CN109749124A - The recovery method of thermosetting resin base fiber reinforced composite material in a mild condition - Google Patents
The recovery method of thermosetting resin base fiber reinforced composite material in a mild condition Download PDFInfo
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- CN109749124A CN109749124A CN201811556210.3A CN201811556210A CN109749124A CN 109749124 A CN109749124 A CN 109749124A CN 201811556210 A CN201811556210 A CN 201811556210A CN 109749124 A CN109749124 A CN 109749124A
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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
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
The invention discloses a kind of recovery method of thermosetting resin base fiber reinforced composite material in a mild condition, for solving the technical problem of existing thermosetting resin based composites recovery method reaction time length.Technical solution is to weigh potassium hydroxide first, in accordance with composite material and potassium hydroxide quality ratio 1:0.54, it is added in reaction kettle together with monoethanolamine, and catalyst and magneton is added, composite material is added in mixed solution again and is warming up to 160~170 DEG C, 80~90min of isothermal reaction, by the solid product separation in mixed solution, the solid product being collected into is cleaned with acetone, remove the residual resin matrix of carbon fiber surface and the degradation solution of adherency in solid product, it is cleaned by ultrasonic 2~3 times with deionized water, solid product after cleaning is placed in 60 DEG C of baking oven to dry 10h and be placed in 40 DEG C of baking oven and dries 12h.Reaction condition of the present invention is mild, and recovery efficiency is high, and the carbon fiber surface pattern of recycling is good.
Description
Technical field
The present invention relates to a kind of recovery method of thermosetting resin based composites, in particular to a kind of thermosetting resin base
The recovery method of fibre reinforced composites in a mild condition.
Background technique
Carbon fiber-reinforced thermosetting polymer matrix composites have high specific strength, high specific stiffness, high temperature resistant, corrosion-resistant, resistance to
The characteristics such as fatigue, thus it is widely used in the industries such as aerospace, machine-building, traffic and sports goods.
In recent years, the composite material of fibre reinforced using carbon fibre composite that is more and more extensive, generating therewith
Waste can not be melted or be dissolved because forming three-dimensional cross-linked reticular structure when curing molding, it is difficult to processing and recycling, therefore cause
Serious environmental problem.To realize sustainable development, more and more countries pay attention to carbon fibre composite waste
It recycles.
Currently, chemical recovery includes chemical-solvent method and supercritical fluid method.Chemical-solvent method is to use in atmospheric conditions
Chemical bond in specific degradation solvent and catalyst fracture carbon fibre composite, to make resin matrix and reinforcement point
From.This method mild condition generates pollution in reaction process.Hydrogen peroxide, can be with as a kind of strong oxidizer
Efficient degradation carbon fibre composite, but corresponding safety problem can be brought.In addition, nitric acid, lewis acid can degrade
Epoxy resin, for example, Tuan Liu et al. people has studied the resin matrix in thermosetting resin based composites at phosphotungstic acid (HPW)
It is degraded to resin monomer molecule or other small molecules in aqueous solution, comprises the concrete steps that: first, 0.2g heteropoly acid is dissolved in
19.8g in water.Second, the epoxy resin of obtained phosphotungstic acid aqueous solution and 6.0g anhydride-cured is added to pressurized reactor.
Pressurized reactor temperature is increased to 190 DEG C, 5~6h of isothermal reaction by third.The resulting carbon fiber surface pattern of the method is preferable
And performance is also relatively good, degradation efficiency is up to 95% or more.However, the time that this method needs is long (5-6h).
Summary of the invention
In order to overcome the shortcomings of that the existing thermosetting resin based composites recovery method reaction time is long, the present invention provides one
The recovery method of kind thermosetting resin base fiber reinforced composite material in a mild condition.This method first, in accordance with composite material with
Potassium hydroxide quality ratio 1:0.54 weighs potassium hydroxide, is added in reaction kettle together with monoethanolamine, and be added catalyst and
Magneton, then composite material is added in mixed solution and is warming up to 160~170 DEG C, 80~90min of isothermal reaction, by mixed solution
In solid product separation, the solid product being collected into is cleaned with acetone, remove solid product in carbon fiber surface remnants
The degradation solution of resin matrix and adherency is cleaned by ultrasonic 2~3 times with deionized water, the solid product after cleaning is placed in 60 DEG C
10h is dried in baking oven and is placed in 40 DEG C of baking oven dries 12h.Reaction condition of the present invention is mild, and recovery efficiency is high, the carbon fiber of recycling
Surface topography is good.
A kind of the technical solution adopted by the present invention to solve the technical problems: thermosetting resin base fiber reinforced composite material
Recovery method in a mild condition, its main feature is that the following steps are included:
Step 1: weighing potassium hydroxide according to composite material and potassium hydroxide quality ratio 1:0.54.
Step 2: potassium hydroxide and monoethanolamine as reaction dissolvent are added in reaction kettle, and catalyst is added
And magneton.
Step 3: composite material is added in mixed solution made from step 2 and is warming up to 160~170 DEG C, constant temperature
React 80~90min.
Step 4: the mixed solution that step 3 is obtained separates, and collect solid product.The solid being collected into is produced
Object is cleaned with acetone, is removed the residual resin matrix of carbon fiber surface and the degradation solution of adherency in solid product, is used deionized water
Solid product after cleaning is placed in 9~10h of baking in 60~65 DEG C of baking oven, is placed in 40~45 DEG C by ultrasonic cleaning 2~3 times
11~12h is dried in baking oven.
The beneficial effects of the present invention are: this method weighs hydrogen first, in accordance with composite material and potassium hydroxide quality ratio 1:0.54
Potassium oxide is added in reaction kettle together with monoethanolamine, and catalyst and magneton is added, then composite material addition mixing is molten
It is warming up to 160~170 DEG C, 80~90min of isothermal reaction in liquid, the solid product in mixed solution is separated, by what is be collected into
Solid product is cleaned with acetone, is removed the residual resin matrix of carbon fiber surface and the degradation solution of adherency in solid product, is spent
Ionized water is cleaned by ultrasonic 2~3 times, the solid product after cleaning is placed in 60 DEG C of baking oven and dries the baking oven that 10h is placed on 40 DEG C
Middle baking 12h.Reaction condition of the present invention is mild, and recovery efficiency is high, and the carbon fiber surface pattern of recycling is good.
After tested, reaction temperature drops to 160~170 DEG C by 190 DEG C of background technique, and the reaction time is by background technique
5h drops to 80~90min.
It elaborates with reference to the accompanying drawings and detailed description to the present invention.
Detailed description of the invention
Fig. 1 is the stereoscan photograph (SEM) for the carbon fiber surface pattern that embodiment of the present invention method 1 recycles.
Fig. 2 is the partial enlarged view of Fig. 1.
Specific embodiment
Following embodiment referring to Fig.1-2.
Embodiment 1:
Step 1: required degradation solvent is monoethanolamine (MEA).Contain amino and hydroxyl in MEA, under alkaline condition may be used
To carry out ester exchange reaction with ester, while amino also can be used as the catalyst of ester exchange reaction.
Step 2: required catalyst is potassium hydroxide, bisphenol A type epoxy resin and quality (g) ratio of potassium hydroxide be
1:0.54。
Step 3: measuring 15mm × 15mm × 3mm composite fiber plate as test specimen, according to test specimen and potassium hydroxide
Mass ratio weigh be 2.659g test specimen and 1.436g potassium hydroxide.
Step 4: being added in reaction kettle using 75ml monoethanolamine as reaction dissolvent, catalyst and magneton is added.
Step 5: test specimen is added in the mixed solution of step 4 and is warming up to 170 DEG C, isothermal reaction 80min.
Step 6: by after reaction solid product and product liquid separated by strainer, and collect solid product.It will
The solid product being collected into is cleaned with acetone, with residual resin matrix and the degradation solution of adherency etc. for removing carbon fiber surface.So
Deionized water is cleaned by ultrasonic 3 times afterwards, the solid product after cleaning is placed in 60 DEG C of baking oven and dries the baking oven that 10h is placed on 40 DEG C
Middle baking 12h.
After tested, the carbon mono-filaments tensile strength of the present embodiment recycling is 2.45GPa, and precursor tensile strength is
2.64GPa maintains 92% or more of precursor tensile strength.
The carbon fiber surface that can see recycling from Fig. 1,2 is very smooth and does not have resin residue.
Embodiment 2:
Step 1: required degradation solvent is monoethanolamine (MEA).Contain amino and hydroxyl in MEA, under alkaline condition may be used
To carry out ester exchange reaction with ester, while amino also can be used as the catalyst of ester exchange reaction.
Step 2: required catalyst is potassium hydroxide, bisphenol A type epoxy resin and quality (g) ratio of potassium hydroxide be
1:0.54。
Step 3: measuring 20mm × 15mm × 3mm composite fiber plate as test specimen, according to test specimen and potassium hydroxide
Mass ratio weigh be 3.157g test specimen and 1.705g potassium hydroxide.
Step 4: being added in reaction kettle using 75ml monoethanolamine as reaction dissolvent, catalyst and magneton is added.
Step 5: test specimen is added in the mixed solution of step 4 and is warming up to 165 DEG C, isothermal reaction 85min.
Step 6: by after reaction solid product and product liquid separated by strainer, and collect solid product.It will
The solid product being collected into is cleaned with acetone, with residual resin matrix and the degradation solution of adherency etc. for removing carbon fiber surface.So
Deionized water is cleaned by ultrasonic 3 times afterwards, the solid product after cleaning is placed in 60 DEG C of baking oven and dries the baking oven that 10h is placed on 40 DEG C
Middle baking 12h.
After tested, the carbon mono-filaments tensile strength of the present embodiment recycling is 2.53GPa, and precursor tensile strength is
2.58GPa maintains 98% or more of precursor tensile strength.
Embodiment 3:
Step 1: required degradation solvent is monoethanolamine (MEA).Contain amino and hydroxyl in MEA, under alkaline condition may be used
To carry out ester exchange reaction with ester, while amino also can be used as the catalyst of ester exchange reaction.
Step 2: required catalyst is potassium hydroxide, bisphenol A type epoxy resin and quality (g) ratio of potassium hydroxide be
1:0.54。
Step 3: measuring 20mm × 20mm × 4mm composite fiber plate as test specimen, according to test specimen and potassium hydroxide
Mass ratio weigh be 3.657g test specimen and 1.975g potassium hydroxide.
Step 4: being added in reaction kettle using 75ml monoethanolamine as reaction dissolvent, catalyst and magneton is added.
Step 5: test specimen is added in the mixed solution of step 4 and is warming up to 160 DEG C, isothermal reaction 90min.
Step 6: by after reaction solid product and product liquid separated by strainer, and collect solid product.It will
The solid product being collected into is cleaned with acetone, with residual resin matrix and the degradation solution of adherency etc. for removing carbon fiber surface.So
Deionized water is cleaned by ultrasonic 2 times afterwards, the solid product after cleaning is placed in 65 DEG C of baking oven and dries the baking oven that 9h is placed on 45 DEG C
Middle baking 11h.
After tested, the carbon mono-filaments tensile strength of the present embodiment recycling is 2.08GPa, and precursor tensile strength is
2.27GPa maintains 92% or more of precursor tensile strength.
Compared with the background art, the required reaction temperature of the present invention is lower, and the reaction time is shorter, resulting carbon fiber surface
It is very smooth and there is no resin residue, and good mechanical property is maintained, substantially increases the increasing of thermosetting resin base fiber
The recovery efficiency of strong composite material.
Claims (1)
1. a kind of recovery method of thermosetting resin base fiber reinforced composite material in a mild condition, it is characterised in that including with
Lower step:
Step 1: weighing potassium hydroxide according to composite material and potassium hydroxide quality ratio 1:0.54；
Step 2: potassium hydroxide and monoethanolamine as reaction dissolvent are added in reaction kettle, and catalyst and magnetic is added
Son；
Step 3: composite material is added in mixed solution made from step 2 and is warming up to 160~170 DEG C, isothermal reaction
80~90min；
Step 4: the mixed solution that step 3 is obtained separates, and collect solid product；The solid product being collected into is used
Acetone cleaning, removes the residual resin matrix of carbon fiber surface and the degradation solution of adherency in solid product, with deionized water ultrasound
Solid product after cleaning is placed in 9~10h of baking in 60~65 DEG C of baking oven, is placed in 40~45 DEG C of baking oven by cleaning 2~3 times
11~12h of middle baking.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111793246A (en) * | 2020-06-30 | 2020-10-20 | 西北工业大学 | Normal-pressure solvent recovery method for amine curing epoxy resin-based carbon fiber reinforced composite material |
| 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 |
| CN113621171A (en) * | 2021-09-11 | 2021-11-09 | 哈尔滨工业大学 | Method for lossless recovery of reinforcement in waste carbonyl-containing thermosetting resin 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 |
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| US20100278716A1 (en) * | 2007-12-19 | 2010-11-04 | Toray Industries, Inc. | Dispersion containing flame-resistant polymer, flame-resistant fiber, and carbon fiber |
| CN105906836A (en) * | 2016-05-09 | 2016-08-31 | 西北工业大学 | Recovering method of carbon fiber reinforced resin matrix composite material under mild conditions |
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- 2018-12-19 CN CN201811556210.3A patent/CN109749124A/en active Pending
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|---|---|---|---|---|
| US20100278716A1 (en) * | 2007-12-19 | 2010-11-04 | Toray Industries, Inc. | Dispersion containing flame-resistant polymer, flame-resistant fiber, and carbon fiber |
| CN105906836A (en) * | 2016-05-09 | 2016-08-31 | 西北工业大学 | Recovering method of carbon fiber reinforced resin matrix composite material under mild conditions |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110172177B (en) * | 2019-05-28 | 2022-06-10 | 西北工业大学 | Method for rapidly and efficiently recovering high-performance resin-based carbon fiber composite material |
| CN111793246A (en) * | 2020-06-30 | 2020-10-20 | 西北工业大学 | Normal-pressure solvent recovery method for amine curing epoxy resin-based carbon fiber reinforced composite material |
| 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 |
| CN113621171A (en) * | 2021-09-11 | 2021-11-09 | 哈尔滨工业大学 | Method for lossless recovery of reinforcement in waste carbonyl-containing thermosetting resin under mild condition |
| CN113621171B (en) * | 2021-09-11 | 2023-08-18 | 哈尔滨工业大学 | Method for nondestructively recycling reinforcement in waste carbonyl-containing thermosetting resin 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 |
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Application publication date: 20190514 |