CN108912389A - The recovery method of carbon fiber in a kind of carbon fiber/bismaleimide resin composite material - Google Patents
The recovery method of carbon fiber in a kind of carbon fiber/bismaleimide resin composite material Download PDFInfo
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- CN108912389A CN108912389A CN201810798606.2A CN201810798606A CN108912389A CN 108912389 A CN108912389 A CN 108912389A CN 201810798606 A CN201810798606 A CN 201810798606A CN 108912389 A CN108912389 A CN 108912389A
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/36—Oxygen or sulfur atoms
- C07D207/40—2,5-Pyrrolidine-diones
- C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
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- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The recovery method of carbon fiber is the degradation system of preparing metal nitrate and protic composition in a kind of carbon fiber/bismaleimide resin composite material, carbon fiber/bismaleimide resin composite material after cutting is completely immersed in degradation system and is degraded, it is cooled to room temperature after the reaction was completed, lytic agent dissolution is added, solid product carbon fiber and resin catabolite solution is obtained by filtration.The advantages of present invention realizes the controllable chemical degradation of carbon fiber/bismaleimide resin composite material, 100% recycling carbon fiber, and carbon mono-filaments loss of tensile strength is less than 3%.
Description
Technical field
The invention belongs to high molecular materials to recycle and recycling field, and in particular to a kind of carbon fiber/bismaleimide resin
The degradation recycling method of composite material.
Technical background
Bimaleimide resin (abbreviation bismaleimide resin, English name Bismaleimide resin, English abbreviation
BMI) it is the another kind of resin system derived from by polyimide resin system, is the difunctionality using maleimide as active end group
Group compound, have with mobility similar in epoxy resin and mouldability, can be carried out with the similar conventional method of epoxy resin
Machine-shaping overcomes the relatively low disadvantage of epoxy resin heat resistance, and therefore, recent two decades are obtained rapidly developing and be answered extensively
With.Bismaleimide is with its excellent heat resistance, electrical insulating property, wave, radiation resistance, good mechanical property and size
The features such as stability, moulding process is similar to epoxy resin, it is widely used in the industrial circles such as Aeronautics and Astronautics, machinery, electronics
In, resin matrix, high-temperature insulation material and adhesive of advanced composite material etc..In bismaleimide resin monomer structure, C=C double bond
By two carbonyls in ortho position electron attraction and become electron-deficient key, thus easily with diamine, amide, hydrazides, hydrogen sulfide, cyanogen urinate
The compound containing active hydrogen such as acid and polyphenol carries out addition reaction, it can also be the same as compound, epoxy containing unsaturated double-bond
Resin and other structures bismaleimide resin carry out copolyreaction, while also can issue raw self-polymeric reaction in catalyst or heat effect.It is double
Horse resin solidify and rear solidification temperature and its structure have very big relationship, the solidification temperature of general bismaleimide resin and its modified resin
Degree is 200oC-220oC, post-processing temperature 230oC-250oC.Bismaleimide resin is due to containing phenyl ring, acid imide heterocycle and friendship
Connection density is higher and its solidfied material is made to have excellent heat resistance, and Tg is generally higher than 250 oC, the use of temperature is 177 oC-
232oC or so.Ethylenediamine is most stable in aliphatic bismaleimide resin, increases initial decomposition temperature (T with methylene numberd) will
Decline.The T of aromatic series bismaleimide resindGenerally all it is higher than aliphatic bismaleimide resin, wherein the T of 2,4- diaminobenzene classesdHigher than other
Type.Secondly, TdThere is close relationship with crosslink density, is increased in a certain range with the increase of crosslink density.It is double
The curing reaction of horse resin resin belongs to polyaddition reaction, releases in forming process without low molecule by-product, and be easy to control,
Solidfied material compact structure, defect is few, thus, bismaleimide resin solidfied material intensity and modulus with higher, chemical structure such as Fig. 1
It is shown.Bismaleimide resin solidfied material thermal decomposition process be it is considerably complicated, to its thermal decomposition of the bismaleimide resin solidfied material of different structure
Process is not also identical, is mainly the following form.(1) thermal decomposition of aliphatic bismaleimide resin solidfied material typically occurs in acyl
C-C chain in the m- R- chain of imide ring, wherein the C-C key mainly near acid imide.(2) aromatic series bismaleimide resin solidfied material
Thermal cracking is different from aliphatic bismaleimide resin solidfied material, their starting degradation reaction is the cracking of maleimide ring.Currently,
There is not been reported for the chemical method degradation recycling of waste and old carbon fiber/bismaleimide resin composite material.
Summary of the invention
The object of the present invention is to provide a kind of degradation condition is mild, the carbon fiber/bismaleimide resin for not generating waste is compound
The degradation recycling method of material.
The present invention utilizes nitrate and proton type since nitrate anion has strong oxidation in the presence of hydrogen ion
Solvent concerted catalysis, the crosslinking to waste and old carbon fiber/bismaleimide resin composite material solid selectively fracture bismaleimide resin solidfied material
Key realizes the controlled degradation of bismaleimide resin.Bismaleimide resin catabolite (hydrogenation bismaleimide monomer) and curing agent are recycled,
Carbon fiber in recyclable bismaleimide resin based composites simultaneously.
The specific technical solution of the present invention is as follows：
The recovery method of carbon fiber, includes the following steps in a kind of carbon fiber/bismaleimide resin composite material：
The metal nitrate of mass fraction 1%-30% and the degradation system of protic composition are prepared, by carbon fiber/span tree
Resin composite material and degradation system quality are than 1:Carbon fiber/bismaleimide resin composite material after cutting is completely immersed in drop by 1-100
Enzymatic hydrolysis system, and be sealed in acid corrosion-resistant reaction kettle, degradation reaction temperature 150-280oC, reaction time 10min-24h, reaction
After the completion, it is cooled to room temperature, is 1 by the mass ratio of catabolite mixture and lytic agent:1-10 is added lytic agent and dissolves 1-
Solid product carbon fiber and resin catabolite solution is obtained by filtration in 10min, and precipitating is added into resin catabolite solution
Agent, bismaleimide resin catabolite are precipitated, are filtered, washed, are dried, obtain bismaleimide resin catabolite；By solvent, lytic agent and
Precipitating reagent is distilled to recover, while obtaining metal nitrate, is recycled after carbon fiber is washed and dry.
When the degradation system quality score that metal nitrate and protic form is lower than 1%, catalyst is in resin
Portion's content is too low, cannot sufficiently be coordinated with resin activity site, and degradation effect is decreased obviously, and when being higher than 30%, catalyst and molten
Agent coordination is precipitated, and causes solvent swell performance to decline, cannot degrade bismaleimide resin.Carbon fiber/bismaleimide resin composite material and drop
System additional amount of degrading in enzymatic hydrolysis system is lower than 1:1（Mass ratio）When, composite material cannot be completely immersed in degradation system, and catalyst is not
It can be diffused not immersing part, cause its degradation insufficient, and be higher than 1:When 100, resin degradation rate is very fast, causes to drop
Under enzymatic hydrolysis system hot conditions, carbon fiber is contacted for a long time, so that the intensity decline of recycling carbon fiber is obvious.When degradation reaction temperature
Lower than 150oWhen C, the activation energy of chemical bond rupture under catalytic condition is not achieved, degradation reaction not can be carried out, and degradation reaction temperature
Degree is higher than 280oWhen C, when bismaleimide resin is degraded, a variety of small molecule compounds containing phenyl ring can be generated, catabolite complicated component, and
It is serious to recycle carbon fiber strength loss.When degradation time is lower than 10min, cannot sufficiently be swollen, catalyst cannot be diffused into tree
Inside rouge, degradation reaction can hardly be carried out, and degradation time be higher than for 24 hours when, cause resin degrade after carbon fiber and degradation body
System contacts for a long time, and the intensity that the oxidisability of nitrate anion will lead to carbon fiber is decreased obviously.When catabolite mixture and dissolution
Lytic agent is less than 1 in the mass ratio of agent:When 1, catabolite mixture cannot sufficiently dissolve, and when catabolite mixture with it is molten
It solves lytic agent in the mass ratio of agent and is higher than 1:When 10, content of degradation products is too low, and solubility is unknown to lytic agent change in polarity
It is aobvious, cause later stage degradation product Precipitation difficult.
The metal nitrate include ferric nitrate, aluminum nitrate, cobalt nitrate, nickel nitrate, chromic nitrate, zinc nitrate, calcium nitrate,
One of magnesium nitrate, copper nitrate, silver nitrate, potassium nitrate or sodium nitrate.
The protic include methanol, ethyl alcohol, normal propyl alcohol, isopropanol, ethylene glycol, glycerine, formic acid, acetic acid,
The mixture that one or more of propionic acid, butyric acid, water are formed, wherein except the mixture of alcohols and acids（Because ester occurs in it
Change reaction）.
The carbon fiber/bismaleimide resin composite material full name is carbon fiber reinforced bismalemide resin composite wood
Material, wherein carbon fiber includes the models such as T300, T700, T800 or T1000, and bimaleimide resin refers to that vinyl is crosslinked
Bismaleimide after the crosslinking curings such as agent, amine curing agent or alcohols curing agent.
It is 1cm that the carbon fiber/bismaleimide resin composite material, which is cut into volume,3-1m3Irregular shape.
It is alloy or Hastelloy etc. that the acid corrosion-resistant reaction kettle material, which includes zirconium material, titanium, illiteracy,.
Lytic agent used in the dissolution catabolite includes dimethyl sulfoxide, tetrahydrofuran, acetone, toluene, N-
One of methyl pyrrolidone or N,N-dimethylformamide.
The precipitating reagent includes one of ethyl acetate, chloroform, acetonitrile or hexamethylene.
The invention has the advantages that：
1, the controllable chemical degradation of carbon fiber/bismaleimide resin composite material may be implemented, (hydrogenation is double for recycling bismaleimide resin catabolite
Maleimide resin monomer) and curing agent, wherein hydrogenation bimaleimide resin monomer can be used for producing bismaleimide
Polyimide resin monomer, while can be with 100% recycling carbon fiber, and carbon mono-filaments loss of tensile strength is less than 3%.
2, degradation condition is relatively mild, and degradation process does not generate waste, and solvent for use and metal nitrate can weigh
It is multiple to utilize.
Detailed description of the invention
Fig. 1 is bismaleimide resin solidfied material molecular structure.Wherein, R is aliphatic or aromatic group.R1And R2It is span tree
Group after rouge double bond and active hydrogen or allyl based cross-linker addition polymerization.
Fig. 2 is the carbon-13 nmr spectra of bismaleimide resin solidfied material catabolite (hydrogenation bimaleimide resin monomer).
Fig. 3 is recycling carbon fiber SEM picture.Wherein, (a) is the carbon fiber after starching, is (b) the carbon fiber warp after starching
Calcium nitrate/acetic acid processing (c) answers the carbon fiber of material recycling, (d) using aluminum nitrate/acetic acid degradation carbon fiber/bismaleimide resin
The carbon fiber of material recycling is answered using calcium nitrate/acetic acid degradation carbon fiber/bismaleimide resin.
Fig. 4 is the thermogravimetric characterization for recycling carbon fiber.Wherein, (a) is the carbon fiber after starching, is (b) carbon fiber after starching
The carbon fiber obtained after calcium nitrate/acetic acid degradation treatment is tieed up, calcium nitrate/acetic acid degradation carbon fiber/span tree (c) is utilized
Rouge answers the carbon fiber of material recycling, (d) fibre reinforced bismaleimide resin composite material.
Specific embodiment
Embodiment 1
Carbon fiber/bismaleimide resin composite material of the present embodiment degradation is handed over by carbon fiber T300, bismaleimide resin monomer and vinyl
Join agent to prepare by pressure sintering, wherein the monofilament tensile strength of carbon fiber T300 is 3530MPa.Degradation process is as follows：
The ferric nitrate of mass fraction 1% and the degradation system of formic acid composition are prepared, by carbon fiber/bismaleimide resin composite material and drop
Enzymatic hydrolysis system mass ratio 1:100,1cm will be cut into3Carbon fiber/bismaleimide resin composite material be completely immersed in degradation system, and it is close
It is encapsulated in zirconium material reaction kettle, degradation reaction temperature 180oC, reaction time 22h.After the reaction was completed, it is cooled to room temperature, N, N- is added
The mass ratio of dimethylformamide, catabolite mixture and n,N-Dimethylformamide is 1:10,1min is dissolved, is filtered
To solid product carbon fiber and liquid bismaleimide resin catabolite.Ethyl acetate, span is added into resin catabolite solution
Resin catabolite is precipitated, and is filtered, washed, is dried, and hydrogenation bismaleimide and curing agent are obtained；By formic acid, N, N- bis-
Methylformamide and ethyl acetate are distilled to recover, while recycling ferric nitrate；It is recycled after carbon fiber is washed and dry, carbon fiber returns
Yield is up to 100%, and monofilament tensile strength is 3495MPa.
Embodiment 2
Carbon fiber/bismaleimide resin composite material of the present embodiment degradation is by carbon fiber T700, bismaleimide resin monomer and amine-type cure
Agent is prepared by pressure sintering, and wherein the monofilament tensile strength of carbon fiber T700 is 4900MPa.Degradation process is as follows：
The aluminum nitrate of mass fraction 30% and the degradation system of acetic acid composition are prepared, by carbon fiber/bismaleimide resin composite material and drop
Enzymatic hydrolysis system mass ratio 1:1,1m will be cut into3Carbon fiber/bismaleimide resin composite material be completely immersed in degradation system, and be sealed in
In titanium reaction kettle, degradation reaction temperature 280oC, reaction time 10min.After the reaction was completed, it is cooled to room temperature, tetrahydro furan is added
It mutters, the mass ratio of catabolite mixture and tetrahydrofuran is 1:1,10min is dissolved, solid product carbon fiber and liquid is obtained by filtration
Body bismaleimide resin catabolite.Chloroform is added into resin catabolite solution, bismaleimide resin catabolite is precipitated, filtered,
Washing, drying, obtain hydrogenation bismaleimide and amine curing agent；Acetic acid, tetrahydrofuran and chloroform are distilled to recover, simultaneously
Recycle aluminum nitrate；It is recycled after carbon fiber is washed and dry, the carbon fiber rate of recovery is up to 100%, and monofilament tensile strength is
4826MPa。
Embodiment 3
Carbon fiber/bismaleimide resin composite material of the present embodiment degradation is solidified by carbon fiber T800, bismaleimide resin monomer and alcohols
Agent is prepared by pressure sintering, and wherein the monofilament tensile strength of carbon fiber T800 is 5490MPa.Degradation process is as follows：
The cobalt nitrate of mass fraction 15% and the degradation system of propionic acid composition are prepared, by carbon fiber/bismaleimide resin composite material and drop
Enzymatic hydrolysis system mass ratio 1:50,10 cm will be cut into3Carbon fiber/bismaleimide resin composite material be completely immersed in degradation system, and it is close
Being encapsulated in illiteracy is degradation reaction temperature 150 in alloy reaction kettleoC, the reaction time is for 24 hours.After the reaction was completed, it is cooled to room temperature, is added
The mass ratio of acetone, catabolite mixture and acetone is 1:8,8min is dissolved, solid product carbon fiber and liquid is obtained by filtration
Bismaleimide resin catabolite.Acetonitrile is added into resin catabolite solution, bismaleimide resin catabolite is precipitated, is filtered, washed
It washs, dry, obtain hydrogenation bismaleimide and alcohols curing agent；Propionic acid, acetone and acetonitrile are distilled to recover, while recycling nitre
Sour cobalt；It is recycled after carbon fiber is washed and dry, the carbon fiber rate of recovery is up to 100%, and monofilament tensile strength is 5374MPa.
Embodiment 4
Carbon fiber/bismaleimide resin composite material of the present embodiment degradation is by carbon fiber T1000, bismaleimide resin monomer and amine-type cure
Agent is prepared by pressure sintering, and wherein the monofilament tensile strength of carbon fiber T1000 is 7020MPa.Degradation process is as follows：
The nickel nitrate of mass fraction 20% and the degradation system of butyric acid composition are prepared, by carbon fiber/bismaleimide resin composite material and drop
Enzymatic hydrolysis system mass ratio 1:80,100 cm will be cut into3Carbon fiber/bismaleimide resin composite material be completely immersed in degradation system, and
It is sealed in Hastelloy reaction kettle, degradation reaction temperature 200oC, reaction time 18h.After the reaction was completed, it is cooled to room temperature, adds
Enter toluene, the mass ratio of catabolite mixture and toluene is 1:2,5min is dissolved, solid product carbon fiber and liquid is obtained by filtration
Body bismaleimide resin catabolite.Hexamethylene is added into resin catabolite solution, bismaleimide resin catabolite is precipitated, and passes through
Filter, washing, drying, obtain hydrogenation bismaleimide and amine curing agent；Butyric acid, toluene and hexamethylene are distilled to recover, together
Shi Huishou nickel nitrate；It is recycled after carbon fiber is washed and dry, the carbon fiber rate of recovery is up to 100%, and monofilament tensile strength is
6893MPa。
Embodiment 5
Carbon fiber/bismaleimide resin composite material of the present embodiment degradation is handed over by carbon fiber T300, bismaleimide resin monomer and vinyl
Join agent to prepare by pressure sintering, wherein the monofilament tensile strength of carbon fiber T300 is 3530MPa.Degradation process is as follows：
The chromic nitrate of mass fraction 25% and the degradation system of methanol composition are prepared, by carbon fiber/bismaleimide resin composite material and drop
Enzymatic hydrolysis system mass ratio 1:25,1cm will be cut into3Carbon fiber/bismaleimide resin composite material be completely immersed in degradation system, and seal
In Hastelloy reaction kettle, degradation reaction temperature 240oC, reaction time 12h.After the reaction was completed, it is cooled to room temperature, N- is added
The mass ratio of methyl pyrrolidone, catabolite mixture and N-Methyl pyrrolidone is 1:7,4min is dissolved, is obtained by filtration solid
Body product carbon fiber and liquid bismaleimide resin catabolite.Ethyl acetate, bismaleimide resin is added into resin catabolite solution
Catabolite is precipitated, and is filtered, washed, is dried, and hydrogenation bismaleimide and curing agent are obtained；By methanol, N- methylpyrrole
Alkanone and ethyl acetate are distilled to recover, while recycling chromic nitrate；It is recycled after carbon fiber is washed and dry, the carbon fiber rate of recovery can
Up to 100%, and monofilament tensile strength is 3491MPa.
Embodiment 6
Carbon fiber/bismaleimide resin composite material of the present embodiment degradation is by carbon fiber T300, bismaleimide resin monomer and amine-type cure
Agent is prepared by pressure sintering, and wherein the monofilament tensile strength of carbon fiber T300 is 3530MPa.Degradation process is as follows：
The calcium nitrate of mass fraction 18% and the degradation system of ethyl alcohol composition are prepared, by carbon fiber/bismaleimide resin composite material and drop
Enzymatic hydrolysis system mass ratio 1:20,1cm will be cut into3Carbon fiber/bismaleimide resin composite material be completely immersed in degradation system, and seal
In Hastelloy reaction kettle, degradation reaction temperature 260oC, reaction time 8h.After the reaction was completed, it is cooled to room temperature, N is added,
The mass ratio of dinethylformamide, catabolite mixture and n,N-Dimethylformamide is 1:5,3min is dissolved, is filtered
To solid product carbon fiber and liquid bismaleimide resin catabolite.Ethyl acetate, span is added into resin catabolite solution
Resin catabolite is precipitated, and is filtered, washed, is dried, and hydrogenation bismaleimide and amine curing agent are obtained；By ethyl alcohol, N,
Dinethylformamide and ethyl acetate are distilled to recover, while recycling calcium nitrate；It is recycled after carbon fiber is washed and dry, carbon fiber
The rate of recovery is tieed up up to 100%, and monofilament tensile strength is 3512MPa.
Embodiment 7
Carbon fiber/bismaleimide resin composite material of the present embodiment degradation is handed over by carbon fiber T700, bismaleimide resin monomer and vinyl
Join agent to prepare by pressure sintering, wherein the monofilament tensile strength of carbon fiber T700 is 4900MPa.Degradation process is as follows：
Prepare mass fraction 10% magnesium nitrate and normal propyl alcohol composition degradation system, by carbon fiber/bismaleimide resin composite material with
System quality degrade than 1:10,1cm will be cut into3Carbon fiber/bismaleimide resin composite material be completely immersed in degradation system, and it is close
It is encapsulated in zirconium material reaction kettle, degradation reaction temperature 220oC, reaction time 20h.After the reaction was completed, it is cooled to room temperature, diformazan is added
The mass ratio of base sulfoxide, catabolite mixture and dimethyl sulfoxide is 1:5,6min is dissolved, solid product carbon fiber is obtained by filtration
Peacekeeping liquid bismaleimide resin catabolite.Chloroform is added into resin catabolite solution, bismaleimide resin catabolite is precipitated, warp
It is filtered, washed, dries, obtain hydrogenation bismaleimide and curing agent；Acetic acid, dimethyl sulfoxide and chloroform are distilled to recover,
Magnesium nitrate is recycled simultaneously；It is recycled after carbon fiber is washed and dry, the carbon fiber rate of recovery is up to 100%, and monofilament tensile strength is
4819MPa。
Embodiment 8
Carbon fiber/bismaleimide resin composite material of the present embodiment degradation is by carbon fiber T700, bismaleimide resin monomer and amine-type cure
Agent is prepared by pressure sintering, and wherein the monofilament tensile strength of carbon fiber T700 is 4900MPa.Degradation process is as follows：
Prepare mass fraction 12% copper nitrate and isopropanol composition degradation system, by carbon fiber/bismaleimide resin composite material with
System quality degrade than 1:5,1cm will be cut into3Carbon fiber/bismaleimide resin composite material be completely immersed in degradation system, and it is close
It is encapsulated in Hastelloy reaction kettle, degradation reaction temperature 210oC, reaction time 18h.After the reaction was completed, it is cooled to room temperature, is added
The mass ratio of n,N-Dimethylformamide, catabolite mixture and n,N-Dimethylformamide is 1:5, dissolve 9min, filtering
Obtain solid product carbon fiber and liquid bismaleimide resin catabolite.Ethyl acetate is added into resin catabolite solution, it is double
Horse resin catabolite is precipitated, and is filtered, washed, is dried, and hydrogenation bismaleimide and amine curing agent are obtained；By formic acid,
N,N-Dimethylformamide and ethyl acetate are distilled to recover, while recycling copper nitrate；It is recycled after carbon fiber is washed and dry, carbon
Fiber recovery is up to 100%, and monofilament tensile strength is 4856MPa.
Embodiment 9
Carbon fiber/bismaleimide resin composite material of the present embodiment degradation is handed over by carbon fiber T300, bismaleimide resin monomer and vinyl
Join agent to prepare by pressure sintering, wherein the monofilament tensile strength of carbon fiber T300 is 3530MPa.Degradation process is as follows：
The potassium nitrate of mass fraction 5% and the degradation system of water composition are prepared, by carbon fiber/bismaleimide resin composite material and degradation
System quality is than 1:20,1cm will be cut into3Carbon fiber/bismaleimide resin composite material be completely immersed in degradation system, and be sealed in
In zirconium material reaction kettle, degradation reaction temperature 240oC, reaction time 12h.After the reaction was completed, it is cooled to room temperature, acetone, drop is added
The mass ratio for solving product mixtures and acetone is 1:5,2min is dissolved, solid product carbon fiber and liquid bismaleimide resin is obtained by filtration
Catabolite.Chloroform is added into resin catabolite solution, bismaleimide resin catabolite is precipitated, is filtered, washed, is dried,
Obtain hydrogenation bismaleimide and curing agent；Propionic acid, acetone and chloroform are distilled to recover, while recycling potassium nitrate；Carbon fiber
It is recycled after washed and dry, the carbon fiber rate of recovery is up to 100%, and monofilament tensile strength is 3494MPa.
Embodiment 10
Carbon fiber/bismaleimide resin composite material of the present embodiment degradation is by carbon fiber T300, bismaleimide resin monomer and amine-type cure
Agent is prepared by pressure sintering, and wherein the monofilament tensile strength of carbon fiber T300 is 3530MPa.Degradation process is as follows：
Prepare the sodium nitrate and acetic acid/water (mass ratio 1 of mass fraction 8%:1) the degradation system formed, by carbon fiber/span tree
Resin composite material and degradation system quality are than 1:50,10cm will be cut into3Carbon fiber/bismaleimide resin composite material be completely immersed in
Degradation system, and be sealed in Hastelloy reaction kettle, degradation reaction temperature 200oC, the reaction time is for 24 hours.After the reaction was completed, cold
But to room temperature, it is added N-Methyl pyrrolidone, the mass ratio of catabolite mixture and N-Methyl pyrrolidone is 1:10, dissolution
Solid product carbon fiber and liquid bismaleimide resin catabolite is obtained by filtration in 10min.Ring is added into resin catabolite solution
Hexane, bismaleimide resin catabolite are precipitated, are filtered, washed, are dried, and obtain hydrogenation bismaleimide and amine curing agent；
Acetic acid, N-Methyl pyrrolidone and hexamethylene are distilled to recover, while recycling sodium nitrate；It is returned after carbon fiber is washed and dry
It receives, the carbon fiber rate of recovery is up to 100%, and monofilament tensile strength is 3505MPa.
Embodiment 11
Carbon fiber/bismaleimide resin composite material of the present embodiment degradation is by carbon fiber T300, bismaleimide resin monomer and amine-type cure
Agent is prepared by pressure sintering, and wherein the monofilament tensile strength of carbon fiber T300 is 3530MPa.Degradation process is as follows：
Prepare the copper nitrate and methanol/ethylene glycol of mass fraction 15%（Mass ratio 1:1）The degradation system of composition, by carbon fiber/bis-
Horse resin composite material and degradation system quality are than 1:25,1cm will be cut into3Carbon fiber/bismaleimide resin composite material it is complete
Degradation system is immersed, and is sealed in Hastelloy reaction kettle, degradation reaction temperature 240oC, reaction time 10h.Reaction is completed
Afterwards, it is cooled to room temperature, addition n,N-Dimethylformamide, the mass ratio of catabolite mixture and n,N-Dimethylformamide is
1:6,3min is dissolved, solid product carbon fiber and liquid bismaleimide resin catabolite is obtained by filtration.To resin catabolite solution
Middle addition ethyl acetate, bismaleimide resin catabolite are precipitated, are filtered, washed, are dried, and obtain hydrogenation bismaleimide and amine
Class curing agent；Methanol, ethylene glycol, n,N-Dimethylformamide and ethyl acetate are distilled to recover, while recycling copper nitrate；Carbon fiber
It is recycled after tieing up washed and drying, the carbon fiber rate of recovery is up to 100%, and monofilament tensile strength is 3484MPa.
Embodiment 12
Carbon fiber/bismaleimide resin composite material of the present embodiment degradation is handed over by carbon fiber T700, bismaleimide resin monomer and vinyl
Join agent to prepare by pressure sintering, wherein the monofilament tensile strength of carbon fiber T700 is 4900MPa.Degradation process is as follows：
Prepare the ferric nitrate and formic acid/propionic acid of mass fraction 20%（Mass ratio 1:1）The degradation system of composition, by carbon fiber/span
Resin composite materials and degradation system quality are than 1:15,1cm will be cut into3Carbon fiber/bismaleimide resin composite material soak completely
Enter degradation system, and is sealed in zirconium material reaction kettle, degradation reaction temperature 230oC, reaction time 18h.After the reaction was completed, cooling
To room temperature, it is added dimethyl sulfoxide, the mass ratio of catabolite mixture and dimethyl sulfoxide is 1:5,6min is dissolved, is filtered
To solid product carbon fiber and liquid bismaleimide resin catabolite.Chloroform, bismaleimide resin is added into resin catabolite solution
Catabolite is precipitated, and is filtered, washed, is dried, and hydrogenation bismaleimide and curing agent are obtained；By formic acid, propionic acid, dimethyl
Sulfoxide and chloroform are distilled to recover, while recycling ferric nitrate；It is recycled after carbon fiber is washed and dry, the carbon fiber rate of recovery is reachable
100%, and monofilament tensile strength is 4797MPa.
Embodiment 13
Carbon fiber/bismaleimide resin composite material of the present embodiment degradation is by carbon fiber T700, bismaleimide resin monomer and amine-type cure
Agent is prepared by pressure sintering, and wherein the monofilament tensile strength of carbon fiber T700 is 4900MPa.Degradation process is as follows：
The aluminum nitrate of mass fraction 12% and the degradation system of methanol/water composition are prepared, by carbon fiber/bismaleimide resin composite material
With degradation system quality than 1:5,1cm will be cut into3Carbon fiber/bismaleimide resin composite material be completely immersed in degradation system, and
It is sealed in Hastelloy reaction kettle, degradation reaction temperature 200oC, the reaction time is for 24 hours.After the reaction was completed, it is cooled to room temperature, adds
Enter n,N-Dimethylformamide, the mass ratio of catabolite mixture and n,N-Dimethylformamide is 1:8, dissolve 9min, mistake
Filter obtains solid product carbon fiber and liquid bismaleimide resin catabolite.Ethyl acetate is added into resin catabolite solution,
Bismaleimide resin catabolite is precipitated, and is filtered, washed, is dried, and hydrogenation bismaleimide and amine curing agent are obtained；By first
Alcohol, n,N-Dimethylformamide and ethyl acetate are distilled to recover, while recycling aluminum nitrate；It is returned after carbon fiber is washed and dry
It receives, the carbon fiber rate of recovery is up to 100%, and monofilament tensile strength is 4855MPa.
Embodiment 14
Carbon fiber/bismaleimide resin composite material of the present embodiment degradation is handed over by carbon fiber T300, bismaleimide resin monomer and vinyl
Join agent to prepare by pressure sintering, wherein the monofilament tensile strength of carbon fiber T300 is 3530MPa.Degradation process is as follows：
Prepare the nickel nitrate and formic acid/acetic acid/butyric acid of mass fraction 5%（Mass ratio 1:1:1）The degradation system of composition, by carbon fiber
Dimension/bismaleimide resin composite material and degradation system quality are than 1:20,1cm will be cut into3Carbon fiber/bismaleimide resin composite material
It is completely immersed in degradation system, and is sealed in zirconium material reaction kettle, degradation reaction temperature 240oC, reaction time 12h.Reaction is completed
Afterwards, it is cooled to room temperature, addition acetone, the mass ratio of catabolite mixture and acetone is 1:5,2min is dissolved, is obtained by filtration solid
Body product carbon fiber and liquid bismaleimide resin catabolite.Chloroform, bismaleimide resin degradation are added into resin catabolite solution
Product is precipitated, and is filtered, washed, is dried, and hydrogenation bismaleimide and curing agent are obtained；By formic acid, acetic acid, butyric acid, acetone
It is distilled to recover with chloroform, while recycling nickel nitrate；Recycled after carbon fiber is washed and dry, the carbon fiber rate of recovery up to 100%,
And monofilament tensile strength is 3441MPa.
Embodiment 15
Carbon fiber/bismaleimide resin composite material of the present embodiment degradation is by carbon fiber T300, bismaleimide resin monomer and amine-type cure
Agent is prepared by pressure sintering, and wherein the monofilament tensile strength of carbon fiber T300 is 3530MPa.Degradation process is as follows：
Prepare the zinc nitrate and methanol/ethanol/water (mass ratio 1 of mass fraction 8%:1:1) form degradation system, by carbon fiber/
Bismaleimide resin composite material and degradation system quality are than 1:50,10cm will be cut into3Carbon fiber/bismaleimide resin composite material it is complete
It is complete to immerse degradation system, and be sealed in Hastelloy reaction kettle, degradation reaction temperature 260oC, reaction time 18h.It has reacted
Cheng Hou is cooled to room temperature, addition N-Methyl pyrrolidone, and the mass ratio of catabolite mixture and N-Methyl pyrrolidone is 1:
10,10min is dissolved, solid product carbon fiber and liquid bismaleimide resin catabolite is obtained by filtration.To resin catabolite solution
Middle addition hexamethylene, bismaleimide resin catabolite are precipitated, are filtered, washed, are dried, and obtain hydrogenation bismaleimide and amine
Curing agent；Methanol, ethyl alcohol, N-Methyl pyrrolidone and hexamethylene are distilled to recover, while recycling zinc nitrate；Carbon fiber is washed
It is recycled with after drying, the carbon fiber rate of recovery is up to 100%, and monofilament tensile strength is 3477MPa.
Claims (8)
1. the recovery method of carbon fiber in a kind of carbon fiber/bismaleimide resin composite material, it is characterised in that include the following steps：
The metal nitrate of mass fraction 1%-30% and the degradation system of protic composition are prepared, by carbon fiber/span tree
Resin composite material and degradation system quality are than 1:Carbon fiber/bismaleimide resin composite material after cutting is completely immersed in drop by 1-100
Enzymatic hydrolysis system, and be sealed in acid corrosion-resistant reaction kettle, degradation reaction temperature 150-280oC, reaction time 10min-24h, reaction
After the completion, it is cooled to room temperature, is 1 by the mass ratio of catabolite mixture and lytic agent:1-10 is added lytic agent and dissolves 1-
Solid product carbon fiber and resin catabolite solution is obtained by filtration in 10min, and precipitating is added into resin catabolite solution
Agent, bismaleimide resin catabolite are precipitated, are filtered, washed, are dried, obtain bismaleimide resin catabolite；By solvent, lytic agent and
Precipitating reagent is distilled to recover, while obtaining metal nitrate, is recycled after carbon fiber is washed and dry.
2. the recovery method of carbon fiber, feature exist in a kind of carbon fiber/bismaleimide resin composite material as described in claim 1
In the metal nitrate include ferric nitrate, aluminum nitrate, cobalt nitrate, nickel nitrate, chromic nitrate, zinc nitrate, calcium nitrate, nitric acid
One of magnesium, copper nitrate, silver nitrate, potassium nitrate or sodium nitrate.
3. the recovery method of carbon fiber, feature exist in a kind of carbon fiber/bismaleimide resin composite material as described in claim 1
In the protic include methanol, ethyl alcohol, normal propyl alcohol, isopropanol, ethylene glycol, glycerine, formic acid, acetic acid, propionic acid, fourth
The mixture that one or more of acid, water are formed, wherein except the mixture of alcohols and acids.
4. the recovery method of carbon fiber, feature exist in a kind of carbon fiber/bismaleimide resin composite material as described in claim 1
In the carbon fiber/bismaleimide resin composite material be carbon fiber reinforced bismalemide resin composite material, wherein carbon fiber
Dimension include T300, T700, T800 or T1000 model, bimaleimide resin refer to ethylene based cross-linker, amine curing agent or
Bismaleimide after alcohols curing agent crosslinking curing.
5. the recovery method of carbon fiber, feature exist in a kind of carbon fiber/bismaleimide resin composite material as described in claim 1
Being cut into volume in the carbon fiber/bismaleimide resin composite material is 1cm3-1m3Irregular shape.
6. the recovery method of carbon fiber, feature exist in a kind of carbon fiber/bismaleimide resin composite material as described in claim 1
In the acid corrosion-resistant reaction kettle material is zirconium material, titanium, illiteracy are alloy or Hastelloy.
7. the recovery method of carbon fiber, feature exist in a kind of carbon fiber/bismaleimide resin composite material as described in claim 1
In the lytic agent be dimethyl sulfoxide, tetrahydrofuran, acetone, toluene, N-Methyl pyrrolidone or N, N- dimethyl formyl
One of amine.
8. the recovery method of carbon fiber, feature exist in a kind of carbon fiber/bismaleimide resin composite material as described in claim 1
In the precipitating reagent be one of ethyl acetate, chloroform, acetonitrile or hexamethylene.
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| CN114736425A (en) * | 2022-04-17 | 2022-07-12 | 西北工业大学 | Method for recycling carbon fiber reinforced bismaleimide resin matrix composite |
| CN115386138A (en) * | 2021-05-24 | 2022-11-25 | 丰田自动车株式会社 | Method for recycling carbon fibers |
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| CN110757682A (en) * | 2019-10-29 | 2020-02-07 | 中国科学院山西煤炭化学研究所 | Method for recycling waste circuit boards in full-component mode through two-step method |
| CN110922633A (en) * | 2019-11-04 | 2020-03-27 | 中国商用飞机有限责任公司北京民用飞机技术研究中心 | Carbon fiber resin matrix composite material thermal degradation catalyst and application method thereof |
| CN110922633B (en) * | 2019-11-04 | 2021-03-12 | 中国商用飞机有限责任公司北京民用飞机技术研究中心 | Carbon fiber resin matrix composite material thermal degradation catalyst and application method thereof |
| CN115386138A (en) * | 2021-05-24 | 2022-11-25 | 丰田自动车株式会社 | Method for recycling carbon fibers |
| 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 |
| 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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