CN114479176B - Method for degrading amine-cured epoxy resin and composite material thereof through DES - Google Patents
Method for degrading amine-cured epoxy resin and composite material thereof through DES Download PDFInfo
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- CN114479176B CN114479176B CN202210154023.2A CN202210154023A CN114479176B CN 114479176 B CN114479176 B CN 114479176B CN 202210154023 A CN202210154023 A CN 202210154023A CN 114479176 B CN114479176 B CN 114479176B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 54
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000000593 degrading effect Effects 0.000 title abstract description 6
- 238000006731 degradation reaction Methods 0.000 claims abstract description 31
- 150000001412 amines Chemical class 0.000 claims abstract description 28
- 230000015556 catabolic process Effects 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 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
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000835 fiber Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 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 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- RTFFRZWAOUGYSN-UHFFFAOYSA-N CCCCC(C=CC=C1)=C1P(C1=CC=CC=C1)C1=CC=CC=C1.Cl Chemical compound CCCCC(C=CC=C1)=C1P(C1=CC=CC=C1)C1=CC=CC=C1.Cl RTFFRZWAOUGYSN-UHFFFAOYSA-N 0.000 claims description 2
- DASNDJBQHOUCAV-UHFFFAOYSA-N CCCCP(CCCC)(CCCC)CCCC.Br Chemical compound CCCCP(CCCC)(CCCC)CCCC.Br DASNDJBQHOUCAV-UHFFFAOYSA-N 0.000 claims description 2
- GBYIPEFQQCCCJP-UHFFFAOYSA-N Cl.C(C)C1=C(C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound Cl.C(C)C1=C(C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 GBYIPEFQQCCCJP-UHFFFAOYSA-N 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
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 2
- 150000004714 phosphonium salts Chemical group 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
- 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
- 238000013478 data encryption standard Methods 0.000 claims 14
- 238000004064 recycling Methods 0.000 claims 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000011084 recovery Methods 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000005496 eutectics Effects 0.000 abstract description 2
- 150000007524 organic acids Chemical class 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
- 238000001556 precipitation Methods 0.000 abstract 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 12
- 239000004917 carbon fiber Substances 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 239000003365 glass fiber Substances 0.000 description 8
- 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
- 239000004593 Epoxy Substances 0.000 description 4
- 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
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 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 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
- 239000000376 reactant Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 1
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- NAPFUZINWJWGRQ-UHFFFAOYSA-N C(C)(=O)O.CF Chemical compound C(C)(=O)O.CF NAPFUZINWJWGRQ-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- BLALBRWEAJQIIL-UHFFFAOYSA-N [Cl].CC(O)=O Chemical compound [Cl].CC(O)=O BLALBRWEAJQIIL-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction 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
- 238000010586 diagram Methods 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 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
- 239000002184 metal Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 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
- 238000000746 purification Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 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
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 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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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a method for curing epoxy resin and a composite material thereof by degrading amine through DES, belonging to the technical field of degradation and recovery of solid wastes. The invention provides a simple and feasible method aiming at the problems of low resource utilization rate, high energy consumption by pyrolysis, easy volatilization of solvent in chemical degradation, difficult recovery, harsh reaction conditions, poor product quality and the like caused by the physical crushing technology in the prior art. The invention prepares the eutectic solvent (DES) by heating and mixing organic acid and choline chloride, and then fully contacts and reacts amine cured epoxy resin or composite material with the DES in a reaction kettle; filtering out undissolved components in the composite material after the reaction is finished, washing and drying, adding water into the filtrate for precipitation, centrifuging and drying to obtain a product; the DES dissolved in water can be recycled by evaporating the water. The invention has the advantages of simple solvent preparation, small loss, mild reaction condition, excellent 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 the epoxy resin by a C-N bond. Compared with the unsaturated polyester resin which is widely used at present, the thermosetting resin has better physical properties, electrical insulation properties, chemical corrosion resistance, heat resistance and adhesion properties, and is commonly applied to aspects of wind power blades, aerospace, transportation and the like. 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 affected. Epoxy resin composites are most commonly found in carbon fiber or glass fiber reinforced classes, which have more excellent mechanical properties. At present, the composite material with the fiber mass fraction of more than 70% is easy to prepare, so that the recovery of the fibers in the composite material is important.
Conventional physical comminution and pyrolysis treatments of amine cured epoxy resins and their composites do not maximize the value of utilizing such waste materials, and the high degree of crosslinking of the epoxy resins can make other processes difficult. The chemical recovery is to degrade the three-dimensional resin macromolecules into oligomers or small molecules by chemical means, and the method can furthest protect the fibers from damage under the condition of separating the fibers with high added value. Patent CN1974641 discloses a method for decomposing thermosetting epoxy resin and its composite material, which takes tetrahydronaphthalene or decalin as solvent and metal powder as catalyst, and degrades the thermosetting epoxy resin 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 recovery process of epoxy resin composite material, which takes ethanol and p-toluic acid as solvents, and adds imidazolium salt or pyridinium ionic liquid to degrade the epoxy resin composite material. However, the ionic liquid used in the method has a complex preparation process and high price. Patent CN 110105619B discloses a method for recovering polyurethane by controllable degradation, which uses choline chloride and ethylene glycol or tetramethyl ammonium chloride and oxalic acid to prepare DES, and catalyzes the cleavage of urethane bond of polyurethane so as to degrade polyurethane. However, the DES cannot break the chemical bond of the amine-cured epoxy resin, so that the DES has no degradation effect on the amine-cured epoxy resin. In summary, the problems of complex preparation of solvent or catalyst, high price, high reaction temperature, poor product quality, difficult recovery of solvent and the like still exist in the method for degrading the amine-cured epoxy resin and the composite material thereof.
Disclosure of Invention
Aiming at the problems in degradation and recovery of amine cured epoxy resin and a composite material thereof, the invention provides a method for degrading the amine cured epoxy resin composite material, which has simple preparation of a solvent system and mild conditions. The method can prepare the DES solvent system by simple heating and mixing, and the DES is used as a solvent, a catalyst and reactants in the reaction process without an additional catalyst; the reaction condition is 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 above purpose, the present invention adopts the following technical scheme:
a method of curing epoxy resins and their composites by DES degradation, comprising the steps of: heating organic strong acid or a mixed solution of the organic strong acid and water and a hydrogen bond acceptor to form clear and transparent DES, and heating the amine cured epoxy resin or the composite material of the amine cured epoxy resin in the DES for degradation reaction; after the degradation is finished, the product is separated and recovered, other components in DES are removed by rotary evaporation, and the solvent is recycled.
Further, the organic strong acid is any one or a mixture of a plurality of the three methyl fluoride sulfonic acid, the three methyl fluoride acetic acid, the three chlorine acetic acid, the mellitic acid, the three nitrobenzene sulfonic acid, the nitrogen sulfur squaric acid, the methane sulfonic acid, the p-toluene sulfonic acid and the dodecyl benzene sulfonic acid in any proportion. The organic strong acid belongs to strong Lewis acid, has strong proton donating ability, and can interact with N in the epoxy resin, so that C-N bond is broken.
Further, the hydrogen bond acceptor is any one or a mixture of two of quaternary ammonium salt and quaternary phosphonium salt in any proportion. The hydrogen bond acceptor is selected to form stable DES with organic strong acid reagent.
Further, the quaternary ammonium salt substance comprises one or a mixture of a plurality of choline chloride, tetramethyl ammonium bromide, tetraethyl ammonium bromide, tetrabutyl ammonium bromide, tetramethyl ammonium chloride and tetraethyl ammonium chloride; the quaternary phosphine salt substance comprises one or a mixture of a plurality of methyl triphenylphosphine bromide, ethyl triphenylphosphine chloride, butyl triphenylphosphine chloride and tetrabutylphosphine bromide in any proportion. The hydrogen bond acceptor property can be stabilized at a lower temperature in a shorter time to form clear and transparent DES with organic strong acid or a mixture of organic strong acid and water.
Further, the mass ratio of the organic strong acid to the water is 1:0.01-0.1. If the water content is too high, the acidity of the system becomes weak, and the selective bond cleavage of the resin by the strong organic acid is affected.
Further, the composite material of the amine-cured epoxy resin is any one or a mixture of two of carbon fiber-reinforced amine-cured epoxy resin and glass fiber-reinforced amine-cured epoxy resin in any proportion. Fiber reinforced epoxy resin composites are the most common and the fibers have high recovery 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 degradation reaction temperature 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 damage to the surface of 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, not only the fiber surface is damaged but also the resin degradation product is carbonized.
Further, the separation and recovery method is that insoluble substances are separated from DES, washed and dried to obtain a clean fiber product; the product dissolved in DES is precipitated by adding a third component, centrifuged and dried. The quality of the fiber product recovered by the method is high; DES is easily recovered and recycled.
Further, the third component is any one of water or a weak polar solvent. The choice of water or a less polar solvent allows better, more convenient separation of the resin degradation products from DES and purification.
Further, the weak polar solvent is any one or a mixture of two of petroleum ether and dichloromethane in any proportion. Petroleum ether and methylene dichloride have low polarity and low boiling point, and when 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 preparation process of the DES 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 little difference from the tensile strength of the precursor.
(5) After the degradation and separation of the system are finished, the DES can be reused only by simple rotary evaporation.
Drawings
FIG. 1 is a carbon fiber/glass fiber reinforced amine cured epoxy feedstock diagram;
FIG. 2 is a graph of recycled fibers after degradation of carbon fiber/glass fiber reinforced amine cured epoxy;
FIG. 3 is an electron micrograph of a recycled glass fiber after degradation of a glass fiber reinforced amine cured epoxy;
FIG. 4 resin degradation products after degradation of carbon fiber reinforced amine cured epoxy resin 1 H NMR chart.
Detailed Description
Example 1
2.5g of trifluoromethanesulfonic acid was mixed with 2.5g of choline chloride in an oil bath at 80℃and stirred until a clear and transparent solution formed. 1g of carbon fiber reinforced epoxy resin was added to the DES prepared above and reacted at 160℃for 20 hours. After the reaction is finished, the system is cooled to room temperature, the fiber is separated from DES, and is washed by ethanol, and a clean carbon fiber product is obtained after drying. The resin degradation rate was 90% by calculation, and the tensile strength of the carbon fiber was 2.812GPa (3.0% lower than the strength of the carbon fiber). The degradation products dissolved in DES are precipitated by adding water as a third component, and after centrifugation, washing, and drying, the epoxy degradation products can be obtained. DES is reusable by rotary evaporation.
The following examples are identical to the procedure of example 1, and the different raw materials or conditions involved are presented in tabular data format.
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 fiber in example 4 and the recycled glass fiber in example 8 are shown in fig. 2; an electron micrograph of the recycled glass fiber in example 8 is shown in FIG. 3; the results of the analysis of the epoxy resin degradation product of example 4 by nuclear magnetic resonance are shown in FIG. 4.
In summary, it can be seen from example 10 that when a non-organic strong acid is selected as the eutectic solvent component, there is no degradation effect on the carbon fiber reinforced epoxy resin; it can be seen from example 11 that there is no degradation effect on the carbon fiber reinforced epoxy resin when the temperature is 140 ℃ (beyond the range of 160-240 ℃).
What is not described in detail in the present specification belongs to the prior art known to those skilled in the art. While the foregoing describes illustrative embodiments of the present invention to facilitate an understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, but is to be construed as protected by the accompanying claims insofar as various changes are within the spirit and scope of the present invention as defined and defined by the appended claims.
Claims (8)
1. A method of curing epoxy resins and their composites by DES degradation of the amine, characterized by: 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 clear and transparent DES, and heating the amine cured epoxy resin or the composite material of the amine cured epoxy resin in the DES for degradation reaction; after degradation is completed, separating and recycling the product, removing other components in DES by rotary evaporation, and recycling the solvent;
the hydrogen bond acceptor is any one or a mixture of two of quaternary ammonium salt and quaternary phosphonium salt in any proportion;
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 degradation reaction temperature is 160-240 ℃ and the degradation reaction time is 1-24 h.
2. A method of curing epoxy resins and their composites by DES degradation amine according to claim 1, characterized in that: the organic strong acid is any one or a mixture of a plurality of the three types of the mixture with any proportion among the three types of the mixture of the three types of the mixture.
3. A method of curing epoxy resins and their composites by DES degradation amine according to claim 1, characterized in that: the quaternary ammonium salt substance comprises one or a mixture of a plurality of choline chloride, tetramethyl ammonium bromide, tetraethyl ammonium bromide, tetrabutyl ammonium bromide, tetramethyl ammonium chloride and tetraethyl ammonium chloride; the quaternary phosphine salt substance comprises one or a mixture of a plurality of methyl triphenylphosphine bromide, ethyl triphenylphosphine chloride, butyl triphenylphosphine chloride and tetrabutylphosphine bromide in any proportion.
4. A method of curing epoxy resins and their composites by DES degradation amine according to claim 1, characterized in that: the mass ratio of the organic strong acid to the water is 1:0.01-0.1.
5. A method of curing epoxy resins and their composites by DES degradation amine according to claim 1, characterized in that: the composite material of the amine-cured epoxy resin is any one or a mixture of two of carbon fiber-reinforced amine-cured epoxy resin and glass fiber-reinforced amine-cured epoxy resin in any proportion.
6. A method of curing epoxy resins and their composites by DES degradation amine according to claim 1, characterized in that: separating insoluble substances from DES, washing and drying to obtain a clean fiber product; the product dissolved in DES is precipitated by adding a third component, centrifuged and dried.
7. A method of curing epoxy resins and their composites by DES degradation amine as claimed in claim 6, wherein: the third component is any one of water or a weak polar solvent.
8. A method of curing epoxy resins and their composites by DES degradation amine as claimed in claim 7, wherein: the weak polar solvent is one or a mixture of petroleum ether and methylene dichloride in any proportion.
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| JP2019104861A (en) * | 2017-12-14 | 2019-06-27 | 埼玉県 | Recycle method of fiber-reinforced resin composite material and system of the same |
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