CN104672488A - Method for degrading and recycling thermosetting epoxy resin material - Google Patents

Method for degrading and recycling thermosetting epoxy resin material Download PDF

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CN104672488A
CN104672488A CN201510056492.0A CN201510056492A CN104672488A CN 104672488 A CN104672488 A CN 104672488A CN 201510056492 A CN201510056492 A CN 201510056492A CN 104672488 A CN104672488 A CN 104672488A
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degraded
resin material
epoxy resin
reclaims
reaction soln
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邓天昇
王玉琪
侯相林
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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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
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    • Y02W30/62—Plastics recycling; Rubber recycling

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Abstract

The invention discloses a method for degrading and recycling a thermosetting epoxy resin material. The method comprises the following steps: adding a catalyst into a solvent to prepare a reaction solution, wherein the solvent is a low-carbon organic acid or a mixed solution of a low-carbon organic acid and water; dipping epoxy resin material in the reaction solution, and degrading at 100-280 DEG C for 10min-72min; adding a separating agent to the reaction solution obtained after degradation so as to separate inorganic packing out of the catalyst and the resin, filtering, and drying and recycling the solid; and drying filtrate by distillation to obtain a resin degradation product. The method has the advantages of high efficiency and high selectivity.

Description

A kind of degraded reclaims the method for thermosetting epoxy resin material
Technical field
The present invention relates to a kind of degraded and reclaim the method for thermosetting epoxy resin material.
Technical background
Epoxide resin material is due to its physico-chemical property is stablized, light weight, electric heating insulation etc. are excellent performance, be widely used in the numerous areas such as aerospace, electron electric power, communications and transportation daily life, its demand rises fast, especially the matrix material made with carbon fiber, excellent performance, Application Areas covers military civilian.But along with the continuous production of epoxy resin material and application, waste and scrap is also increasing, brings heavy environmental stress.Epoxide resin material is degraded under relatively mild conditions, not only can alleviate environmental stress, reduce industry and pollute, and can carbon fiber be reclaimed, reduce product cost, there is important economic implications.
The method of current process thermoset resin material 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.Thermochemistry edman degradation Edman under the action of heat thermosetting epoxy resin is degraded to various small-molecule substance, 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 of generation is complicated, and environmental pollution is serious.Chemical degradation method is in certain solvent system, utilize the effect of high temperature or strong oxidizer that the partial chemical key of resin is ruptured under the effect of catalyzer, reaction conditions relaxes, and is a kind of novel method recycling thermosetting resin of current most application prospect.
Patent of invention " a kind of method reclaiming carbon-fibre reinforced epoxy resin composite material " (CN102181071A) 100 ~ 250 DEG C, pass through supercritical CO under 7.5 ~ 25.0MPa 2organic solvent mixed system utilizes strong acid degradative resin matrix material; 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) SO 4 2-/ 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 cooling, solid-liquid separation, isolate carbon fiber and SO by after the solids wash obtained, drying 4 2-/ MxOy type solid super-strong acid, obtains the thermosetting epoxy resin resistates after decomposing 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 epoxy resin composite material 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.Our seminar adopts water/alcohol system to utilize the undersaturated metal ion catalysis epoxy resin degraded of coordination, and reclaim high performance carbon fiber a kind of (method of epoxy resin carbon fiber matrix material of degrading, 201310163799.1) can C-O or C-N key optionally in breaking ring epoxy resins, the degraded realizing epoxy resin is reclaimed.Due to water and the wetting property of alcoholic solvent to thermosetting epoxy resin poor, need comparatively high temps that resin just can be made to occur swelling, limit the diffusion of catalyzer and the degraded of resin, in addition in order to make the heteroatoms complexing in metal ion and resin, thus the chemical bond in reduction resin, this technology must use the salts solution of high density.If improve catalytic activity (reduce temperature or improve speed of response) while catalyst concn being reduced further, there is important using value undoubtedly.
Summary of the invention
The object of this invention is to provide a kind of method that thermosetting epoxy resin material is reclaimed in efficient highly selective degraded.
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 contriver selects 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.Contriver finds that the wetting property of low carbon fatty acid to epoxy resin is good simultaneously, the swelling of thermosetting epoxy resin can be realized at a lower temperature, and due to low carbon fatty acid be a kind of than water and the weak part solvent of alcohol, the heteroatoms that the metal ion be dissolved in wherein is easy in swelling rear resin is combined, and does not need too high concentration also can its cracking of catalysis.
The method that thermosetting epoxy resin material is reclaimed in degraded provided by the invention is first by epoxide resin material, catalyzer and reaction solution heat temperature raising reaction degraded, then will react degraded product Separation and Recovery.
The concrete operation step of the inventive method is as follows:
(1) with the mixed solution of low carbon organic acid or low carbon organic acid and water for solvent, add catalyzer, be mixed with reaction soln;
(2) epoxide resin material is immersed in reaction soln, carries out degraded 10min-72h at 100-280 DEG C;
(3) add separating agent in the reaction soln after degraded, the mineral filler in catalyzer and resin is separated out, filter, solid drying reclaims; Filtrate evaporate to dryness, obtains resin degradation product.
Low carbon organic acid described in step (1) refers to acetic acid, propionic acid, butyric acid or levulinic acid.
Mixed solvent described in step (1) refers to that the mass ratio of low carbon organic acid and water is 1:0.1-10;
Catalyzer described in step (1) mass concentration in reaction soln is 5-40wt%;
Catalyzer described in step (1) is metal-salt, and it is that metal-salt positively charged ion comprises Al 3+, Zn 2+, Cu 2+, Ni 3+, Co 2+, Fe 3+, Cr 3+or Mn 2+deng, negatively charged ion comprises the salt of the compositions such as halide-ions, sulfate ion or acetate ion.
Epoxide resin material described in step (2) the reaction soln volume be immersed in reaction soln is at least can submergence epoxide resin material.
Separating agent described in step (3) refers to the weak polar solvents such as tetrahydrofuran (THF), acetone, chloroform, methylene dichloride, ethyl acetate, methyl acetate, ether, gamma-butyrolactone or γ-valerolactone.
The volume ratio of the reaction soln after the volume of the separating agent described in step (3) and degraded be 1:0.01-1. the present invention compared with the prior art tool have the following advantages:
1, the solvent adopted due to the present invention can swellable resins well, makes catalyzer easily immerse resin body, can efficient catalytic C-N bond rupture.
2, because catalyzer is conventional metal acid-salt, wide material sources, cheap, degraded cost recovery can be reduced further.
3, solvent for use of the present invention (whether being separating agent) is with low cost, and boiling point is lower, can Separation and Recovery.
4, selectivity scission of link, becomes monomer or oligopolymer by resin degradation, thus the overall high value realizing thermosetting resin reclaims.
5, the inventive method have efficiently, the advantage of green, economic dispatch, degradation efficiency is high, and process easily controls, and by product is few, and therefore the inventive method easily realizes industrialization running.
Embodiment
Prepare degradable material
Its chemical constitution of epoxy resin common be at present similar to, bond valence structure phase class, the present invention using following several formula produce solidification unsaturated polyester material and glass fibre reinforcement as degraded raw material:
Formula (1): first epoxy resin AG-80/Laromin C-260 solidifying agent (two (4-amino-3-methyl cyclohexane alkyl)-methane)/acetone is uniformly mixed into Matrix Solution with weight ratio 200:66.6:300, be placed in 12h under room temperature, acetone in glue is vapored away completely, be cured at about 80 DEG C, time 2h.
Formula (2): first epoxy resin E-51 (DGEBA)/Meng alkane diamine curing agent/acetone is uniformly mixed into Matrix Solution with weight ratio 200:100:300, be placed in 12h under room temperature, acetone in glue is vapored away completely, Procuring is carried out at about 80 DEG C, time 25min, after fixing is carried out, time 30min at 130 DEG C.
Formula (3): first epoxy resin E-51//Laromin C-260 solidifying agent/acetone is uniformly mixed into Matrix Solution with weight ratio 200:10:30, be placed in 12h under room temperature, acetone in glue is vapored away completely, is cured at about 80 DEG C, time 2h.
Formula (4): first epoxy resin AG-80/ alkane in Meng diamine curing agent/acetone is uniformly mixed into Matrix Solution with weight ratio 200:100:300, be placed in 12h under room temperature, acetone in glue is vapored away completely, Procuring is carried out at about 80 DEG C, time 25min, after fixing is carried out, time 30min at 130 DEG C.
Embodiment 1
(1) it is the reaction soln of 40% that the acetic acid aqueous solution being 90% by zinc chloride and quality of acetic acid concentration mixes the catalyst quality percentage composition being made into 50ml;
(2) in reaction soln, add the epoxide resin material that 0.5g formula (1) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 100 DEG C of degraded 72h;
(3) after the reaction and cool, in degraded material, add the acetone of 1000ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:
Embodiment 2
(1) it is the reaction soln of 30% that the acetic acid aqueous solution being 95% by zinc bromide and quality of acetic acid concentration mixes the catalyst quality percentage composition being made into 50ml;
(2) in reaction soln, add the epoxide resin material that 1.0g formula (2) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 120 DEG C of degraded 48h;
(3) after the reaction and cool, in degraded material, add the tetrahydrofuran (THF) of 5000ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:
Wherein: m=1-5, n=2-4
Embodiment 3
(1) it is the reaction soln of 10% that the acetic acid aqueous solution being 99% by aluminum chloride and quality of acetic acid concentration mixes the catalyst quality percentage composition being made into 50ml;
(2) in reaction soln, add the epoxide resin material that 1.5g formula (3) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 140 DEG C of degraded 36h;
(3) after the reaction and cool, in degraded material, add the chloroform of 500ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:
Wherein: m=1-5, n=2-4
Embodiment 4
(1) it is the reaction soln of 5% that the acetic acid aqueous solution being 90% by iron(ic) chloride and quality of acetic acid concentration mixes the catalyst quality percentage composition being made into 50ml;
(2) in reaction soln, add the epoxide resin material that 2.0g formula (4) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 160 DEG C of degraded 36h;
(3) after the reaction and cool, in degraded material, add the methylene dichloride of 100ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:
Embodiment 5
(1) cupric chloride being mixed the catalyst quality percentage composition being made into 50ml with propionic acid is the reaction soln of 15%;
(2) in reaction soln, add the epoxide resin material that 0.5g formula (1) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 180 DEG C of degraded 24h;
(3) after the reaction and cool, in degraded material, add the ethyl acetate of 50ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:
Embodiment 6
(1) tri-chlorination nickel being mixed the catalyst quality percentage composition being made into 50ml with levulinic acid is the reaction soln of 20%;
(2) in reaction soln, add the epoxide resin material that 0.5g formula (2) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 200 DEG C of degraded 12h;
(3) after the reaction and cool, in degraded material, add the methyl acetate of 500ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:
Embodiment 7
(1) it is the reaction soln of 10% that the acetic acid aqueous solution being 95% by cobalt dichloride and quality of acetic acid concentration mixes the catalyst quality percentage composition being made into 50ml;
(2) in reaction soln, add the epoxide resin material that 3.0g formula (3) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 220 DEG C of degraded 6h;
(3) after the reaction and cool, in degraded material, add the ether of 1000ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:
Embodiment 8
(1) chromium trichloride being mixed the catalyst quality percentage composition being made into 50ml with acetic acid is the reaction soln of 20%;
(2) in reaction soln, add the epoxide resin material that 15g formula (4) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 240 DEG C of degraded 10h;
(3) after the reaction and cool, in degraded material, add the gamma-butyrolactone of 500ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:
Embodiment 9
(1) it is the reaction soln of 5% that the acetic acid aqueous solution being 90% by manganous chloride and quality of acetic acid concentration mixes the catalyst quality percentage composition being made into 50ml;
(2) in reaction soln, add the epoxide resin material that 10g formula (1) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 280 DEG C of degraded 1h;
(3) after the reaction and cool, in degraded material, add the γ-valerolactone of 100ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:
Embodiment 10
(1) aluminum bromide being mixed the catalyst quality percentage composition being made into 50ml with acetic acid is the reaction soln of 10%;
(2) in reaction soln, add the epoxide resin material that 5.0g formula (2) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 180 DEG C of degraded 6h;
(3) after the reaction and cool, in degraded material, add the tetrahydrofuran (THF) of 1000ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:
Embodiment 11
(1) the catalyst quality percentage composition that the propionic acid aqueous solution being 95% by zinc sulfate and propionic acid mass concentration is made into 50ml is the reaction soln of 5%;
(2) in reaction soln, add the epoxide resin material that 0.5g formula (3) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 180 DEG C of degraded 6h;
(3) after the reaction and cool, in degraded material, add the acetone of 1000ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:
Embodiment 12
(1) the catalyst quality percentage composition that the butyric acid aqueous solution being 99% by Tai-Ace S 150 and butyric acid mass concentration is made into 50ml is the reaction soln of 8%;
(2) in reaction soln, add the epoxide resin material that 1.5g formula (4) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 200 DEG C of degraded 6h;
(3) after the reaction and cool, in degraded material, add the acetone of 1000ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:
Embodiment 13
(1) copper sulfate being mixed the catalyst quality percentage composition being made into 50ml with acetic acid is the reaction soln of 10%;
(2) in reaction soln, add the epoxide resin material that 0.5g formula (1) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 180 DEG C of degraded 30min;
(3) after the reaction and cool, in degraded material, add the gamma-butyrolactone of 500ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:
Embodiment 14
(1) ferric sulfate being mixed the catalyst quality percentage composition being made into 50ml with acetic acid is the reaction soln of 15%;
(2) in reaction soln, add the epoxide resin material that 0.5g formula (2) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 280 DEG C of degraded 10min;
(3) after the reaction and cool, in degraded material, add the acetone of 100ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:
Embodiment 15
(1) it is the reaction soln of 8% that the acetic acid aqueous solution being 90% by zinc acetate and quality of acetic acid concentration mixes the catalyst quality percentage composition being made into 50ml;
(2) in reaction soln, add the epoxide resin material that 0.5g formula (3) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 200 DEG C of degraded 30min;
(3) after the reaction and cool, in degraded material, add the acetone of 600ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:
Embodiment 16
(1) it is the reaction soln of 5% that the acetic acid aqueous solution being 90% by aluminum acetate and quality of acetic acid concentration mixes the catalyst quality percentage composition being made into 50ml;
(2) in reaction soln, add the epoxide resin material that 0.5g formula (4) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 240 DEG C of degraded 2h;
(3) after the reaction and cool, in degraded material, add the acetone of 1000ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:
Embodiment 17
(1) it is the reaction soln of 15% that the acetic acid aqueous solution being 99% by aluminum chloride and quality of acetic acid concentration mixes the catalyst quality percentage composition being made into 50ml;
(2) in reaction soln, add the epoxide resin material that 0.5g formula (1) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 260 DEG C of degraded 10min;
(3) after the reaction and cool, in degraded material, add the acetone of 1000ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:
Embodiment 18
(1) zinc chloride being mixed the catalyst quality percentage composition being made into 50ml with acetic acid is the reaction soln of 40%;
(2) in reaction soln, add the epoxide resin material that 0.5g formula (2) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 240 DEG C of degraded 2h;
(3) after the reaction and cool, in degraded material, add the acetone of 1000ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:
Embodiment 19
(1) aluminum chloride being mixed the catalyst quality percentage composition being made into 50ml with acetic acid is the reaction soln of 10%;
(2) in reaction soln, add the epoxide resin material that 0.5g formula (3) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 140 DEG C of degraded 12h;
(3) after the reaction and cool, in degraded material, add the ether of 1000ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:
Embodiment 20
(1) zinc chloride being mixed the catalyst quality percentage composition being made into 50ml with acetic acid is the reaction soln of 30%;
(2) in reaction soln, add the epoxide resin material that 0.5g formula (4) synthesizes, epoxide resin material is immersed under reaction solution liquid level, at 120 DEG C of degraded 36h;
(3) after the reaction and cool, in degraded material, add the tetrahydrofuran (THF) of 1000ml, filter, the solid after filtration is fortifying fibre and catalyzer, reclaims after super-dry, screening; Filtrate evaporate to dryness, obtains resin degradation product, and the structural formula of degraded product is by analysis:

Claims (8)

1. degrade and reclaim a method for thermosetting epoxy resin material, it is characterized in that comprising the steps:
(1) with the mixed solution of low carbon organic acid or low carbon organic acid and water for solvent, add catalyzer, be mixed with reaction soln;
(2) epoxide resin material is immersed in reaction soln, carries out degraded 10min-72h at 100-280 DEG C;
(3) add separating agent in the reaction soln after degraded, the mineral filler in catalyzer and resin is separated out, filter, solid drying reclaims; Filtrate evaporate to dryness, obtains resin degradation product.
2. a kind of degraded as claimed in claim 1 reclaims the method for thermosetting epoxy resin material, it is characterized in that the low carbon organic acid described in step (1) is acetic acid, propionic acid, butyric acid or levulinic acid.
3. a kind of degraded as claimed in claim 1 reclaims the method for thermosetting epoxy resin material, and the mixed solvent that it is characterized in that described in step (1) is the mass ratio of low carbon organic acid and water is 1:0.1-10.
4. a kind of degraded as claimed in claim 1 reclaims the method for thermosetting epoxy resin material, it is characterized in that the catalyzer mass concentration in reaction soln described in step (1) is 5-40wt%.
5. a kind of degraded as claimed in claim 1 reclaims the method for thermosetting epoxy resin material, and it is characterized in that the catalyzer described in step (1) is metal-salt, its metal-salt positively charged ion comprises Al 3+, Zn 2+, Cu 2+, Ni 3+, Co 2+, Fe 3+, Cr 3+or Mn 2+, negatively charged ion comprises the salt of halide-ions, sulfate ion or acetate ion composition.
6. a kind of degraded as claimed in claim 1 reclaims the method for thermosetting epoxy resin material, it is characterized in that the epoxide resin material reaction soln volume be immersed in reaction soln described in step (2) is at least can submergence epoxide resin material.
7. a kind of degraded as claimed in claim 1 reclaims the method for thermosetting epoxy resin material, it is characterized in that the separating agent described in step (3) is tetrahydrofuran (THF), acetone, chloroform, methylene dichloride, ethyl acetate, methyl acetate, ether, gamma-butyrolactone or γ-valerolactone.
8. a kind of degraded as claimed in claim 1 reclaims the method for thermosetting epoxy resin material, and the volume ratio of the reaction soln after it is characterized in that the volume of the separating agent described in step (3) and degrading is 1:0.01-1.
CN201510056492.0A 2015-02-03 2015-02-03 Method for degrading and recycling thermosetting epoxy resin material Pending CN104672488A (en)

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CN109651645A (en) * 2018-12-07 2019-04-19 上海第二工业大学 A kind of method that wet oxidation separates glass fibre and epoxy resin in WPCB non-metal powder
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CN109651645A (en) * 2018-12-07 2019-04-19 上海第二工业大学 A kind of method that wet oxidation separates glass fibre and epoxy resin in WPCB non-metal powder
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CN113087964A (en) * 2019-12-23 2021-07-09 财团法人工业技术研究院 Method for degrading thermosetting resin, catalyst composition used therein, and resin composition obtained thereby
CN113087964B (en) * 2019-12-23 2023-08-08 财团法人工业技术研究院 Method for degrading thermosetting resin, catalyst composition used therein, and resin composition obtained thereby
WO2022007906A1 (en) * 2020-07-08 2022-01-13 中国科学院山西煤炭化学研究所 Method for catalyzing degradation of anhydride-cured epoxy resin
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CN111777566A (en) * 2020-07-15 2020-10-16 中国科学院山西煤炭化学研究所 Method for degrading waste melamine resin and recycling melamine by two-step method
CN111747901A (en) * 2020-07-15 2020-10-09 中国科学院山西煤炭化学研究所 Method for selectively breaking C-N bond in melamine resin
CN111675827A (en) * 2020-07-15 2020-09-18 中国科学院山西煤炭化学研究所 Method for recovering melamine by catalytically degrading melamine resin
CN113522885A (en) * 2021-07-09 2021-10-22 东莞理工学院 Method for treating waste printed circuit board by supercritical fluid
CN114456439A (en) * 2022-02-20 2022-05-10 中国科学院山西煤炭化学研究所 Method for degrading amine cured epoxy resin composite material
CN114456439B (en) * 2022-02-20 2024-02-06 中国科学院山西煤炭化学研究所 Method for degrading amine-cured epoxy resin composite material
CN114589196A (en) * 2022-03-06 2022-06-07 四川大学 Method for recycling thermosetting resin and composite material thereof through mild oxidative degradation
WO2023222975A1 (en) * 2022-05-20 2023-11-23 Expleo France Use of a composition for recycling a material based on epoxy resin, and associated recycling method and composition
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