CN111793246A - Normal-pressure solvent recovery method for amine curing epoxy resin-based carbon fiber reinforced composite material - Google Patents
Normal-pressure solvent recovery method for amine curing epoxy resin-based carbon fiber reinforced composite material Download PDFInfo
- Publication number
- CN111793246A CN111793246A CN202010613895.1A CN202010613895A CN111793246A CN 111793246 A CN111793246 A CN 111793246A CN 202010613895 A CN202010613895 A CN 202010613895A CN 111793246 A CN111793246 A CN 111793246A
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- composite material
- solid product
- fiber reinforced
- reinforced composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
Abstract
The invention relates to a normal-pressure solvent recovery method for an amine cured epoxy resin-based carbon fiber reinforced composite material, which adopts a monoethanolamine and potassium hydroxide solution system to degrade the carbon fiber reinforced composite material. Glacial acetic acid is used as a reaction solvent, an alkali metal catalyst and a magnetic stirring rotor are added, a CFRP layered inside is obtained through constant temperature reaction, the CFRP is placed in a solvent filled with monoethanolamine, potassium hydroxide is added, a solid product and a liquid product after constant temperature reaction are separated through a filter screen, the solid product is collected, the collected solid product is washed for a plurality of times by absolute ethyl alcohol to remove residual resin matrixes, adhered degradation liquid and the like on the surface of the solid product, then the solid product is ultrasonically washed for 2-3 times by deionized water, and the washed solid product is placed in an oven at the temperature of about 80 ℃ and is dried for 12 hours. And weighing the dried carbon fiber filament product, and calculating the degradation rate. The method has the advantages of short reaction time, low reaction temperature and high recovery efficiency, and the obtained carbon fiber has good surface appearance and good performance retention.
Description
Technical Field
The invention belongs to the technical field of recycling of waste carbon fiber reinforced resin matrix composite materials, and relates to a normal-pressure solvent recycling method of an amine cured epoxy resin matrix carbon fiber reinforced composite material.
Background
The carbon fiber reinforced thermosetting resin-based composite material (CFRP) has the characteristics of high strength and rigidity, light weight, good thermal stability and the like, is one of the most advanced composite materials at present, is widely applied to various industries, and is manufactured from aerospace, automobiles and sports goods.
In recent years, the increase of the CFRP production has brought about a large increase of waste, which is a serious environmental problem because the waste forms a three-dimensional crosslinked network structure during curing molding and cannot be melted or dissolved. Aiming at the problem that the CFRP waste is difficult to recycle, relevant laws and regulations at home and abroad guide the development of recycling research of the thermosetting carbon fiber reinforced composite material, and the resource recycling of the waste is realized.
Currently, chemical recovery includes supercritical fluid processes and atmospheric solvent decomposition processes. The normal pressure solvent decomposition method adopts some solvents with high boiling point and adds proper catalyst to degrade the resin matrix in CFRP into soluble substance under normal pressure condition, and then separates out high value carbon fiber. Aiming at the epoxy resin-based carbon fiber reinforced composite material cured by amine, a two-step method is mostly adopted to degrade a resin matrix, and comprises the following steps: various acids are pretreated and then subjected to solvent degradation or subjected to solvent treatment and then microwave-assisted degradation. For example, Pinglai Xu, et al, have studied the presence of hydrogen peroxide (H) in the resin matrix of amine-based cured epoxy resin-based composites2O2)Degrading the resin monomer molecules into resin monomer molecules in a mixed solution of the resin monomer molecules and Dimethylformamide (DMF), and specifically comprising the following steps: first, the sample was pretreated in acetic acid (120 ℃/30min) to allow for expansion and delamination, resulting in a larger surface area. Second, the pre-treated, layered sample was placed in an oven to dry (100 ℃/12 h). Thirdly, putting the dried sample into H2O2Heating the mixed solution of DMF and DMF to 120 ℃, and reacting for 2 hours at constant temperature. The carbon fiber obtained by the method has good surface appearance and relatively good performance, and the degradation efficiency is as high as more than 95%. However, this method requires timeIs longer (14-15 h). In contrast, the development of another method for efficiently and quickly recovering the employ 5015 epoxy resin matrix (resin matrix commonly used in RTM molding process) carbon fiber reinforced composite material by a two-step method has a good development prospect.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a normal-pressure solvent recovery method of an amine curing epoxy resin-based carbon fiber reinforced composite material, which solves the problem of long reaction time in the existing normal-pressure solvent decomposition method.
Technical scheme
A normal pressure solvent recovery method of an amine curing epoxy resin based carbon fiber reinforced composite material is characterized by comprising the following steps:
step 1: mixing the amine cured epoxy resin-based carbon fiber reinforced composite material CFRP with 30ml of glacial acetic acid according to the weight of 3-4 g, and adding an alkali metal catalyst and magnetic magnetons;
step 2: heating to 80-90 ℃, and reacting at constant temperature for 30-40 min to obtain CFRP internally layered;
and step 3: washing with deionized water for several times, and drying in an oven at 100 deg.C for 2h to obtain pretreated CFRP;
and 4, step 4: adding the pretreated CFRP into a mixed solution containing monoethanolamine MEA and potassium hydroxide KOH, heating to 150-170 ℃, and reacting at constant temperature for 90-100 min;
the potassium hydroxide KOH of the mixed solution is 2.02-6.06 g, and the monoethanolamine MEA is 60 ml;
and 5: separating the reacted solid product and the liquid product through a filter screen, and removing the residual resin matrix and the adhered degradation liquid on the surface of the solid product by adopting absolute ethyl alcohol to the solid product;
step 6: ultrasonically cleaning the carbon fiber reinforced composite material by deionized water for 2-3 times, and drying the cleaned solid product in an oven at the temperature of about 80 ℃ for 12 hours to complete the recovery of the amine cured epoxy resin-based carbon fiber reinforced composite material.
The concentration of the catalyst KOH is 2-10 wt%.
Advantageous effects
The invention provides a normal-pressure solvent recovery method for an amine cured epoxy resin-based carbon fiber reinforced composite material, which adopts a monoethanolamine and potassium hydroxide solution system to degrade an employ 5015 epoxy resin cured carbon fiber reinforced composite material. Firstly, measuring the volume of a test piece, weighing the weight (3-4 g) of the test piece, adding glacial acetic acid (30ml) serving as a reaction solvent into a three-neck flask with a condensation reflux pipe, adding an alkali metal catalyst and a magnetic stirring rotor, heating the solution to 80-90 ℃, and reacting at constant temperature for 30-40 min to obtain an internally layered CFRP sample. And then placing the pretreated CFRP sample into an oven at about 100 ℃ for 2 h. And finally, putting the CFRP sample into a three-neck flask filled with a monoethanolamine solvent (60ml), adding potassium hydroxide (1.20-6.06 g), and reacting for 90-100 min at the constant temperature of 150-170 ℃. And separating the reacted solid product and the liquid product through a filter screen, collecting the solid product, cleaning the collected solid product with absolute ethyl alcohol for a plurality of times to remove residual resin matrix, adhered degradation liquid and the like on the surface of the solid product, then ultrasonically cleaning the solid product with deionized water for 2-3 times, and placing the cleaned solid product in an oven at about 80 ℃ for drying for 12 hours. And weighing the dried carbon fiber filament product, and calculating the degradation rate. The method has the advantages of short reaction time, low reaction temperature and high recovery efficiency, and the obtained carbon fiber has good surface appearance and good performance retention.
The invention provides a method for recovering an epoxy 5015 resin-based carbon fiber reinforced composite material under the conditions of normal pressure and low temperature, which can effectively remove residual resin on the surface of the recovered carbon fiber and liquid products adhered to the surface of the carbon fiber by adopting deionized water ultrasonic cleaning after being cleaned for a plurality of times by absolute ethyl alcohol.
Experiments show that a test piece is placed in a mixed solution of an organic solvent and an alkaline catalyst, the employ 5015 epoxy resin-based carbon fiber reinforced composite material can be degraded and recovered under the conditions of normal pressure and low temperature, the temperature is 180 ℃ in the literature, the reaction time is 6 hours, the process conditions are milder (the reaction temperature is 150-170 ℃) and the reaction time is short (90-100 min). The obtained carbon fiber has clean and tidy surface without resin residue, maintains 90 percent of the monofilament tensile strength of the original carbon fiber, and the resin degradation rate of the employ 5015 epoxy resin-based carbon fiber reinforced composite material reaches more than 98 percent.
The employ 5015 epoxy resin-based carbon fiber reinforced composite material is successfully degraded at a lower temperature in a shorter time, the performance retention rate of the obtained fiber is high, no toxic gas is generated in the whole process, and the method is green and environment-friendly and is beneficial to the realization of industrial recycling of the thermosetting carbon fiber reinforced composite material.
Drawings
FIG. 1: schematic of the recovery Process
FIG. 2: scanning Electron Microscope (SEM) picture of surface appearance of carbon fiber after recovery of carbon fiber reinforced composite material in embodiment of the invention
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
the following examples refer to fig. 1 and 2.
In this example, the epoxy resin-based carbon fiber reinforced composite material of the employ 5015 is recovered by the following steps:
the first embodiment is as follows:
the method comprises the following steps: mixing the amine cured epoxy resin-based carbon fiber reinforced composite material CFRP with 30ml of glacial acetic acid, and adding a magnetic stirring rotor, wherein the weight of each 3.26g of the amine cured epoxy resin-based carbon fiber reinforced composite material CFRP is mixed with 30ml of glacial acetic acid;
step two: heating to 80-90 ℃, and reacting at constant temperature for 30-40 min to obtain CFRP internally layered;
step three: washing with deionized water for several times, and drying in an oven at 100 deg.C for 2h to obtain pretreated CFRP;
step four: adding the pretreated CFRP into a mixed solution containing monoethanolamine MEA and potassium hydroxide KOH, heating to 150-170 ℃, and reacting at constant temperature for 90-100 min;
the potassium hydroxide KOH of the mixed solution is 1.20g, and the monoethanolamine MEA is 60 ml;
step five: separating the reacted solid product and liquid product by a filter screen, cleaning the solid product by absolute ethyl alcohol, and removing the residual resin matrix and the adhered degradation liquid on the surface of the solid product
Step six: ultrasonically cleaning the solid product for 2-3 times by using deionized water, and drying the cleaned solid product in a drying oven at the temperature of about 80 ℃ for 12 hours to complete the recovery of the amine cured epoxy resin-based carbon fiber reinforced composite material.
The concentration of the catalyst KOH is 2 wt%.
Example two:
the method comprises the following steps: mixing the amine cured epoxy resin-based carbon fiber reinforced composite material CFRP with 30ml of glacial acetic acid, and adding a magnetic stirring rotor, wherein the weight of each 3.57g of the amine cured epoxy resin-based carbon fiber reinforced composite material CFRP is mixed with 30ml of glacial acetic acid;
step two: heating to 80-90 ℃, and reacting at constant temperature for 30-40 min to obtain CFRP internally layered;
step three: washing with deionized water for several times, and drying in an oven at 100 deg.C for 2h to obtain pretreated CFRP;
step four: adding the pretreated CFRP into a mixed solution containing monoethanolamine MEA and potassium hydroxide KOH, heating to 150-170 ℃, and reacting at constant temperature for 90-100 min;
the potassium hydroxide KOH of the mixed solution is 3.03g, and the monoethanolamine MEA is 60 ml;
step five: separating the reacted solid product and liquid product by a filter screen, cleaning the solid product by absolute ethyl alcohol, and removing the residual resin matrix and the adhered degradation liquid on the surface of the solid product
Step six: ultrasonically cleaning the solid product for 2-3 times by using deionized water, and drying the cleaned solid product in a drying oven at the temperature of about 80 ℃ for 12 hours to complete the recovery of the amine cured epoxy resin-based carbon fiber reinforced composite material.
The concentration of the catalyst KOH was 5 wt%.
Example three:
the method comprises the following steps: mixing the amine cured epoxy resin-based carbon fiber reinforced composite material CFRP with 30ml of glacial acetic acid, and adding a magnetic stirring rotor, wherein the weight of each 3.72g of the amine cured epoxy resin-based carbon fiber reinforced composite material CFRP is mixed with 30ml of glacial acetic acid;
step two: heating to 80-90 ℃, and reacting at constant temperature for 30-40 min to obtain CFRP internally layered;
step three: washing with deionized water for several times, and drying in an oven at 100 deg.C for 2h to obtain pretreated CFRP;
step four: adding the pretreated CFRP into a mixed solution containing monoethanolamine MEA and potassium hydroxide KOH, heating to 150-170 ℃, and reacting at constant temperature for 90-100 min;
the potassium hydroxide KOH of the mixed solution is 6.06g, and the monoethanolamine MEA is 60 ml;
step five: separating the reacted solid product and liquid product by a filter screen, cleaning the solid product by absolute ethyl alcohol, and removing the residual resin matrix and the adhered degradation liquid on the surface of the solid product
Step six: ultrasonically cleaning the solid product for 2-3 times by using deionized water, and drying the cleaned solid product in a drying oven at the temperature of about 80 ℃ for 12 hours to complete the recovery of the amine cured epoxy resin-based carbon fiber reinforced composite material.
The concentration of the catalyst KOH is 10 wt%.
Claims (2)
1. A normal pressure solvent recovery method of an amine curing epoxy resin based carbon fiber reinforced composite material is characterized by comprising the following steps:
step 1: mixing the amine cured epoxy resin-based carbon fiber reinforced composite material CFRP with 30ml of glacial acetic acid according to the weight of 3-4 g, and adding an alkali metal catalyst and magnetic magnetons;
step 2: heating to 80-90 ℃, and reacting at constant temperature for 30-40 min to obtain CFRP internally layered;
and step 3: washing with deionized water for several times, and drying in an oven at 100 deg.C for 2h to obtain pretreated CFRP;
and 4, step 4: adding the pretreated CFRP into a mixed solution containing monoethanolamine MEA and potassium hydroxide KOH, heating to 150-170 ℃, and reacting at constant temperature for 90-100 min;
the potassium hydroxide KOH of the mixed solution is 2.02-6.06 g, and the monoethanolamine MEA is 60 ml;
and 5: separating the reacted solid product and the liquid product through a filter screen, and removing the residual resin matrix and the adhered degradation liquid on the surface of the solid product by adopting absolute ethyl alcohol to the solid product;
step 6: ultrasonically cleaning the carbon fiber reinforced composite material by deionized water for 2-3 times, and drying the cleaned solid product in an oven at the temperature of about 80 ℃ for 12 hours to complete the recovery of the amine cured epoxy resin-based carbon fiber reinforced composite material.
2. The method for recovering the normal-pressure solvent of the amine curing epoxy resin-based carbon fiber reinforced composite material as claimed in claim 1, wherein the method comprises the following steps: the concentration of the catalyst KOH is 2-10 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010613895.1A CN111793246A (en) | 2020-06-30 | 2020-06-30 | Normal-pressure solvent recovery method for amine curing epoxy resin-based carbon fiber reinforced composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010613895.1A CN111793246A (en) | 2020-06-30 | 2020-06-30 | Normal-pressure solvent recovery method for amine curing epoxy resin-based carbon fiber reinforced composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111793246A true CN111793246A (en) | 2020-10-20 |
Family
ID=72809904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010613895.1A Pending CN111793246A (en) | 2020-06-30 | 2020-06-30 | Normal-pressure solvent recovery method for amine curing epoxy resin-based carbon fiber reinforced composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111793246A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876734A (en) * | 2021-01-13 | 2021-06-01 | 西北工业大学 | Method for recycling epoxy resin-based carbon fiber composite material under mild condition |
| CN114736425A (en) * | 2022-04-17 | 2022-07-12 | 西北工业大学 | Method for recycling carbon fiber reinforced bismaleimide resin matrix composite |
| WO2024060177A1 (en) * | 2022-09-23 | 2024-03-28 | 上纬创新育成股份有限公司 | Method for degrading anhydride epoxy cured product, polyol prepared therefrom, and thermosetting resin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013075950A (en) * | 2011-09-29 | 2013-04-25 | Kaneko Kagaku:Kk | Solvent composition for dissolving synthetic resin |
| WO2018183847A1 (en) * | 2017-04-01 | 2018-10-04 | The Boeing Company | Method for recovering carbon fibers from composite waste |
| CN109749124A (en) * | 2018-12-19 | 2019-05-14 | 西北工业大学 | The recovery method of thermosetting resin base fiber reinforced composite material in a mild condition |
| CN110172177A (en) * | 2019-05-28 | 2019-08-27 | 西北工业大学 | Rapidly and efficiently recycle the method for high performance resin base carbon fiber composite material |
-
2020
- 2020-06-30 CN CN202010613895.1A patent/CN111793246A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013075950A (en) * | 2011-09-29 | 2013-04-25 | Kaneko Kagaku:Kk | Solvent composition for dissolving synthetic resin |
| WO2018183847A1 (en) * | 2017-04-01 | 2018-10-04 | The Boeing Company | Method for recovering carbon fibers from composite waste |
| CN109749124A (en) * | 2018-12-19 | 2019-05-14 | 西北工业大学 | The recovery method of thermosetting resin base fiber reinforced composite material in a mild condition |
| CN110172177A (en) * | 2019-05-28 | 2019-08-27 | 西北工业大学 | Rapidly and efficiently recycle the method for high performance resin base carbon fiber composite material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876734A (en) * | 2021-01-13 | 2021-06-01 | 西北工业大学 | Method for recycling epoxy resin-based carbon fiber composite material under mild condition |
| CN114736425A (en) * | 2022-04-17 | 2022-07-12 | 西北工业大学 | Method for recycling carbon fiber reinforced bismaleimide resin matrix composite |
| CN114736425B (en) * | 2022-04-17 | 2024-02-09 | 西北工业大学 | Method for recycling carbon fiber reinforced bismaleimide resin matrix composite material |
| WO2024060177A1 (en) * | 2022-09-23 | 2024-03-28 | 上纬创新育成股份有限公司 | Method for degrading anhydride epoxy cured product, polyol prepared therefrom, and thermosetting resin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111793246A (en) | Normal-pressure solvent recovery method for amine curing epoxy resin-based carbon fiber reinforced composite material | |
| CN102181071B (en) | Method for reclaiming carbon fiber reinforced epoxy resin composite material | |
| CN105906836A (en) | Recovering method of carbon fiber reinforced resin matrix composite material under mild conditions | |
| CN112961403B (en) | Recovery method of fiber-reinforced epoxy resin composite material | |
| CN109897216A (en) | A kind of recoverying and utilizing method of waste and old thermosetting resin and its composite material | |
| CN109320918A (en) | Recyclable carbon-fibre reinforced epoxy resin composite material, preparation method and application | |
| CN1213096C (en) | Chenical recovery method for thermosetting epoxy compound material | |
| CN101429100B (en) | Chemical recovery method for waste polycarbonate material in ionic liquid surrounding | |
| CN100497507C (en) | Process of preparing ester from rosin and acrylate | |
| CN114773667B (en) | Method for recycling wind power blade under mild condition by using transition metal catalyst | |
| CN106496631A (en) | The method that overcritical fluid-mixing reclaims carbon fiber enhancement resin base composite material | |
| CN103333360B (en) | Reinforcement mode based high-performance fiber reinforced resin based composite material recovery method | |
| CN109749124A (en) | The recovery method of thermosetting resin base fiber reinforced composite material in a mild condition | |
| CN113603929A (en) | Recovery method of epoxy resin composite material, obtained glass fiber and application thereof | |
| CN104971774A (en) | Preparation method for hydrofluoroether and catalyst thereof | |
| CN110172177B (en) | Method for rapidly and efficiently recovering high-performance resin-based carbon fiber composite material | |
| CN112029147A (en) | Chemical recovery method of aramid fiber reinforced composite material | |
| CN112679797A (en) | Method for recovering carbon fiber reinforced resin matrix composite material by subcritical fluid | |
| CN111196879A (en) | Method for recovering carbon fibers from carbon fiber reinforced thermosetting resin-based composite material | |
| Gao et al. | NaOH/urea swelling treatment and hydrothermal degradation of waste cotton fiber | |
| CN114736425B (en) | Method for recycling carbon fiber reinforced bismaleimide resin matrix composite material | |
| CN115850910A (en) | Bio-based hyperbranched polymer epoxy resin and preparation method and application thereof | |
| CN113980305A (en) | Preparation method of degradable high-performance fiber-reinforced epoxy resin-based composite material | |
| CN109384872B (en) | Chelate resin and preparation method and application thereof | |
| CN114589196B (en) | Method for recycling thermosetting resin and composite material thereof through mild oxidative degradation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |