CN103232615B - A kind of method of epoxy resin carbon fiber matrix material of degrading - Google Patents
A kind of method of epoxy resin carbon fiber matrix material of degrading Download PDFInfo
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Abstract
The method of epoxy resin carbon fiber matrix material of degrading be with water, methyl alcohol, ethanol or propyl alcohol for a solvent, add metal-salt, be mixed with reaction soln; Epoxy resin carbon fiber matrix material is immersed in reaction soln, carries out degraded 1-20 hour at 160-240 DEG C; Separation and Recovery metal salt, and obtain epoxy resin degraded product and carbon fiber.It is simple that the present invention has technique, mild condition, low cost and the advantage to the low damage of carbon fiber strength.
Description
Technical field
The present invention relates to a kind of method of epoxy resin carbon fiber matrix material of degrading.
Technical background
Carbon fiber/epoxy resin composite material due to its physico-chemical property stablize, light weight, the excellent performance such as high-strength, be widely used in the numerous areas such as aerospace, electron electric power, communications and transportation, its demand rises fast, Global Carbon fiber year the growth rate of demand more than 12%, the demand of Global Carbon fiber in 2008 is about 35000 tons, and estimates to reach 70000 tons to the demand of Global Carbon fiber in 2014.But along with the continuous production of carbon fiber/epoxy resin composite material and application, waste and scrap is also increasing, brings heavy environmental stress.Carbon fiber/epoxy resin composite material is degraded under relatively mild conditions, reclaims carbon fiber and ensure the loss that its intensity is little as far as possible, not only can alleviate environmental stress, reduce industry and pollute, and can product cost be reduced, there is important economic implications.
The method of current process thermoset ting resin composite mainly contains physical pulverization method, thermochemistry edman degradation Edman and chemical degradation method.Physical pulverization method recycles by the filler as other materials after the pulverizing of thermosetting epoxy resin mechanical force, and the energy needed for this method is very high, and the added value of product obtained is than low, and the carbon fiber in product is not effectively reclaimed and utilizes.Thermochemistry edman degradation Edman under the action of heat thermosetting epoxy resin is degraded to various small-molecule substance, by a kind of method that the carbon fiber of materialization inertia is recycled, but the energy needed for the method is very high, and the destruction of pyroprocess to materials chemistry key does not have selectivity, the small molecules product generated is complicated, and environmental pollution is serious.Chemical degradation method is in certain solvent system, the partial chemical key of resin in matrix material is selectively ruptured under the effect of catalyzer, the product types that reaction process generates is controlled, convenient recycling, energy consumption is lower, and the damage of carbon fiber is less, it is a kind of novel method recycling thermosetting resin/matrix material.Patent of invention " a kind of method reclaiming carbon-fibre reinforced epoxy resin composite material " (CN102181071A) passes through supercritical CO
2organic solvent mixed system utilizes strong acid degradative resin matrix material, and 100 ~ 250 DEG C, reaction 1 ~ 24 hour under 7.5 ~ 25.0MPa, the techniques such as then washing is dry obtain carbon fiber, patent of invention " recovery method of thermosetting epoxy resin or its matrix material " (CN201110346114.8) is at ionic liquid and heating degraded epoxy resin, patent of invention " a kind of chemical recovery method of thermoset epoxy matrix material " (CN03132542.4) utilizes aqueous nitric acid as catalyzed degradation system, realizes the degraded of epoxy resin carbon fiber matrix material, patent of invention " a kind of method of catalytically decomposing carbon fiber-reinforced thermosetting epoxy resin composite material " (CN201010274001.7) SO42-/MxOy type solid super-strong acid is catalyzer, hydrogen peroxide is that oxygenant and carbon fiber-reinforced thermosetting epoxy resin composite material react, thermosetting epoxy resin oxygenolysis is made to be dissolved in organic solvent after the homologue of benzene or phenol, then cool, solid-liquid separation, by the solids wash obtained, carbon fiber and SO42-/MxOy type solid super-strong acid is isolated after drying, the thermosetting epoxy resin resistates after decomposing is obtained after being distilled by the liquid pressure-reducing obtained, patent of invention " reclaims the method for carbon-fibre reinforced epoxy resin composite material ", and pretreated carbon-fibre composite is added organic solvent and oxygenant by (CN201110257706.2), and carbon fiber is reclaimed in heatable catalytic oxidative degradation.Aforesaid method or condition harshness, temperature, pressure is very high, affects the industrialization of Technology; Use oxidizing species, the method of thermosetting resin by oxidative degradation is decomposed, resin monomer after this not only causes oxidative degradation can not reuse the synthesis with resin material, and strong oxidizing substance can corrode the defect point of carbon fiber surface and destroy, and affects the intensity of carbon fiber; Use a large amount of ionic liquid, and the chemical substance of this costliness of ionic liquid can cause larger cost pressure, limit its use in industrialization.
Summary of the invention
The object of this invention is to provide a kind of technique simple, mild condition, the method for low cost and the degraded epoxy resin carbon fiber matrix material to the low damage of carbon fiber strength.
Be rich in N in thermosetting epoxy resin material, the heteroatomss such as O, monomer small molecules is joined together to form the macromole of tridimensional network by these heteroatomss with the form of C-O or C-N key.The key of selective catalysis degraded opens some or all of for C-O or the C-N key of material internal, and this just requires that selected catalytic active center has the stronger ability be combined with O or N.The L acid of divalence or trivalent has stronger complex ability, so we select metal-salt as catalytic active center, C-O or the C-N key in activated resin material, makes it optionally disconnect, thus reclaims carbon fiber and small molecules resin fragment.The present invention is in water, methyl alcohol, ethanol or propyl alcohol, is catalytic center, realizes the degraded of epoxy resin carbon fiber matrix material with metal ion.
The concrete operation step of the inventive method is as follows:
(1) with water, methyl alcohol, ethanol or propyl alcohol for solvent, add metal-salt, be mixed with reaction soln;
(2) epoxy resin carbon fiber matrix material is immersed in reaction soln, carries out degraded 1-20 hour at 160-240 DEG C;
(3) Separation and Recovery metal salt, and obtain epoxy resin degraded product and carbon fiber.
Reaction soln described in step (1) refers to that concentration is the salts solution of 8-80wt%;
Metal-salt described in step (1) is positively charged ion is Al
3+, Zn
2+, Cu
2+, Ni
3+, Co
2+, Fe
3+, Cr, Mn
2+deng, negatively charged ion is the salt of halide-ions, sulfate ion composition.
The quality of the epoxy resin carbon fiber matrix material described in step (2) and the volume ratio of reaction soln are 1-20g:100ml.
Separation and Recovery described in step (3) refer to filter or centrifugal, carbon fiber is separated from reaction system, washing and recycling; The molecular thick liquid of resin chips after reaction solution frozen cooling to 0 DEG C is degraded to-10 DEG C of removings; Remaining reaction solution can continue to recycle.
The inventive method has efficiently, the advantage of green, economic dispatch, epoxy resin composite material can be can't harm after degrading, the clean fiber (fiber that recovery obtains, fibre strength is more than 90% of pristine fibre, and surperficial noresidue, can with epoxy resin compound again), and degradation temperature is no more than 240 DEG C, degraded product is easily separated.Epoxy resin after degraded, conjugated fibre and catalyst system are all recyclable, realize the recycle of resource, thus largely solve discarded thermosetting epoxy resin and matrix material thereof to the pollution problem of environment.Process easily controls, and by product is few, and therefore the inventive method very easily realizes industrialization running.
Embodiment
Embodiment 1:
The preparation of epoxy resin carbon fiber matrix material: first epoxy resin AG-80/DDS solidifying agent/acetone is uniformly mixed into Matrix Solution with weight ratio 200:66.6:300; By the T300 carbon fiber of 3.45GPa through steeping vat, flood this solution 10s, make and be unidirectionally placed on 12h under room temperature without latitude cloth, the acetone in glue is vapored away completely.Carry out cutting without latitude cloth by the length and width size of 60 × 40mm, and by cut out without the unidirectional folded 8-12 layer of latitude cloth, make multiple material thickness of slab remain on 2mm, then sample put into mould, and mould is put into autoclave; Carry out Procuring at about 147 DEG C, time 25min(also slowly passes into air pressurized to 7MPa at about 90 DEG C); Carry out after fixing at 196 DEG C, time 2h, still internal pressure 6-8Mpa, obtain epoxy resin carbon fiber matrix material.
The degraded of epoxy resin carbon fiber matrix material: the solder(ing)acid being 70% by 100 milliliters of massfractions adds in reactor, restrains 1 the epoxy resin carbon fiber compound resin got ready and puts into still, sealed reactor, 210 DEG C of reaction 1h.By strongtheners such as carbon fibers from reaction system centrifugation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 3.22GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after 0 DEG C of cooling, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.
Embodiment 2:
The preparation of epoxy resin carbon fiber matrix material: first epoxy resin AG-80/DDS solidifying agent/acetone is uniformly mixed into Matrix Solution with weight ratio 200:66.6:300; By the T700 carbon fiber of 7.34GPa through steeping vat, flood this solution 10s, make and be unidirectionally placed on 12h under room temperature without latitude cloth, the acetone in glue is vapored away completely.Carry out cutting without latitude cloth by the length and width size of 60 × 40mm, and by cut out without the unidirectional folded 8-12 layer of latitude cloth, make multiple material thickness of slab remain on 2mm, then sample put into mould, and mould is put into autoclave; Carry out Procuring at about 147 DEG C, time 25min(also slowly passes into air pressurized to 7MPa at about 90 DEG C); Carry out after fixing at 196 DEG C, time 2h, still internal pressure 6-8Mpa, obtain epoxy resin carbon fiber matrix material.
The degraded of epoxy resin carbon fiber matrix material: the aluminum chloride methanol solution being 20% by 100 milliliters of massfractions adds in reactor, restrains 1 the epoxy resin carbon fiber matrix material got ready and puts into still, sealed reactor, 220 DEG C of reaction 10h.By strongtheners such as carbon fibers from reaction system centrifugation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 7.16GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after-5 DEG C of coolings, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.
Embodiment 3:
The preparation of epoxy resin carbon fiber matrix material: first epoxy resin AG-80/DDS solidifying agent/acetone is uniformly mixed into Matrix Solution with weight ratio 200:66.6:300; By the T800 carbon fiber of 8.26GPa through steeping vat, flood this solution 10s, make and be unidirectionally placed on 12h under room temperature without latitude cloth, the acetone in glue is vapored away completely.Carry out cutting without latitude cloth by the length and width size of 60 × 40mm, and by cut out without the unidirectional folded 8-12 layer of latitude cloth, make multiple material thickness of slab remain on 2mm, then sample put into mould, and mould is put into autoclave; Carry out Procuring at about 147 DEG C, time 25min(also slowly passes into air pressurized to 7MPa at about 90 DEG C); Carry out after fixing at 196 DEG C, time 2h, still internal pressure 6-8Mpa, obtain epoxy resin carbon fiber matrix material.
The degraded of epoxy resin carbon fiber matrix material: the solder(ing)acid being 40% by 100 milliliters of massfractions adds in reactor, restrains 1 the epoxy resin carbon fiber matrix material got ready and puts into still, sealed reactor, 210 DEG C of reaction 10h.By strongtheners such as carbon fibers from reaction system centrifugation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 8.01GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after 0 DEG C of cooling, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.
Embodiment 4:
The preparation of epoxy resin carbon fiber matrix material: first epoxy resin AG-80/DDS solidifying agent/acetone is uniformly mixed into Matrix Solution with weight ratio 200:66.6:300; By the T300 carbon fiber of 3.45GPa through steeping vat, flood this solution 10s, make and be unidirectionally placed on 12h under room temperature without latitude cloth, the acetone in glue is vapored away completely.Carry out cutting without latitude cloth by the length and width size of 60 × 40mm, and by cut out without the unidirectional folded 8-12 layer of latitude cloth, make multiple material thickness of slab remain on 2mm, then sample put into mould, and mould is put into autoclave; Carry out Procuring at about 147 DEG C, time 25min(also slowly passes into air pressurized to 7MPa at about 90 DEG C); Carry out after fixing at 196 DEG C, time 2h, still internal pressure 6-8Mpa, obtain epoxy resin carbon fiber matrix material.
The degraded of epoxy resin carbon fiber matrix material: the solder(ing)acid being 70% by 100 milliliters of massfractions adds in reactor, restrains 2 the epoxy resin carbon fiber matrix material got ready and puts into still, sealed reactor, 160 DEG C of reaction 10h.By strongtheners such as carbon fibers from reaction system filtering separation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 3.16GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after 0 DEG C of cooling, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.
Embodiment 5:
The preparation of epoxy resin carbon fiber matrix material: first epoxy resin TGDDM/DDS solidifying agent/acetone is uniformly mixed into Matrix Solution with weight ratio 200:100:300; By the T300 carbon fiber of 3.45GPa through steeping vat, flood this solution 10s, make and be unidirectionally placed on 12h under room temperature without latitude cloth, the acetone in glue is vapored away completely.Carry out cutting without latitude cloth by the length and width size of 60 × 40mm, and by cut out without the unidirectional folded 8-12 layer of latitude cloth, make multiple material thickness of slab remain on 2mm, then sample put into mould, and mould is put into autoclave; Carry out Procuring at about 147 DEG C, time 25min(also slowly passes into air pressurized to 7MPa at about 90 DEG C); Carry out after fixing at 196 DEG C, time 2h, still internal pressure 6-8Mpa, obtain epoxy resin carbon fiber matrix material.
The degraded of epoxy resin carbon fiber matrix material: the solder(ing)acid being 60% by 100 milliliters of massfractions adds in reactor, restrains 5 the epoxy resin carbon fiber matrix material got ready and puts into still, sealed reactor, 210 DEG C of reaction 5h.By strongtheners such as carbon fibers from reaction system centrifugation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 3.36GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after 0 DEG C of cooling, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.
Embodiment 6:
The preparation of epoxy resin carbon fiber matrix material: first epoxy resin E-51/ triethylene tetramine solidifying agent/acetone is uniformly mixed into Matrix Solution with weight ratio 200:10:30; By the T300 carbon fiber of 3.45GPa through steeping vat, flood this solution 10s, make and be unidirectionally placed on 12h under room temperature without latitude cloth, the acetone in glue is vapored away completely.Carry out cutting without latitude cloth by the length and width size of 60 × 40mm, and by cut out without the unidirectional folded 8-12 layer of latitude cloth, make multiple material thickness of slab remain on 2mm, then sample put into mould, and mould is put into autoclave; Carry out Procuring at about 147 DEG C, time 25min(also slowly passes into air pressurized to 7MPa at about 90 DEG C); Carry out after fixing at 196 DEG C, time 2h, still internal pressure 6-8Mpa, obtain epoxy resin carbon fiber matrix material.
The degraded of epoxy resin carbon fiber matrix material:
The zinc chloride ethanolic soln being 60% by 100 milliliters of massfractions adds in reactor, restrains the epoxy resin carbon fiber matrix material got ready put into still, sealed reactor by 1,220 DEG C of reaction 5h.By strongtheners such as carbon fibers from reaction system centrifugation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 3.22GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after-10 DEG C of coolings, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.
The preparation method of following examples 7-20 epoxy resin carbon fiber matrix material is with embodiment 1.
Embodiment 7:
The solder(ing)acid being 60% by 100 milliliters of massfractions adds in reactor, restrains the epoxy resin carbon fiber matrix material got ready put into still, sealed reactor by 1,220 DEG C of reaction 5h.By strongtheners such as carbon fibers from reaction system centrifugation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 3.40GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after 0 DEG C of cooling, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.
Embodiment 8:
The zinc sulfate solution being 20% by 100 milliliters of massfractions adds in reactor, restrains the epoxy resin carbon fiber matrix material got ready put into still, sealed reactor by 1,220 DEG C of reaction 9h.By strongtheners such as carbon fibers from reaction system centrifugation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 3.38GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after-5 DEG C of coolings, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.
Embodiment 9:
The Manganous chloride tetrahydrate aqueous solution being 20% by 100 milliliters of massfractions adds in reactor, restrain 1 the epoxy resin carbon fiber matrix material got ready and put into still, sealed reactor, 160 DEG C of reaction 5h.By strongtheners such as carbon fibers from reaction system centrifugation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 3.26GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after 0 DEG C of cooling, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.
Embodiment 10:
The copper chloride solution being 40% by 100 milliliters of massfractions adds in reactor, restrains the epoxy resin carbon fiber matrix material got ready put into still, sealed reactor by 1,220 DEG C of reaction 8h.By strongtheners such as carbon fibers from reaction system centrifugation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 3.20GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after 0 DEG C of cooling, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.Embodiment 11:
The ferric chloride in aqueous solution being 25% by 100 milliliters of massfractions adds in reactor, restrains the epoxy resin carbon fiber matrix material got ready put into still, sealed reactor by 1,220 DEG C of reaction 8h.By strongtheners such as carbon fibers from reaction system centrifugation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 3.18GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after 0 DEG C of cooling, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.
Embodiment 12:
The cobalt chloride solution being 27% by 100 milliliters of massfractions adds in reactor, restrains the epoxy resin carbon fiber matrix material got ready put into still, sealed reactor by 1,200 DEG C of reaction 8h.By strongtheners such as carbon fibers from reaction system centrifugation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 3.36GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after 0 DEG C of cooling, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.
Embodiment 13:
The copper sulfate solution being 14% by 100 milliliters of massfractions adds in reactor, restrains the epoxy resin carbon fiber matrix material got ready put into still, sealed reactor by 1,220 DEG C of reaction 8h.By strongtheners such as carbon fibers from reaction system centrifugation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 3.42GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after 0 DEG C of cooling, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.
Embodiment 14:
The ferric sulfate aqueous solution being 19% by 100 milliliters of massfractions adds in reactor, restrains the epoxy resin carbon fiber matrix material got ready put into still, sealed reactor by 1,220 DEG C of reaction 8h.By strongtheners such as carbon fibers from reaction system centrifugation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 3.30GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after 0 DEG C of cooling, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.
Embodiment 15:
The nickel chloride aqueous solution being 20% by 100 milliliters of massfractions adds in reactor, restrains the epoxy resin carbon fiber matrix material got ready put into still, sealed reactor by 1,220 DEG C of reaction 8h.By strongtheners such as carbon fibers from reaction system centrifugation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 3.26GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after 0 DEG C of cooling, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.
Embodiment 16:
The chromium chloride solution being 8% by 100 milliliters of massfractions adds in reactor, restrains the epoxy resin carbon fiber matrix material got ready put into still, sealed reactor by 1,220 DEG C of reaction 8h.By strongtheners such as carbon fibers from reaction system centrifugation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 3.18GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after 0 DEG C of cooling, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.
Embodiment 17:
The zinc chloride ethanolic soln being 70% by 100 milliliters of massfractions adds in reactor, restrains the epoxy resin carbon fiber matrix material got ready put into still, sealed reactor by 20,180 DEG C of reaction 20h.By strongtheners such as carbon fibers from reaction system centrifugation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 3.43GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after-10 DEG C of coolings, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.
Embodiment 18:
The zinc chloride methanol solution being 70% by 100 milliliters of massfractions adds in reactor, restrains the epoxy resin carbon fiber matrix material got ready put into still, sealed reactor by 15,200 DEG C of reaction 15h.By strongtheners such as carbon fibers from reaction system centrifugation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 3.20GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after-5 DEG C of coolings, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.
Embodiment 19:
By 100 milliliters of massfractions be 70% zinc bromide n-propyl alcohol solution add in reactor, restrain 10 the epoxy resin carbon fiber matrix material got ready and put into still, sealed reactor, 200 DEG C reaction 8h.By strongtheners such as carbon fibers from reaction system centrifugation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 3.37GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after-10 DEG C of coolings, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.
Embodiment 20:
The Tai-Ace S 150 aqueous isopropanol being 8% by 100 milliliters of massfractions adds in reactor, restrain 3 the epoxy resin carbon fiber matrix material got ready and put into still, sealed reactor, 240 DEG C are reacted 5h. by strongtheners such as carbon fibers from reaction system centrifugation, washing and recycling, the carbon fiber strength after detecting and reclaiming is 3.16GPa; DeR liquid after separation of carbon fiber is centrifugal by degradation solution after-10 DEG C of coolings, obtains slightly faint yellow DeR solution and brown sticky degraded product, the degraded product after testing containing minute quantity in DeR solution.
Claims (1)
1. to degrade the method for epoxy resin carbon fiber matrix material, it is characterized in that comprising the steps:
(1) be solvent with water, add metal-salt, be mixed with reaction soln;
(2) epoxy resin carbon fiber matrix material is immersed in reaction soln, carries out degraded 1-20 hour at 160-240 DEG C;
(3) Separation and Recovery metal salt, and obtain epoxy resin degraded product and carbon fiber;
The salts solution of to be concentration the be 8-80wt% of the reaction soln described in step (1);
Metal-salt described in step (1) is positively charged ion is Al
3+, Zn
2+, Cu
2+, Ni
3+, Co
2+, Fe
3+, Cr or Mn
2+, negatively charged ion is the salt of halide-ions or sulfate ion composition;
The quality of the epoxy resin carbon fiber matrix material described in step (2) and the volume ratio of reaction soln are 1-20g:100ml;
Separation and Recovery described in step (3) be filter or centrifugal, carbon fiber is separated from reaction system, washing and recycling; The molecular thick liquid of resin chips after reaction solution frozen cooling to 0 DEG C is degraded to-10 DEG C of removings; Remaining reaction solution can continue to recycle.
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| TWI744750B (en) * | 2019-12-23 | 2021-11-01 | 財團法人工業技術研究院 | Method for degradating thermosetting resin, catalyst composition used therein and resin composition obtained thereby |
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| CN114589196B (en) * | 2022-03-06 | 2023-03-31 | 四川大学 | Method for recycling thermosetting resin and composite material thereof through mild oxidative degradation |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343377A (en) * | 2007-07-13 | 2009-01-14 | 株式会社日立产机系统 | Recycle of electrical equipment |
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| US20140174257A1 (en) * | 2011-03-08 | 2014-06-26 | Panasonic Corporation | Method for decomposing cured epoxy resin |
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| CN101343377A (en) * | 2007-07-13 | 2009-01-14 | 株式会社日立产机系统 | Recycle of electrical equipment |
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