CN109853087A - A kind of lignin/cellulose acetate basic ring oxygen modified carbon fiber and the preparation method and application thereof - Google Patents
A kind of lignin/cellulose acetate basic ring oxygen modified carbon fiber and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of lignin/cellulose acetate basic ring oxygen modified carbon fiber and preparation method and applications.By lignin and cellulose acetate in the presence of epoxychloropropane, lignin/cellulose acetate base spinning solution that chemical modification reaction is made described is carried out, carbon fiber precursor is made through electrospinning process, then carbon fiber is made through pre-oxidation treatment and carbonization treatment.Suitable epoxychloropropane, which is added, makes it react with the hydroxyl on lignin and cellulose acetate but epoxy not open loop, it is made to be easier into silk during the spinning process.Make to form chemical bond between lignin and cellulose acetate in epoxy addition in preoxidation process, increase its thermal stability, reduces the generation of phenomenon of phase separation.Carbon fiber made from the method for the present invention has good fibre morphology, high mechanicalness and absorption property, there is applications well prospect in terms of as electrode, reinforcing material and adsorbent, the full biomass base carbon fibre for production high quality, green, low cost provides guarantee.
Description
Technical field
The invention belongs to biological material processing technique fields, and in particular to a kind of lignin/cellulose acetate basic ring oxygen
Modified carbon fiber and the preparation method and application thereof.
Background technique
In recent years, global warming, energy crisis and environmental pollution have caused the extensive concern of people.Using alternative energy source
It is the effective means solved these problems, such as various electrochemical energy storages and conversion equipment.Low energy densities and Gao Chengben
It is the bottleneck for restricting electrochemical capacitor development.To solve this problem, developing the new electrode material of electrochemical capacitor is one
A important and effective and feasible approach.Carbon fiber because its specific discharge capacity height, good conductivity, surface aperture, can provide it is good
Response path has the characteristics that excellent intensity and processability, is increasingly closed as electrochemical capacitor electrode material
Note.
For at present, the main raw material(s) for preparing carbon fiber is the petroleum high polymers such as polyacrylonitrile, however, due to fossil energy
The non-renewable and fancy price in source constrains carbon fiber further the answering in civil field prepared using it as raw material
With and development.Lignin because the high and low cost of its phosphorus content, it is renewable the advantages that have been developed as substitution petroleum-based feedstock production
The excellent raw material of the civilian carbon fiber of low cost.
However, due to, there are large number of hydroxyl, make in the chemical structure of cellulose its with containing fragrant hydrocarbon structure
Lignin physical mixed spinning process in will appear and mutually separate situation, greatly reduce its service performance.
Summary of the invention
In view of above-mentioned problems of the prior art, the purpose of the present invention is to provide a kind of lignin/acetate fibers
The preparation method of plain basic ring oxygen modified carbon fiber, the carbon fiber that this method is prepared is using full biomass raw material as substrate.
Technical scheme is as follows:
A kind of preparation method of lignin/cellulose acetate basic ring oxygen modified carbon fiber will be wooden by electrospinning process
Carbon fiber precursor is made in quality/cellulose acetate base spinning solution, then carbon fiber is made through pre-oxidation treatment and carbonization treatment, will
It is fine to carry out lignin/acetic acid that chemical modification reaction is made described in the presence of epoxychloropropane for lignin and cellulose acetate
Tie up plain base spinning solution.
In the above-mentioned technical solutions, the reaction temperature of the chemical modification reaction be 0~10 DEG C, the reaction time be 6~
12h。
In the above-mentioned technical solutions, in the chemical modification reaction, the lignin and cellulose acetate plus
Enter amount for 30:70~70:30 in mass ratio, the additional amount of the lignin and cellulose acetate is the 10 of reaction system quality
~30%.
In the above-mentioned technical solutions, in the chemical modification reaction, the epoxychloropropane additional amount is reaction
The 2~20% of system quality, preferably 5~16%, more preferably 8~12%,.
In the above-mentioned technical solutions, in the chemical modification reaction, lignin and cellulose acetate are dissolved in solvent A
With the in the mixed solvent of solvent B, wherein the mixed proportion of solvent A and solvent B are 1~2:1 by volume, in the mixed solution
Solvent A/solvent B is acetone/N, N-dimethylformamide, glacial acetic acid/N, N-dimethylformamide, acetone/N, N dimethyl acetamide
Or glacial acetic acid/N, N dimethyl acetamide.
In the above-mentioned technical solutions, in the electrospinning process, 15~35KV of electrostatic potential receives distance 10-35cm,
Accepted roll 200~700r/min of revolving speed, spinning solution push away 0.1~1ml/h of speed.
In the above-mentioned technical solutions, the pre-oxidation treatment is to pre-oxidize carbon fiber precursor in air atmosphere,
Pre-oxidation is by room temperature, 200 DEG C -300 DEG C are warming up to the rate of 0.01 DEG C~2.00 DEG C/min, and keep the temperature at this temperature
8~12h obtains pre-oxidized fibers.
In the above-mentioned technical solutions, the carbonization treatment be will be through pre-oxidized fibers indifferent gas that pre-oxidation treatment obtains
Body protection is lower to heat carbonization treatment, is warming up to 600 DEG C~1400 DEG C with 2 DEG C~10 DEG C/min rate, and keep the temperature 2 at this temperature
~6h obtains lignin/cellulose acetate base electrostatic spinning carbon fiber.
In the present invention, the quality of above-mentioned reaction system refers in chemical modification reaction, anti-after each reactant is added
The gross mass of liquid is answered, reaction solution carries out 6~12h of chemical modification reaction, system under suitable condition such as 0~10 DEG C of reaction temperature
Obtain the lignin/cellulose acetate base spinning solution.
The lignin being prepared the present invention also provides above-mentioned method/cellulose acetate basic ring oxygen modified carbon fiber is being made
Application in the electrode material of standby capacitor.
In the present invention, used lignin derives from biomass, such as includes that needlebush, leaf wood and non-timber are fine
The lignin isolated in dimension raw material, according to separation method difference can obtain wooden to be known as formic acid lignin, acetic acid wooden
Element and ethyl alcohol lignin etc..The isolated lignin of this means of different can be bought from the market, can also be voluntarily
It is prepared according to the document having disclosed.
In the present invention, cellulose acetate is modified from the acetic acid of biomass native cellulose.Acetic acid of the present invention is fine
Dimension element, preferably its acetyl content is 37%~40%.
For the present invention during preparing lignin/cellulose acetate spinning solution, suitable epoxychloropropane, which is added, makes it
It reacts with the hydroxyl on lignin and cellulose acetate, forms epoxy construction, the hydrogen bond between biomass hydroxyl can be reduced
Effect, makes it be easier into silk during the spinning process.And the epoxychloropropane not open loop before spinning of addition, it is pre-oxidizing
Epoxy addition makes to form chemical bond between lignin and cellulose acetate in the process, as the open loop of epoxy increases its thermostabilization
Property, largely reduce the generation of phenomenon of phase separation.
On the other hand, the present invention just handles lignin and cellulose acetate during preparing spinning solution,
Spinning solution is directly used in spinning, sustainable to go to prepare lignin/cellulose acetate base carbon fibre, overcomes well current
The production that preparation method is post-processed after preparing because of precursor fibre without can be carried out carbon fiber serialization increases system
The problem of standby energy consumption.
Carbon fiber of the invention prepares raw material not comprising any fossil feedstock, uses biomass material lignin and acetic acid
Cellulose is from a wealth of sources, price is cheap, is easy to regenerate, is environmentally protective as carbon fiber carbon usually source.The carbon fiber being prepared
With good fibre morphology, high mechanicalness, good absorption property can substitute the fine base carbon fibre of polypropylene, as electrode
There is applications well prospect in terms of reinforcing material.
Detailed description of the invention
Fig. 1 is the resulting lignin of the embodiment of the present invention 1/cellulose acetate basic ring oxygen modified carbon fiber SEM figure.A is ring
Preparation gained carbon fiber electron microscope when oxygen chloropropane additive amount 0wt%, preparation gained when b is epoxychloropropane additive amount 2wt%
Carbon fiber electron microscope, preparation gained carbon fiber electron microscope when c is epoxychloropropane additive amount 4wt%, d are epoxychloropropane addition
Preparation gained carbon fiber electron microscope when measuring 6wt%, preparation gained carbon fiber electron microscope when e is epoxychloropropane additive amount 8wt%,
Preparation gained carbon fiber electron microscope when f is epoxychloropropane additive amount 10wt%.
Fig. 2 is the resulting lignin of the embodiment of the present invention 1/cellulose acetate basic ring oxygen modified carbon fiber precursor molecule amount
Distribution map.
Fig. 3 is the resulting lignin of the embodiment of the present invention 1/cellulose acetate basic ring oxygen modified carbon fiber cyclic voltammetry spectrum
Figure.
Specific embodiment
Present invention will be described in further detail below with reference to the accompanying drawings and specific embodiments, but the present invention does not limit to
In these embodiments.In following embodiments, unless otherwise specified, used experimental method is conventional method, material used
Material, reagent etc. can be bought from biological or chemical company.
Following embodiment material therefors:
Poplar pre-hydrolyzed solution lignin: being purchased from Shanghai Dong Sheng Science and Technology Ltd., and lignin purity is 93%.
Cellulose acetate: Shanghai Aladdin biochemical technology limited liability company, model 9004-35-7, acetyl content
For 39.8wt%
Electrostatic spinning machine: the micro-nano Science and Technology Ltd. of Shenzhen concerted effort, model TL-Pro.
GPC detection uses waters (waters company).
Embodiment 1
It is prepared as follows lignin/cellulose acetate basic ring oxygen modified carbon fiber:
(1) poplar pre-hydrolyzed solution lignin/and cellulose acetate are dissolved in acetone/N according to mass ratio 50/:50 (w/w),
A certain amount of epoxychloropropane (ECH) is added, instead in the in the mixed solvent of dinethylformamide (v/v:2:1) after being completely dissolved
Answering epoxychloropropane final concentration in system is respectively 0wt%, 2wt%, 4wt%, 6wt%, 8wt% and 10wt%, and poplar is pre-
Final concentration of the 20% of hydrolyzate lignin and cellulose acetate, reacts 6h, after reaction filtering and removing unreacted at 0 DEG C
ECH, stand 1h, obtain lignin and cellulose acetate copolymer spinning fluid；
(2) spinning solution made from step (1) is prepared into lignin/cellulose acetate base carbon fibre by electrospinning process
Precursor, the condition of electrostatic spinning are as follows: electrostatic pressure 25KV, receiving distance is 20cm, receives rod revolving speed 500r/min, spinning is molten
The fltting speed of liquid is 0.2mL/h；
(3) carbon fiber precursor obtained is placed in tube furnace, with the heating of 0.01 DEG C/min in air atmosphere
Rate is warming up to 200 DEG C, and keeps the temperature 200min and carry out pre-oxidation treatment；Then under nitrogen protection with the rate liter of 4 DEG C/min
Temperature keeps the temperature 480min and carries out heating carbonization treatment to 600 DEG C, obtains lignin/cellulose acetate base electrostatic spinning carbon fiber.
Carbon fiber electron microscope such as Fig. 1 a~Fig. 1 f obtained by embodiment respectively is epoxychloropropane additive amount 0wt%
(ECH-0), 2wt% (ECH-2), 4wt% (ECH-4), 6wt% (ECH-6), 8wt% (ECH-8) and 10wt% (ECH-10)
When preparation gained carbon fiber electron microscope.Fig. 1 as it can be seen that with ECH additive amount increase, fiber gluing phenomenon fades away, Filamentous
Pattern tends to uniformly, illustrate that the addition of epoxy can effectively improve the thermal stability of carbon fiber.
Fig. 2 is the GPC testing result for precursor fibre obtained by embodiment step (2), finds adding for epoxychloropropane
Enter and have not been changed its molecular weight distribution, illustrates epoxy not open loop in spinning process.Lignin and CA respectively indicate conduct in Fig. 2
The lignin and cellulose acetate of raw material.Mw, Mn and PDI of each product are respectively as follows: Lignan:Mw=1280g in Fig. 2
mol-1, Mn=213g mol-1, PDI=6.01；CA:Mw=33325g mol-1, Mn=2857g mol-1, PDI=11.66；
ECH-0:Mw=15220g mol-1, Mn=750g mol-1, PDI=20.29；ECH-2:Mw=15275g mol-1, Mn=
749g mol-1, PDI=20.40；ECH-4:Mw=15880g mol-1, Mn=804g mol-1, PDI=19.65；ECH-6:Mw
=15488g mol-1, Mn=718g mol-1, PDI=21.57；ECH-8:Mw=15668g mol-1, Mn=748g mol-1,
PDI=20.95；ECH-10:Mw=15820g mol-1, Mn=757g mol-1, PDI=20.89.
Detection can be carried out using electrochemistry of the cyclic voltammetry to carbon fiber obtained by embodiment, Fig. 3 is the circulation that side obtains
Volt-ampere spectrogram illustrates that specific capacitance is increasing as it can be seen that rectangular area becomes larger as ECH additive amount increases in figure.By following
Ring volt-ampere spectrogram can be seen that the increase with epoxy additive amount, and the specific capacitance of capacitor gradually increases.
Embodiment 2
It is prepared as follows lignin/cellulose acetate basic ring oxygen modified carbon fiber:
(1) poplar pre-hydrolyzed solution lignin/and cellulose acetate are dissolved in acetone/N according to mass ratio 40/:60 (w/w),
Epoxychloropropane is added in the in the mixed solvent of dinethylformamide (v/v:2:1) after being completely dissolved, epoxy chlorine in reaction system
Final concentration of the 15% of the final concentration of 10wt% of propane, poplar pre-hydrolyzed solution lignin and cellulose acetate, reacts at 0 DEG C
6h, the unreacted ECH of filtering and removing, stands 2h, obtains lignin and cellulose acetate copolymer spinning fluid after reaction；
(2) spinning solution made from step (1) is prepared into lignin/cellulose acetate base carbon fibre by electrospinning process
Precursor, the condition of electrostatic spinning are as follows: electrostatic pressure 25KV, receiving distance is 25cm, accepted roll revolving speed 600r/min, and spinning is molten
The fltting speed of liquid is 0.5mL/h；
(3) carbon fiber precursor obtained is placed in tube furnace, with the heating speed of 0.2 DEG C/min in air atmosphere
Rate is warming up to 250 DEG C, and keeps the temperature 480min and carry out pre-oxidation treatment；Then it is heated up under nitrogen protection with the rate of 5 DEG C/min
It to 800 DEG C, and keeps the temperature 120min and carries out heating carbonization treatment, obtain lignin/cellulose acetate base electrostatic spinning carbon fiber.Electricity
Chemical property test result shows excellent chemical property.
Embodiment 3
It is prepared as follows lignin/cellulose acetate basic ring oxygen modified carbon fiber:
(1) poplar pre-hydrolyzed solution lignin/and cellulose acetate are dissolved in acetone/N according to mass ratio 60/:40 (w/w),
Epoxychloropropane is added in the in the mixed solvent of dinethylformamide (v/v:2:1) after being completely dissolved, epoxy chlorine in reaction system
Final concentration of the 25% of the final concentration of 12wt% of propane, poplar pre-hydrolyzed solution lignin and cellulose acetate, reacts at 0 DEG C
6h, the unreacted ECH of filtering and removing stands 2h after reaction, obtains lignin and cellulose acetate copolymer spinning fluid；
(2) spinning solution made from step (1) is prepared into lignin/cellulose acetate base carbon fibre by electrospinning process
Precursor, the condition of electrostatic spinning are as follows: electrostatic pressure 20KV, receiving distance is 30cm, receives rod revolving speed 700r/min, spinning is molten
The fltting speed of liquid is 0.8mL/h；
(3) carbon fiber precursor obtained is placed in tube furnace, with the heating speed of 0.5 DEG C/min in air atmosphere
Rate is warming up to 220 DEG C, and keeps the temperature 720min and carry out pre-oxidation treatment；Then it is heated up under nitrogen protection with the rate of 8 DEG C/min
It to 1000 DEG C, and keeps the temperature 480min and carries out heating carbonization treatment, obtain lignin/cellulose acetate base electrostatic spinning carbon fiber.
Gained carbon fiber electron microscope still maintains excellent form, can be seen that by cyclic voltammetric spectrogram as epoxy adds
The specific capacitance of the increase of dosage, capacitor gradually increases.
The preferred embodiment of the present invention has been described in detail above, but the invention be not limited to it is described
Embodiment, those skilled in the art can also make various equivalent on the premise of not violating the inventive spirit of the present invention
Variation or replacement, these equivalent variation or replacement are all included in the scope defined by the claims of the present application.
Claims (9)
1. a kind of lignin/cellulose acetate basic ring oxygen modified carbon fiber preparation method will be wooden by electrospinning process
Carbon fiber precursor is made in element/cellulose acetate base spinning solution, then carbon fiber is made through pre-oxidation treatment and carbonization treatment, special
Sign is, by lignin and cellulose acetate in the presence of epoxychloropropane, carries out chemical modification reaction and is made described wooden
Element/cellulose acetate base spinning solution.
2. preparation method according to claim 1, which is characterized in that the reaction temperature of the chemical modification reaction is 0
~10 DEG C, the reaction time is 6~12h.
3. preparation method according to claim 1, which is characterized in that in the chemical modification reaction, the wood
Quality and the additional amount of cellulose acetate are 30:70~70:30 in mass ratio, the addition of the lignin and cellulose acetate
Amount is the 10~30% of reaction system quality.
4. preparation method according to claim 1, which is characterized in that in the chemical modification reaction, the ring
Oxygen chloropropane additional amount is the 2~20% of reaction system quality.
5. preparation method according to claim 1, which is characterized in that in the chemical modification reaction, by lignin
The in the mixed solvent of solvent A and solvent B is dissolved in cellulose acetate, wherein the mixed proportion of solvent A and solvent B are by volume
1~2:1, solvent A/solvent B is acetone/n,N dimethylformamide, glacial acetic acid/N, N dimethyl formyl in the mixed solution
Amine, acetone/N, N dimethyl acetamide or glacial acetic acid/N, N dimethyl acetamide.
6. preparation method according to claim 1, which is characterized in that in the electrospinning process, electrostatic potential 15~
35KV receives 10~35cm of distance, receives rod 200~700r/min of revolving speed, spinning solution pushes away 0.1~1ml/h of speed.
7. preparation method according to claim 1, which is characterized in that the pre-oxidation treatment is by carbon fiber precursor
Pre-oxidized in air atmosphere, pre-oxidation by room temperature, with the rate of 0.01 DEG C~2.00 DEG C/min be warming up to 200 DEG C~
300 DEG C, and 8-12h is kept the temperature at this temperature, obtain pre-oxidized fibers.
8. preparation method according to claim 1, which is characterized in that the carbonization treatment is will to obtain through pre-oxidation treatment
To pre-oxidized fibers heat carbonization treatment under inert gas protection, with 2 DEG C~10 DEG C/min rate be warming up to 600 DEG C~
1400 DEG C, and 2~6h is kept the temperature at this temperature, obtain lignin/cellulose acetate base electrostatic spinning carbon fiber.
9. the modified carbon fiber of the lignin that described in any item methods of claim 1~8 are prepared/cellulose acetate basic ring oxygen
Tie up the application in the electrode material for preparing capacitor.
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