CN111171373A - Recovery method of fiber reinforced composite material - Google Patents
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- 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
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- 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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Abstract
The invention discloses a method for recovering fiber reinforced composite materials, which depolymerizes thermosetting epoxy resin into thermoplastic linear macromolecules through catalytic oxidation of an organic catalyst and quickly dissolves the thermoplastic linear macromolecules into an organic solvent so as to separate and recover fiber materials and thermoplastic polymers.
Description
Technical Field
The invention relates to the technical field of degradation and recovery of fiber reinforced composite materials, in particular to a recovery method of a fiber reinforced composite material.
Background
The carbon fiber belongs to high and new technology and high value-added products, has incomparable excellent performance of other materials, has gradually permeated from the initial aerospace and military departments to the civil field since the commercialization, and is expanded to various fields of the whole industry and the civil at present.
Carbon fiber composite waste is a generic term for carbon fibers, carbon fiber prepregs, and carbon fiber composite waste. With the increasing depth of carbon fiber composite materials into the lives of people, carbon fiber products are gradually increased, and the treatment of carbon fiber composite material waste is an inevitable problem. The existing processing technology of the carbon fiber composite material is a thermosetting molding technology, and once all carbon fiber products are scrapped, the carbon fiber products cannot be recycled like other thermoplastic composite materials. In the future, waste treatment and recycling of carbon fiber composite materials will also become a main direction for research in the carbon fiber industry. At present, the research on the recycling method of the fiber reinforced composite materials at home and abroad mainly aims at non-degradable thermosetting resin matrix composite material garbage wastes and comprises a landfill method, an incineration method, a crushing method, a heat treatment method and a chemical method. Landfill and incineration will be increasingly prohibited. The crushing method is to crush the composite garbage waste into reclaimed materials with different particle sizes by means of cutting and grinding, and the reclaimed materials are used as low-value fillers.
Heat treatment processes include incineration, thermal cracking, fluidized bed and cement kiln processes, which have in common: gasifying organic matter components (30-40%) in the composite material garbage at the high temperature of 500-950 ℃, and simultaneously recovering energy. Wherein, the cement kiln method can also convert inorganic components (60-70%) into raw materials required by cement manufacture; the thermal cracking method and the fluidized bed method can separate and recover fiber materials, the recovered glass fiber is used for manufacturing glass, coke often remains on the surface of the recovered carbon fiber, the mechanical property is reduced, and only 70-80% of the original carbon fiber is left, so that the recycling value of the carbon fiber is greatly influenced. The chemical methods comprise a solvent hydrolysis method, an acid digestion method, an alkali hydrolysis method, a catalytic depolymerization method, an oxidative degradation method and the like, and the methods are characterized in that: the high-crosslinking organic polymer components are degraded by chemical reaction by using high-temperature and high-pressure solvents (supercritical, subcritical or near-critical water, methanol, ethanol, propanol and the like), high-concentration strong oxidizing acids (8-12N concentrated nitric acid), strong alkali, strong corrosive reagents (phenol) or strong oxidants and the like, so that the separation and recovery of the fiber reinforced material are realized. The current solvent decomposition method is also in a laboratory test stage, needs high-temperature and high-pressure conditions, has extremely high equipment requirements, and is difficult to realize industrial scale operation; other chemical methods have strict requirements on equipment and operating environment, have low production efficiency, generate a large number of secondary pollution sources and are not suitable for industrial operation. It can be seen that the above recovery methods all have the disadvantage of being unavoidable, and there are many problems from the industrial requirement.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at various problems in the existing fiber reinforced material separation and recovery technology, the invention provides a recovery method of a fiber reinforced composite material to solve the problems.
In order to solve the technical problems, the invention provides the following technical scheme:
a method for recovering a fiber-reinforced composite material, which is obtained by oxidatively dissolving a thermosetting resin in an organic solvent by catalytic oxidation with an organic catalyst to separate and recover the fiber material, comprising the steps of:
step 1: crushing the fiber reinforced composite material into composite material fragments of 3-5 cm;
step 2: putting the fiber reinforced composite material fragments into a reaction vessel filled with an organic catalyst and an organic solvent, and heating to 80-140 ℃ to preheat for 0.5-5 hours to ensure that the composite material is completely unfolded in the organic solvent;
and step 3: adding a certain amount of oxidant into a reaction container and reacting for 2-12 hours to ensure that the thermosetting epoxy resin is completely depolymerized into a low molecular weight thermoplastic polymer and is quickly dissolved in an organic solvent;
and 4, step 4: after the epoxy resin in the fiber composite material is completely depolymerized and dissolved, a secondary solution containing the thermoplastic polymer is centrifugally separated, and after physical and chemical means for separation, the recovered degradation liquid can be directly applied mechanically, and the separated thermoplastic polymer has excellent physical and chemical properties;
and 5: and further washing, centrifugally separating and drying free fibers in the centrifuge to obtain high-valued recycled fibers.
Preferably, the organic catalyst is one or more of formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, benzoic acid, oxalic acid, methyl ethyl ketone and cyclohexanone.
Preferably, the fibers in the fiber-reinforced composite material include one or more of carbon fibers, glass fibers, aramid fibers, polyester fibers, polyamide fibers, polyvinyl alcohol fibers, polyacrylonitrile fibers, polypropylene fibers, and polyvinyl chloride fibers.
Preferably, the epoxy resin in the fiber-reinforced composite material includes one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin, and alicyclic epoxy resin.
Preferably, the organic solvent is one or more of 1-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, chloroform, dichloroethane, dioxane, acetonitrile, benzene, toluene, xylene and water or is not added.
Preferably, the oxidant is one or more of aqueous hydrogen peroxide, oxygen, ozone, nitric acid, chlorine and hypochlorous acid.
Preferably, the concentration of the aqueous hydrogen peroxide solution is 5 to 40 percent; the concentration of the nitric acid is 10-70%; the concentration of the hypochlorous acid is 5-40%.
Preferably, the mass ratio of active oxygen in the organic catalyst to active oxygen in the oxidant is 0.05-20: 1.
preferably, the mass ratio of the fiber reinforced composite material to the organic solvent is 0.01-0.25: 1.
preferably, the mass ratio of active oxygen in the fiber reinforced composite material and the oxidant is 0.1-5: 1.
the invention has the following beneficial effects:
compared with the prior art, the method adopts an organic catalytic oxidation method to depolymerize the thermosetting epoxy resin into thermoplastic linear macromolecules and quickly dissolve the thermoplastic linear macromolecules into the organic solvent, thereby separating and recycling the carbon fibers and realizing resource recycling. The method specifically comprises the following steps:
(1) the compatibility of the organic catalyst and the organic solvent is good, and the catalytic oxidation efficiency of the fiber reinforced material can be obviously improved;
(2) the organic catalyst is dissolved in the organic solvent, and the separation of the fiber material and the catalyst/organic solvent system can be easily realized.
(3) The recovery rate of the fiber can reach more than 95 percent, and the recovered fiber has basically no defect and no residual impurity on the surface and can be reused;
(4) the thermosetting cross-linked epoxy resin is oxidized and degraded into low molecular weight thermoplastic polymer, then the low molecular weight thermoplastic polymer is dissolved in an organic solvent, and can be reused as a high molecular material additive and the like after being separated;
(5) the degraded organic catalyst and organic solvent can be directly distilled, recovered and recycled.
Drawings
FIG. 1 is a diagram showing carbon fibers obtained by degradation recovery in example 1.
Fig. 2 is an SEM comparison of carbon fiber precursor filaments and recycled carbon fiber filaments.
Wherein, (a) is carbon fiber precursor; (b) to recover carbon fiber filaments.
Detailed Description
The following examples are included to provide further detailed description of the present invention and to provide those skilled in the art with a more complete, concise, and exact understanding of the principles and spirit of the invention.
Example 1:
the fiber reinforced composite leftover material is prepared from fibers and epoxy resin, wherein the fibers are carbon fibers; the epoxy resin is glycidyl ether epoxy resin. The fiber reinforced composite leftover materials are crushed into uniform fragments with the particle size of 3cm by a commercial crusher before being degraded.
Adding 1 g of carbon fiber composite material fragments, 0.5 g of formic acid serving as an organic catalyst and 15 g of toluene serving as an organic solvent into a three-neck flask, starting a stirrer for stirring, heating in a water bath to 110 ℃, keeping the temperature for 1 hour, slowly dropping 10 g of 5% hydrogen peroxide aqueous solution, carrying out degradation reaction for 12 hours, cooling after the reaction is finished, filtering, and carrying out solid-liquid separation to obtain a solid intermediate product, namely carbon fiber and a liquid intermediate product degradation solution; washing the obtained solid intermediate product with water, drying, and separating clean carbon fibers (shown in figure 1); and carrying out reduced pressure distillation on the obtained liquid intermediate product to obtain the low molecular weight thermoplastic polymer which can be recycled after oxidative degradation and a mixed solvent of the recovered organic solvent and the recovered organic catalyst, wherein the recovery rate of the carbon fiber is 97%. The SEM image of the recovered carbon fiber is shown in fig. 2, and the SEM comparison image of the carbon fiber yarn before and after recovery shows that the surface of the precursor (fig. 2a) and the surface of the regenerated carbon fiber yarn (fig. 2b) have the same morphology and almost no significant damage. It can be seen that the surface thereof is substantially free of defects and impurities, and can be reused.
Example 2:
the fiber reinforced composite leftover material is prepared from fibers and epoxy resin, wherein the fibers are glass fibers; the epoxy resin is glycidyl ester epoxy resin. The fiber reinforced composite leftover materials are crushed into uniform fragments with the particle size of 5cm by a commercial crusher before being degraded.
Adding 1 g of carbon fiber composite material fragments and 15.5 g of formic acid into a three-neck flask, wherein the carbon fiber composite material fragments and the formic acid have double functions of an organic catalyst and an organic solvent, starting a stirrer for stirring, heating in a water bath to 100 ℃, keeping the temperature for 1 hour, slowly dropping 10 g of 40% hydrogen peroxide aqueous solution, performing degradation reaction for 10 hours, cooling after the reaction is finished, filtering, and performing solid-liquid separation to obtain a solid intermediate product, namely carbon fiber and a liquid intermediate product degradation solution; washing the obtained solid intermediate product with water, and separating clean carbon fibers after drying; and carrying out reduced pressure distillation on the obtained liquid intermediate product to obtain the low molecular weight thermoplastic polymer which can be recycled after oxidative degradation and a mixed solvent of the recovered organic solvent and the recovered organic catalyst, wherein the recovery rate of the carbon fiber is 97%.
Example 3:
the fiber reinforced composite leftover material is prepared from fibers and epoxy resin, wherein the fibers are aramid fibers; the epoxy resin is glycidyl amine epoxy resin. The fiber reinforced composite leftover materials are crushed into uniform fragments with the particle size of 4cm by a commercial crusher before being degraded.
Adding 1 g of carbon fiber composite material fragments and 15.5 g of acetic acid into a three-neck flask, wherein the carbon fiber composite material fragments and the acetic acid have dual functions of an organic catalyst and an organic solvent, starting a stirrer for stirring, heating in a water bath to 115 ℃, keeping the temperature for 1 hour, slowly dropping 10 g of 30% hydrogen peroxide aqueous solution, performing degradation reaction for 6 hours, cooling after the reaction is finished, filtering, and performing solid-liquid separation to obtain a solid intermediate product, namely carbon fiber and a liquid intermediate product degradation solution; washing the obtained solid intermediate product with water, and separating clean carbon fibers after drying; and carrying out reduced pressure distillation on the obtained liquid intermediate product to obtain the low molecular weight thermoplastic polymer which can be recycled after oxidative degradation and a mixed solvent of the recovered organic solvent and the recovered organic catalyst, wherein the recovery rate of the carbon fiber is 98%.
Example 4:
the fiber reinforced composite leftover material is prepared from fibers and epoxy resin, wherein the fibers are polyester fibers (terylene); the epoxy resin is linear aliphatic epoxy resin. The fiber reinforced composite leftover materials are crushed into uniform fragments with the particle size of 3.5cm by a commercial crusher before being degraded.
Adding 1 g of carbon fiber composite material fragments, 0.5 g of methyl ethyl ketone as an organic catalyst and 15 g of toluene as an organic solvent into a three-neck flask, starting a stirrer for stirring, heating in a water bath to 115 ℃, keeping for 1 hour, slowly introducing 1.5L of ozone through an ozone generator, performing degradation reaction for 4 hours, cooling after the reaction is finished, filtering, and performing solid-liquid separation to obtain a solid intermediate product, namely carbon fiber and a liquid intermediate product degradation liquid; washing the obtained solid intermediate product with water, and separating clean carbon fibers after drying; and carrying out reduced pressure distillation on the obtained liquid intermediate product to obtain the low molecular weight thermoplastic polymer which can be recycled after oxidative degradation and a mixed solvent of the recovered organic solvent and the recovered organic catalyst, wherein the recovery rate of the carbon fiber is 96%.
Example 5:
the fiber reinforced composite leftover material is prepared from fibers and epoxy resin, wherein the fibers are polyamide fibers (chinlon or nylon); the epoxy resin is alicyclic epoxy resin. The fiber reinforced composite leftover materials are crushed into uniform fragments with the particle size of 4.5cm by a commercial crusher before being degraded.
Adding 1 g of glass fiber composite material fragments, 0.5 g of cyclohexanone as an organic catalyst and 15 g of dichloroethane as an organic solvent into a three-neck flask, starting a stirrer for stirring, heating in a water bath to 115 ℃, keeping for 1 hour, slowly introducing 15L of oxygen, performing degradation reaction for 60 hours, cooling after the reaction is finished, filtering, and performing solid-liquid separation to obtain a solid intermediate product glass fiber and a liquid intermediate product degradation liquid; washing the obtained solid intermediate product with water, and separating clean glass fiber after drying; and carrying out reduced pressure distillation on the obtained liquid intermediate product to obtain the low molecular weight thermoplastic polymer which can be recycled after oxidative degradation and a mixed solvent of the recovered organic solvent and the recovered organic catalyst, wherein the recovery rate of the glass fiber is 98%.
Example 6:
the fiber reinforced composite leftover material is prepared from fibers and epoxy resin, wherein the fibers are polyvinyl alcohol fibers (vinylon); the epoxy resin includes glycidyl ether epoxy resin and glycidyl ester epoxy resin. The fiber reinforced composite leftover materials are crushed into uniform fragments with the particle size of 3cm by a commercial crusher before being degraded.
Adding 1 g of carbon fiber composite material chips, 0.5 g of benzoic acid serving as an organic catalyst and 15 g of toluene serving as an organic solvent into a three-neck flask, starting a stirrer for stirring, heating in a water bath to 115 ℃, keeping the temperature for 1 hour, slowly dropping 10 g of 25% hydrogen peroxide aqueous solution, performing degradation reaction for 20 hours, cooling after the reaction is finished, filtering, and performing solid-liquid separation to obtain a solid intermediate product, namely carbon fiber and a liquid intermediate product degradation solution; washing the obtained solid intermediate product with water, and separating clean carbon fibers after drying; and carrying out reduced pressure distillation on the obtained liquid intermediate product to obtain the low molecular weight thermoplastic polymer which can be recycled after oxidative degradation and a mixed solvent of the recovered organic solvent and the recovered organic catalyst, wherein the recovery rate of the carbon fiber is 95%.
Example 7:
the fiber reinforced composite leftover material is prepared from fibers and epoxy resin, wherein the fibers are polyacrylonitrile fibers (acrylon); the epoxy resin is glycidyl amine epoxy resin and linear aliphatic epoxy resin. The fiber reinforced composite leftover materials are crushed into uniform fragments with the particle size of 5cm by a commercial crusher before being degraded.
Adding 1 g of carbon fiber composite material fragments and 15.5 g of acetic acid into a three-neck flask, wherein the carbon fiber composite material fragments and the acetic acid have double functions of an organic catalyst and an organic solvent, starting a stirrer for stirring, heating in a water bath to 115 ℃, keeping for 1 hour, slowly introducing 1.5L of ozone through an ozone generator, performing degradation reaction for 8 hours, cooling after the reaction is finished, filtering, and performing solid-liquid separation to obtain solid intermediate product carbon fibers and liquid intermediate product degradation liquid; washing the obtained solid intermediate product with water, and separating clean carbon fibers after drying; and carrying out reduced pressure distillation on the obtained liquid intermediate product to obtain the low molecular weight thermoplastic polymer which can be recycled after oxidative degradation and a mixed solvent of the recovered organic solvent and the recovered organic catalyst, wherein the recovery rate of the carbon fiber is 97%.
Example 8:
the fiber reinforced composite leftover material is prepared from fibers and epoxy resin, wherein the fibers are carbon fibers; the epoxy resin is glycidyl amine epoxy resin. The fiber reinforced composite leftover materials are crushed into uniform fragments with the particle size of 3cm by a commercial crusher before being degraded.
Adding 1 g of carbon fiber composite material fragments and 15.5 g of acetic acid into a three-neck flask, wherein the carbon fiber composite material fragments and the acetic acid have dual functions of an organic catalyst and an organic solvent, starting a stirrer for stirring, heating in a water bath to 110 ℃, keeping the temperature for 1 hour, slowly dropping 1 g of 65% nitric acid aqueous solution, performing degradation reaction for 6 hours, cooling after the reaction is finished, filtering, and performing solid-liquid separation to obtain a solid intermediate product, namely carbon fiber and a liquid intermediate product degradation solution; washing the obtained solid intermediate product with water, and separating clean carbon fibers after drying; and carrying out reduced pressure distillation on the obtained liquid intermediate product to obtain the low molecular weight thermoplastic polymer which can be recycled after oxidative degradation and a mixed solvent of the recovered organic solvent and the recovered organic catalyst, wherein the recovery rate of the carbon fiber is 97%.
Example 9: the rest is the same as example 8, except that:
in the carbon fiber, the glass fiber, the aramid fiber, the polyester fiber, the polyamide fiber, the polyvinyl alcohol fiber, the polyacrylonitrile fiber, the polypropylene fiber and the polyvinyl chloride fiber, the fiber of the fiber reinforced composite leftover material is the polypropylene fiber and the polyvinyl chloride fiber;
the organic catalyst in the above embodiment can be equivalently replaced by one or more of formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, benzoic acid, oxalic acid, methyl ethyl ketone and cyclohexanone.
The organic solvent in the above examples can be replaced by one or more of 1-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, ethyl acetate, chloroform, dichloroethane, dioxane, acetonitrile, benzene, toluene, xylene, and water.
The organic solvent and the organic catalyst are used in amounts satisfying the following conditions:
the mass ratio of active oxygen in the organic catalyst to active oxygen in the oxidant is 0.05-20: 1.
the mass ratio of the fiber reinforced composite material to the organic solvent is 0.01-0.25: 1.
the mass ratio of active oxygen in the fiber reinforced composite material to the active oxygen in the oxidant is 0.1-5: 1.
the above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention cannot be limited thereby, and any modification made on the basis of the technical scheme according to the technical idea proposed by the present invention falls within the protection scope of the present invention; the technology not related to the invention can be realized by the prior art.
Claims (10)
1. A method for recycling a fiber reinforced composite material, which is characterized in that the fiber reinforced composite material is subjected to catalytic oxidation by an organic catalyst so as to depolymerize a thermosetting epoxy resin and rapidly dissolve the thermosetting epoxy resin in an organic solvent, thereby separating and recycling the fiber material, and comprises the following steps:
step 1: crushing the fiber reinforced composite material into composite material fragments of 3-5 cm;
step 2: putting the fiber reinforced composite material fragments into a reaction vessel filled with an organic catalyst and an organic solvent, and heating to 80-140 ℃ to preheat for 0.5-5 hours to completely spread the composite material in the organic solvent;
and step 3: adding a certain amount of oxidant into a reaction container, reacting for 2-12 hours, completely depolymerizing the thermosetting epoxy resin into a low molecular weight thermoplastic polymer, and rapidly dissolving the low molecular weight thermoplastic polymer in an organic solvent;
and 4, step 4: after the epoxy resin in the fiber composite material is completely depolymerized and dissolved, a secondary solution containing the thermoplastic polymer is centrifugally separated, and after physical and chemical means for separation, the recovered degradation liquid can be directly applied mechanically, and the separated thermoplastic polymer has excellent physical and chemical properties;
and 5: and further washing, centrifugally separating and drying free fibers in the centrifuge to obtain high-valued recycled fibers.
2. The method for recovering the fiber reinforced composite material according to claim 1, wherein the organic catalyst is one or more of formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, benzoic acid, oxalic acid, methyl ethyl ketone and cyclohexanone.
3. The method of claim 1, wherein the fibers of the fiber-reinforced composite material comprise one or more of carbon fibers, glass fibers, aramid fibers, polyester fibers, polyamide fibers, polyvinyl alcohol fibers, polyacrylonitrile fibers, polypropylene fibers, and polyvinyl chloride fibers.
4. The method of claim 1, wherein the epoxy resin in the fiber-reinforced composite material comprises one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin, and alicyclic epoxy resin.
5. The method for recycling a fiber reinforced composite material according to claim 1, wherein the organic solvent is one or more selected from the group consisting of 1-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, ethyl acetate, chloroform, dichloroethane, dioxane, acetonitrile, benzene, toluene, xylene, and water, or is not added.
6. The method of claim 1, wherein the oxidant is one or more selected from the group consisting of aqueous hydrogen peroxide, oxygen, ozone, nitric acid, chlorine, and hypochlorous acid.
7. The method of claim 6, wherein the concentration of the aqueous hydrogen peroxide solution is 5% to 40%; the concentration of the nitric acid is 10-70%; the concentration of the hypochlorous acid is 5-40%.
8. The method for recycling the fiber reinforced composite material according to claim 2, wherein the mass ratio of active oxygen in the organic catalyst to active oxygen in the oxidant is 0.05-20: 1.
9. the method for recycling the fiber-reinforced composite material according to claim 5, wherein the mass ratio of the fiber-reinforced composite material to the organic solvent is 0.01 to 0.25: 1.
10. the method for recycling the fiber reinforced composite material according to claim 6, wherein the mass ratio of the active oxygen in the fiber reinforced composite material to the oxidant is 0.1-5: 1.
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Cited By (6)
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CN112029147A (en) * | 2020-07-22 | 2020-12-04 | 艾达索高新材料芜湖有限公司 | Chemical recovery method of aramid fiber reinforced composite material |
CN113861506A (en) * | 2021-10-26 | 2021-12-31 | 胜利油田东方鹏达非金属材料制品有限公司 | Method for degrading and separating glass fiber reinforced composite material waste and preparing sulfonated asphalt by using same |
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 |
WO2022138764A1 (en) * | 2020-12-23 | 2022-06-30 | 株式会社ミライ化成 | Manufacturing method for recycled reinforcing fibers |
WO2023097534A1 (en) * | 2021-12-01 | 2023-06-08 | Solvay Sa | Chemoenzymatic degradation of epoxy composites |
WO2024125740A1 (en) * | 2022-12-13 | 2024-06-20 | Teknologisk Institut | A method of extracting thermoset resin fractions for decomposition and reuse |
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WO2022138764A1 (en) * | 2020-12-23 | 2022-06-30 | 株式会社ミライ化成 | Manufacturing method for recycled reinforcing fibers |
JPWO2022138764A1 (en) * | 2020-12-23 | 2022-06-30 | ||
JP7240567B2 (en) | 2020-12-23 | 2023-03-15 | 株式会社ミライ化成 | Method for producing recycled reinforcing fiber |
CN113861506A (en) * | 2021-10-26 | 2021-12-31 | 胜利油田东方鹏达非金属材料制品有限公司 | Method for degrading and separating glass fiber reinforced composite material waste and preparing sulfonated asphalt by using same |
WO2023097534A1 (en) * | 2021-12-01 | 2023-06-08 | Solvay Sa | Chemoenzymatic degradation of epoxy composites |
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 |
WO2024125740A1 (en) * | 2022-12-13 | 2024-06-20 | Teknologisk Institut | A method of extracting thermoset resin fractions for decomposition and reuse |
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