in fig. 1; the recycled carbon fibers of example 4 and the recycled glass fibers of example 8 are shown in FIG. 2; an electron micrograph of the recycled glass fiber of example 8 is shown in FIG. 3; the degradation products of the epoxy resin of example 4 were analyzed by nmr and the results are shown in fig. 4.
In conclusion, it can be seen from example 10 that when the non-organic strong acid is selected as the eutectic solvent component, no degradation effect is generated on the carbon fiber reinforced epoxy resin; from example 11, it can be seen that when the temperature is 140 ℃ (out of the range of 160-240 ℃), there is no degradation effect on the carbon fiber reinforced epoxy resin.
Those skilled in the art will appreciate that the invention may be practiced without these specific details. Although the illustrative embodiments of the present invention have been described in order to facilitate those skilled in the art to understand the present invention, it is to be understood that the present invention is not limited to the scope of the embodiments, and that various changes may be made apparent to those skilled in the art as long as they are within the spirit and scope of the present invention as defined and defined in the appended claims, and all changes that can be made by the inventive concept are protected.
Claims (10)
1. A method for degrading amine curing epoxy resin and composite material thereof by DES is characterized in that: the method comprises the following steps: heating organic strong acid or a mixed solution of the organic strong acid and water and a hydrogen bond acceptor to form a clear and transparent DES, and placing amine cured epoxy resin or a composite material of the amine cured epoxy resin in the DES for heating and degradation reaction; and after degradation is finished, separating and recovering the product, removing other components in the DES through rotary evaporation, and recycling the solvent.
2. The method for curing epoxy resin and composite material thereof by DES degradation of amine according to claim 1, wherein: the organic strong acid is one or a mixture of more than one of trifluoromethane sulfonic acid, trifluoroacetic acid, trichloroacetic acid, mellitic acid, trinitrobenzene sulfonic acid, nitrothiosquaric acid, methane sulfonic acid, p-toluenesulfonic acid and dodecyl benzene sulfonic acid in any proportion.
3. The method for curing epoxy resin and composite material thereof by DES degradation of amine according to claim 1, wherein: the hydrogen bond acceptor is any one of quaternary ammonium salt and quaternary phosphonium salt or a mixture of two of the quaternary ammonium salt and the quaternary phosphonium salt in any proportion.
4. The method for curing epoxy resin and composite material thereof by DES degradation of amine according to claim 3, wherein: the quaternary ammonium salt substance comprises one or a mixture of choline chloride, tetramethyl ammonium bromide, tetraethyl ammonium bromide, tetrabutyl ammonium bromide, tetramethyl ammonium chloride and tetraethyl ammonium chloride; the quaternary phosphonium salt substance comprises one or a mixture of more than one of methyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium chloride, butyl triphenyl phosphonium chloride and tetrabutyl phosphonium bromide in any proportion.
5. The method for curing epoxy resin and composite material thereof by DES degradation of amine according to claim 1, wherein: the mass ratio of the organic strong acid to the water is 1: 0.01-0.1.
6. The method for curing epoxy resin and composite material thereof by DES degradation of amine according to claim 1, wherein: the composite material of the amine cured epoxy resin is any one of carbon fiber reinforced amine cured epoxy resin or glass fiber reinforced amine cured epoxy resin or a mixture of two of the carbon fiber reinforced amine cured epoxy resin and the glass fiber reinforced amine cured epoxy resin in any proportion.
7. The method for curing epoxy resin and composite material thereof by DES degradation of amine according to claim 1, wherein: the mass ratio of the amine cured epoxy resin or the composite material of the amine cured epoxy resin to the DES is 1: 5-25; the temperature of the degradation reaction is 160-240 ℃, and the time is 1-24 h.
8. The method for curing epoxy resin and composite material thereof by DES degradation of amine according to claim 1, wherein: the separation and recovery method comprises the steps of separating insoluble substances from DES, washing and drying to obtain a clean fiber product; the product dissolved in DES is obtained by adding the third component to precipitate, centrifuging, and drying.
9. The method for curing epoxy resin and composite material thereof by DES degradation of amine according to claim 8, wherein: the third component is any one of water or a weak polar solvent.
10. The method for curing epoxy resin and its composite material by DES degradation of amine according to claim 9, wherein: the weak polar solvent is any one of petroleum ether and dichloromethane or a mixture of two of petroleum ether and dichloromethane in any proportion.
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