CN104947247B - A kind of preparation method of lignin-base carbon nano-fiber - Google Patents
A kind of preparation method of lignin-base carbon nano-fiber Download PDFInfo
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Abstract
The invention provides a kind of preparation method of lignin-base carbon nano-fiber.This method uses electrostatic spinning process, fiber is prepared using the copolymer of lignin and acrylonitrile as spinning solution, then carbon fiber is made through thermostabilization processing and charing process.Due to grafted propylene nitrile segments on lignin molecule, make to form chemical bond between lignin and propylene nitrile segments, using propylene nitrile segments there is good heat endurance to improve resistance to meltbility of the fiber in thermostabilization processing procedure, so as to avoid occurring to melt simultaneously between fiber, and the heating rate during can thermostabilization be handled brings up to 10~50 DEG C/min even more highs, effectively increases preparation efficiency.
Description
Technical field
The invention belongs to technical field of carbon fiber preparation, and in particular to a kind of preparation side of lignin-base carbon nano-fiber
Method.
Background technology
Carbon nano-fiber (carbon nanofiber, CNF) be a kind of diameter between CNT and conventional carbon fiber it
Between new carbon, with excellent physics, mechanics, electricity and chemical property, such as high-specific surface area, high intensity and good
Electric conductivity, heat endurance and chemical stability, in structure and functional composite material, electrode material, energy storage material, filter material
The fields such as material, adsorbent, catalyst have important application value.
Preparing CNF method mainly has two kinds of chemical vapour deposition technique and method of electrostatic spinning.The former passes through hydrocarbon
Occur pyrolytic reaction in metallic catalyst surfaces and obtain CNF.This method has realized prepared by CNF commercialization, but due to made
Remaining metal ions in the CNF obtained, cause its application by certain influence.The latter is by Polymer Solution or melt in Gao Jing
Voltage forms a diameter of tens nanometers to several microns of protofilament under acting on, thermostabilization and charing process system are then passed through again
Into CNF.This method is the currently the only method that continuous CNF can be made.Although the macromolecule available for electrostatic spinning has a lot,
But two kinds of polyacrylonitrile and lignin will be had by being used for preparing CNF polymeric main at present.Wherein, lignin is content in nature
The natural macromolecular material of cellulose is only second to, abundance is with low cost.The problems such as crisis of resource and environmental pollution increasingly
Serious today, prepare CNF using reproducible lignin significant.
But, lignin molecule is to be answered by the benzene oxide monomer of hydroxyl or methoxy substitution through the unordered three-dimensional being polymerized
Miscellaneous structure, molecular weight is relatively low and wider distribution, and lignin molecule in contain substantial amounts of alcoholic extract hydroxyl group and phenolic hydroxyl group, exist very strong
Hyarogen-bonding, make the spinning moulding of lignin fibre extremely difficult.
In order to improve lignin and thermoplasticity in the spinnability of lignin, Chinese patent literature CN200710043185.4
Macromolecule polypropylene, PET or polybutylene terephthalate (PBT) carry out physical blending, are then melted
Melt spinning, then carbon nano-fiber is made by thermostabilization processing.Using super in Chinese patent literature CN201010104518.1
Lignin of the membrane retention relative molecular mass between 5000~50000, then carries out electrostatic spinning, then by thermally-stabilised
Change processing and carbon nano-fiber is made.But, because lignin is thermal plastic high polymer, with fusible characteristic, in thermostabilization
During easily melt, cause between monofilament easily occur it is molten simultaneously (.Macromol.Mater.Eng.2014 such as Dallmeyer I.,
299,540-551).It is molten and the specific surface area for causing final CNF is reduced, intensity decreases, and other performance variation.
, must be in extremely slow heating using the thermostabilization processing of precursor made from electrostatic spinning in order to prevent molten and occur
Carried out under speed (such as 0.05~0.25 DEG C/min), it is changed into non-fusible structure (Baker D A. etc.
.J.Appl.Polym.Sci.2013,130:713-728).However, this is extremely low by the preparation efficiency for causing CNF.
The content of the invention
For the above-mentioned state of the art, the present invention is intended to provide a kind of preparation method of lignin-base carbon fiber, this method profit
Fiber is made in lignin-base spinning solution with electrostatic spinning process, then carbon fiber is made through thermostabilization processing and charing process,
Molten generation simultaneously between carbon fiber can not only be prevented effectively from, and can be carried out under faster heating rate at thermostabilization
Reason, so as to effectively improve preparation efficiency.
In order to realize above-mentioned technical purpose, the present inventor using the copolymer of lignin and acrylonitrile as spinning solution, i.e.,
The grafted propylene nitrile segments on lignin molecule, make to form chemical bond between lignin and propylene nitrile segments, then carry out electrostatic
Fiber is made in spinning.Because propylene nitrile segments have good heat endurance, it is in thermostabilization processing procedure by occurring
Cyclization is changed into insoluble trapezium structure, so as to improve the resistance to meltbility of fiber, it is to avoid fiber is in thermostabilization mistake
Occur to melt simultaneously in journey, and thermostabilization processing can be carried out under faster heating rate, improve preparation efficiency.
That is, the technical solution used in the present invention is：A kind of preparation method of lignin-base carbon nano-fiber, utilizes electrostatic
Spinning technique, fiber is made by lignin-base spinning solution, then carbon fiber is made through thermostabilization processing and charing process, its feature
It is：Described lignin-base spinning solution is the copolymer of lignin and acrylonitrile, i.e., the grafted propylene nitrile chain on lignin molecule
Section.
In described electrostatic spinning process, voltage is preferably 5~50KV, receives distance preferably 5~20cm, and spinning solution is squeezed
It is preferably 0.1~1ml/h to go out speed.
Preferably, described thermostabilization is processed as:In air atmosphere from room temperature to 200~300 DEG C, then
Constant temperature keeps 10~60min.Described heating rate is preferably 5~60 DEG C/min, more preferably 10~50 DEG C/min.
Preferably, described charing process is：In a nitrogen atmosphere with from room temperature to 800~1500 DEG C, then
Constant temperature keeps 10~60min.Described heating rate is preferably 10~50 DEG C/min speed.
In the copolymerization process of lignin and acrylonitrile, the present inventor has found a kind of excellent after the exploration of long-term many experiments
The copolymerization process of choosing, can not only form chemical bond between lignin and propylene nitrile segments using this method, realize copolymerization mesh
, and the copolyreaction efficiency of lignin and acrylonitrile can be effectively improved, realize the efficient utilization of lignin.This is preferred
Copolymerization process is as follows：
Esterification is occurred into for unsaturated acyl chlorides and lignin first, using unsaturated acyl chlorides modified lignin resin, made wooden
Hydroxyl in plain molecule is changed into ester group, while introducing unsaturated carbon-carbon double bond in lignin molecule, obtains being esterified lignin；
Then the esterification lignin and acrylonitrile monemer are subjected to homogeneous phase solution free radical copolymerization, grafted propylene nitrile segments are obtained
To esterification lignin and the copolymer of acrylonitrile.
In the copolymerization process, the hydroxyl in lignin molecule is changed into ester group, has slackened intermolecular Hyarogen-bonding, drop
Its low obstruction to free radicals copolymerization reaction；Meanwhile, unsaturated carbon-carbon double bond is introduced in lignin molecule, is that free radical is total to
Poly- reaction provides avtive spot, therefore the copolymerization process effectively increases the copolyreaction efficiency of lignin and acrylonitrile, real
The efficient utilization of lignin is showed.
Described unsaturated acyl chlorides refers to the chloride compounds containing unsaturated carbon-carbon double bond (C=C), includes but is not limited to
Acryloyl chloride, methacrylic chloride etc., preferably acryloyl chloride.
In described esterification, preferably, the part by weight of lignin and unsaturated acyl chlorides is 1000:1~1:1.
When unsaturated acyl chlorides is acryloyl chloride, the part by weight of lignin and acryloyl chloride is preferably 100:1~1:1.
In described esterification, reaction temperature is preferably 0~50 DEG C, and the reaction time is preferably 0.1~10h.
In described homogeneous phase solution free radical copolymerization, reaction medium includes but is not limited to dimethyl sulfoxide (DMSO), diformazan
Base formamide, dimethyl acetamide, solder(ing)acid, sodium thiocyanate water solution, concentrated nitric acid etc., preferably dimethyl sulfoxide (DMSO),
The highly polar organic solvent such as dimethylformamide, dimethyl acetamide is reaction medium.
In described homogeneous phase solution free radical copolymerization, it is preferred to use initiator.Described initiator is oil-soluble
Azo-initiator, preferably using one kind in azodiisobutyronitrile, AMBN, ABVN etc. or two
Plant the mixing of the above.
In described homogeneous phase solution free radical copolymerization, reaction temperature is preferably 50~70 DEG C, and the reaction time is preferred
For 5~25h.
After described homogeneous phase solution free radical copolymerization terminates, preferably, removing unreacting propylene nitrile monomer and
Bubble.
In summary, the present invention passes through electrostatic spinning process system using the copolymer of lignin and acrylonitrile as spinning solution
Standby fiber, makes grafted propylene nitrile segments on lignin molecule, has the advantages that good heat endurance using propylene nitrile segments, carry
High resistance to meltbility of the fiber in thermostabilization processing procedure, thus occur between avoiding fiber it is molten simultaneously, and can be by
Heating rate in thermostabilization processing brings up to 10~50 DEG C/min even more highs, so as to effectively increase preparation efficiency.
Brief description of the drawings
Fig. 1 is the esterification lignin of acryloyl chloride modification in the embodiment of the present invention 1 and the infrared spectrum of acrylonitrile copolymer
Figure；
Fig. 2 be the esterification lignin being modified using acryloyl chloride in the embodiment of the present invention 1 with acrylonitrile copolymer as spinning solution,
Fiber is made through electrostatic spinning, then handled through thermostabilization, the SEM for the carbon nano-fiber that carbonization treatment is made
Photo.
Embodiment
The present invention is described in further detail with reference to embodiment, it should be pointed out that embodiment described below purport
It is being easy to the understanding of the present invention, and is not playing any restriction effect to it.
Embodiment 1：
In the present embodiment, the preparation method of lignin-base carbon nano-fiber comprises the following steps：
(1) in the reactor by weight 100:30:30 sequentially add dimethyl sulfoxide (DMSO), lignin and acryloyl chloride,
Esterification 1h is stirred at 25 DEG C, reaction adds a small amount of triethylamine (TEA) and neutralizes the HCl that esterification is produced after terminating, then adds
Entering ether makes modified lignin deposit, then filters, and is washed repeatedly with absolute ethyl alcohol, removes TEA hydrochlorides, obtains third
The esterification lignin that alkene acyl chlorides is modified；
(2) in the reactor by weight 100:25:25:1, which sequentially adds dimethylformamide, above-mentioned steps (1), is made
Acryloyl chloride be modified esterification lignin, acrylonitrile, azodiisobutyronitrile, under nitrogen protection in 60 DEG C carry out homogeneous phase solutions
Free radical copolymerization 20 hours, reaction removes the unreacting propylene nitrile monomer in polymer fluid under vacuo after terminating, then
Removing bubble is stood, obtains being esterified the copolymer spinning fluid of lignin and acrylonitrile；
The infrared spectrogram of the copolymer spinning fluid of the esterification lignin and acrylonitrile is as shown in Figure 1.2243cm in figure- 1Place
Absworption peak is the characteristic absorption peak of acrylonitrile cyano group stretching vibration, 1721cm- 1Place's absworption peak shakes for esterification lignin carbonyl is flexible
Dynamic characteristic absorption peak, in addition, in 1410,1510 and 1610cm- 1There is the characteristic absorption peak of lignin benzene ring structure in place,
Show that the copolymer for being esterified lignin and acrylonitrile is successfully made.
(3) method of electrostatic spinning is used, by the obtained esterification lignin of above-mentioned steps (2) and acrylonitrile copolymer system
Into electrospinning fibre, voltage is 15KV, and it is 10cm to receive distance, and spinning solution extruded velocity is 0.1ml/h, and electrospinning fibre is made；
(4) electrospinning fibre made from step (3) is risen to 300 with 10 DEG C/min speed from room temperature in air atmosphere
DEG C, constant temperature keeps 30min to carry out thermostabilization processing；Then risen in a nitrogen atmosphere with 20 DEG C/min speed from room temperature
1000 DEG C, constant temperature keeps 10min to carry out charing process, and carbon nano-fiber is made.
The carbon nano-fiber is characterized using SEM, its section is as shown in Fig. 2 find do not occur between fiber
Adhesion, the average diameter of carbon nano-fiber is about 250nm.
Embodiment 2：
In the present embodiment, the preparation method of lignin-base carbon nano-fiber comprises the following steps：
(1) in the reactor by weight 100:30:20 sequentially add dimethyl sulfoxide (DMSO), lignin and acryloyl chloride,
Esterification 1h is stirred at 35 DEG C, reaction adds a small amount of triethylamine (TEA) and neutralizes the HCl that esterification is produced after terminating, then adds
Entering ether makes modified lignin deposit, then filters, and is washed repeatedly with absolute ethyl alcohol, removes TEA hydrochlorides, obtains third
The esterification lignin that alkene acyl chlorides is modified；
(2) in the reactor by weight 100:30:20:1 sequentially adds made from dimethyl sulfoxide (DMSO), above-mentioned steps (1)
Esterification lignin, acrylonitrile, the azodiisobutyronitrile of acryloyl chloride modification, carry out homogeneous phase solutions certainly in 65 DEG C under nitrogen protection
By base copolymerization 18 hours, after reaction terminates, the unreacting propylene nitrile monomer in polymer fluid, Ran Houjing were removed under vacuo
Removing bubble is put, obtains being esterified the copolymer spinning fluid of lignin and acrylonitrile；
(3) method of electrostatic spinning is used, by the obtained esterification lignin of above-mentioned steps (2) and acrylonitrile copolymer system
Into electrospinning fibre, voltage is 25KV, and it is 15cm to receive distance, and spinning solution extruded velocity is 0.3ml/h, electrospinning fibre is made；
(4) electrospinning fibre made from step (3) is risen to 300 with 30 DEG C/min speed from room temperature in air atmosphere
DEG C, constant temperature keeps 30min to carry out thermostabilization processing；Then risen in a nitrogen atmosphere with 50 DEG C/min speed from room temperature
1000 DEG C, constant temperature keeps 10min to carry out charing process, and carbon nano-fiber is made.
The carbon nano-fiber is characterized using SEM, finds not stick together between fiber, carbon nano-fiber
Average diameter be about 640nm.
Embodiment 3：
In the present embodiment, the preparation method of lignin-base carbon nano-fiber comprises the following steps：
(1) in the reactor by weight 100:30:10 sequentially add dimethyl sulfoxide (DMSO), unmodified lignin and acryloyl
Chlorine, stirs esterification 4h at 25 DEG C, and reaction adds a small amount of triethylamine (TEA) and neutralizes the HCl that esterification is produced after terminating,
Adding ether makes modified lignin deposit, then filters, and is washed repeatedly with absolute ethyl alcohol, removes TEA hydrochlorides, obtains
The esterification lignin being modified to acryloyl chloride；
(2) in the reactor by weight 100:30:20:1, which sequentially adds dimethylformamide, above-mentioned steps (1), is made
Acryloyl chloride be modified esterification lignin, acrylonitrile, AMBN, under nitrogen protection in 65 DEG C carry out homogeneous phase solutions
Free radical copolymerization 20 hours, reaction removes the unreacting propylene nitrile monomer in polymer fluid under vacuo after terminating, then
Removing bubble is stood, lignin-acrylonitrile copolymer is obtained；
(3) method of electrostatic spinning is used, by the obtained esterification lignin of above-mentioned steps (2) and acrylonitrile copolymer system
Into electrospinning fibre, voltage is 15KV, and it is 10cm to receive distance, and spinning solution extruded velocity is 0.1ml/h, and electrospinning fibre is made；
(4) electrospinning fibre made from step (3) is risen to 300 with 20 DEG C/min speed from room temperature in air atmosphere
DEG C, constant temperature keeps 50min to carry out thermostabilization processing；Then risen in a nitrogen atmosphere with 50 DEG C/min speed from room temperature
1000 DEG C, constant temperature keeps 20min to carry out charing process, and carbon nano-fiber is made.
The carbon nano-fiber is characterized using SEM, finds not stick together between fiber, carbon nano-fiber
Average diameter be about 530nm.
Embodiment 4：
In the present embodiment, the preparation method of lignin-base carbon nano-fiber comprises the following steps：
(1) in the reactor by weight 100:30:20 sequentially add dimethyl sulfoxide (DMSO), lignin and acryloyl chloride,
Esterification 1h is stirred at 25 DEG C, reaction adds a small amount of triethylamine (TEA) and neutralizes the HCl that esterification is produced after terminating, then adds
Entering ether makes modified lignin deposit, then filters, and is washed repeatedly with absolute ethyl alcohol, removes TEA hydrochlorides, obtains third
The esterification lignin that alkene acyl chlorides is modified；
(2) in the reactor by weight 100:30:20:1, which sequentially adds dimethyl acetamide, above-mentioned steps (1), is made
Acryloyl chloride be modified esterification lignin, acrylonitrile, ABVN, under nitrogen protection in 58 DEG C carry out homogeneous phase solutions
Free radical copolymerization 18 hours, after reaction terminates, removes the unreacting propylene nitrile monomer in polymer fluid, then under vacuo
Removing bubble is stood, lignin-acrylonitrile copolymer is obtained；
(3) method of electrostatic spinning is used, by the obtained esterification lignin of above-mentioned steps (2) and acrylonitrile copolymer system
Into electrospinning fibre, voltage is 10KV, and it is 8cm to receive distance, and spinning solution extruded velocity is 0.1ml/h, and electrospinning fibre is made；
(4) electrospinning fibre made from step (3) is risen to 300 with 35 DEG C/min speed from room temperature in air atmosphere
DEG C, constant temperature keeps 50min to carry out thermostabilization processing；Then risen in a nitrogen atmosphere with 30 DEG C/min speed from room temperature
1000 DEG C, constant temperature keeps 30min to carry out charing process, and carbon nano-fiber is made.
The carbon nano-fiber is characterized using SEM, finds not stick together between fiber, carbon nano-fiber
Average diameter be about 700nm.
Embodiment 5：
In the present embodiment, the preparation method of lignin-base carbon nano-fiber comprises the following steps：
(1) in the reactor by weight 100:30:5 sequentially add dimethyl sulfoxide (DMSO), lignin and methacrylic chloride,
Esterification 4h is stirred at 25 DEG C, reaction adds a small amount of triethylamine (TEA) and neutralizes the HCl that esterification is produced after terminating, then
Adding ether makes modified lignin deposit, then filters, and is washed repeatedly with absolute ethyl alcohol, removes TEA hydrochlorides, obtains
The esterification lignin that acryloyl chloride is modified；
(2) in the reactor by weight 100:30:20:1, which sequentially adds dimethylformamide, above-mentioned steps (1), is made
Methacrylic chloride be modified esterification lignin, acrylonitrile, azodiisobutyronitrile.Carried out under nitrogen protection in 60 DEG C homogeneous
Solution Free Radical copolymerization 22 hours, after reaction terminates, removes the unreacting propylene nitrile monomer in polymer fluid under vacuo,
Then removing bubble is stood, obtains being esterified the copolymer spinning fluid of lignin and acrylonitrile；
(3) method of electrostatic spinning is used, by the obtained esterification lignin of above-mentioned steps (2) and acrylonitrile copolymer system
Into electrospinning fibre, voltage is 15KV, and it is 10cm to receive distance, and spinning solution extruded velocity is 0.1ml/h, and electrospinning fibre is made；
(4) electrospinning fibre made from step (3) is risen to 300 with 10 DEG C/min speed from room temperature in air atmosphere
DEG C, constant temperature keeps 20min to carry out thermostabilization processing；Then risen in a nitrogen atmosphere with 10 DEG C/min speed from room temperature
1000 DEG C, constant temperature keeps 10min to carry out charing process, and carbon nano-fiber is made.
The carbon nano-fiber is characterized using SEM, finds not stick together between fiber, carbon nano-fiber
Average diameter be about 380nm.
Embodiment 6：
In the present embodiment, the preparation method of lignin-base carbon nano-fiber comprises the following steps：
(1) in the reactor by weight 100:30:30 sequentially add dimethyl sulfoxide (DMSO), lignin and methacryl
Chlorine, stirs esterification 1h at 25 DEG C, and reaction adds a small amount of triethylamine (TEA) and neutralizes the HCl that esterification is produced after terminating,
Adding ether makes modified lignin deposit, then filters, and is washed repeatedly with absolute ethyl alcohol, removes TEA hydrochlorides, obtains
The esterification lignin being modified to methacrylic chloride；
(2) in the reactor by weight 100:30:20:1, which sequentially adds dimethyl acetamide, above-mentioned steps (1), is made
Methacrylic chloride be modified esterification lignin, acrylonitrile, azodiisobutyronitrile.Carried out under nitrogen protection in 65 DEG C homogeneous
Solution Free Radical copolymerization 18 hours, after reaction terminates, removes the unreacting propylene nitrile monomer in polymer fluid under vacuo,
Then removing bubble is stood, obtains being esterified the copolymer spinning fluid of lignin and acrylonitrile；
(3) use method of electrostatic spinning, will the obtained esterification lignin of above-mentioned steps (2) and acrylonitrile copolymer its
Electrospinning fibre is made, voltage is 10KV, it is 6cm to receive distance, spinning solution extruded velocity is 1ml/h, and electrospinning fibre is made；
(4) electrospinning fibre made from step (3) is risen to 300 with 50 DEG C/min speed from room temperature in air atmosphere
DEG C, constant temperature keeps 50min to carry out thermostabilization processing；Then risen in a nitrogen atmosphere with 20 DEG C/min speed from room temperature
1000 DEG C, constant temperature keeps 10min to carry out charing process, and carbon nano-fiber is made.
The carbon nano-fiber is characterized using SEM, finds not stick together between fiber, carbon nano-fiber
Average diameter be about 940nm.
Technical scheme is described in detail embodiment described above, it should be understood that it is described above only
For the specific embodiment of the present invention, it is not intended to limit the invention, all any modifications made in the spirit of the present invention,
Supplement or similar fashion replacement etc., should be included in the scope of the protection.
Claims (9)
1. a kind of preparation method of lignin-base carbon nano-fiber, using electrostatic spinning process, lignin-base spinning solution is made
Fiber, then carbon fiber is made through thermostabilization processing and charing process, it is characterized in that：Described lignin-base spinning solution is wooden
The copolymer spinning fluid of element and acrylonitrile；
Described thermostabilization is processed as in air atmosphere from room temperature to 200 DEG C~300 DEG C, then constant temperature keep 10~
60min；Heating rate is 5~60 DEG C/min；
The copolymerization process of lignin and acrylonitrile is：
Esterification is occurred into for unsaturated acyl chlorides and lignin first, the hydroxyl in lignin molecule is changed into ester group, simultaneously
Unsaturated carbon-carbon double bond is introduced in lignin molecule, obtains being esterified in lignin, described esterification, reaction temperature is 0
~50 DEG C, the reaction time is 0.1~10h；Then the esterification lignin and acrylonitrile monemer are carried out into homogeneous phase solution free radical to be total to
Polymerisation, grafted propylene nitrile segments obtain being esterified the copolymer spinning fluid of lignin and acrylonitrile；
In described homogeneous phase solution free radical copolymerization, using initiator；Described initiator is azodiisobutyronitrile, idol
One or more kinds of mixing in nitrogen diisoamyl nitrile, ABVN.
2. the preparation method of lignin-base carbon nano-fiber as claimed in claim 1, it is characterized in that：Described electrostatic spinning work
In skill, voltage is 5~50KV, and it is 5~20cm to receive distance, and spinning solution extruded velocity is 0.1~1mL/h.
3. the preparation method of lignin-base carbon nano-fiber as claimed in claim 1, it is characterized in that：Described heating rate is
10~50 DEG C/min.
4. the preparation method of lignin-base carbon nano-fiber as claimed in claim 1, it is characterized in that：Described charing process is
In a nitrogen atmosphere from room temperature to 800 DEG C~1500 DEG C, then constant temperature keeps 10~60min.
5. the preparation method of lignin-base carbon nano-fiber as claimed in claim 4, it is characterized in that：Described heating rate is
10~50 DEG C/min.
6. the preparation method of lignin-base carbon nano-fiber as claimed in claim 1, it is characterized in that：Unsaturated acyl chlorides is propylene
Acyl chlorides and/or methacrylic chloride.
7. the preparation method of lignin-base carbon nano-fiber as claimed in claim 1, it is characterized in that：Described esterification
In, the part by weight of lignin and unsaturated acyl chlorides is 1000:1~1:1.
8. the preparation method of lignin-base carbon nano-fiber as claimed in claim 1, it is characterized in that：Unsaturated acyl chlorides is propylene
The part by weight of acyl chlorides, lignin and acryloyl chloride is 100:1~1:1.
9. the preparation method of lignin-base carbon nano-fiber as claimed in claim 1, it is characterized in that：Described homogeneous phase solution is certainly
In base copolymerization, reaction temperature is 50~70 DEG C, and the reaction time is 5~25h.
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