CN104947247A - Preparation method of lignin-based carbon nanofiber - Google Patents
Preparation method of lignin-based carbon nanofiber Download PDFInfo
- Publication number
- CN104947247A CN104947247A CN201510330420.0A CN201510330420A CN104947247A CN 104947247 A CN104947247 A CN 104947247A CN 201510330420 A CN201510330420 A CN 201510330420A CN 104947247 A CN104947247 A CN 104947247A
- Authority
- CN
- China
- Prior art keywords
- lignin
- fiber
- preparation
- carbon nano
- esterification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention provides a preparation method of lignin-based carbon nanofiber. According to the preparation method, electrostatic spinning technology is adopted; a copolymer of lignin and acrylonitrile is adopted as a spinning solution to prepare fiber; the fiber is subjected to thermal stabilizing treatment and carbonizing treatment to be prepared into carbon fiber. Acrylonitrile chain segments are grafted on lignin molecules, chemical bonds are generated between lignin and acrylonitrile chain segments, and the melting resistance of fiber in the thermal stabilizing treatment process is improved by using the fact that acrylonitrile chain segments are good in heat stability, so that melting and merging between fibers are avoided, the heating rate in thermal stabilizing treatment can be improved to 10-50 DEG C/min or above, and the preparation efficiency is effectively improved.
Description
Technical field
The invention belongs to technical field of carbon fiber preparation, be specifically related to a kind of preparation method of lignin-base carbon nano-fiber.
Background technology
Carbon nano-fiber (carbon nanofiber, CNF) be the new carbon of a kind of diameter between CNT and conventional carbon fiber, there is excellent physics, mechanics, electricity and chemical property, as high-specific surface area, high strength and good electric conductivity, heat endurance and chemical stability, in fields such as structure and fuction composite, electrode material, energy storage material, filtering material, adsorbent, catalyst, there is important using value.
The method preparing CNF mainly contains chemical vapour deposition technique and method of electrostatic spinning two kinds.The former obtains CNF by hydrocarbon in metallic catalyst surfaces generation pyrolytic reaction.The method has realized the commercialization preparation of CNF, but due to remaining metal ions in obtained CNF, causes its application to be subject to certain impact.By Polymer Solution or melt, under high electrostatic pressure effect, form diameter be tens nanometers to the latter to the protofilament of several microns, and then make CNF through thermostabilization and charing process.The method is the method that uniquely can obtain continuous CNF at present.Although the macromolecule that can be used for electrostatic spinning has a lot, the macromolecule being used for preparing CNF at present mainly contains polyacrylonitrile and two kinds, lignin.Wherein, lignin is that occurring in nature content is only second to cellulosic natural macromolecular material, abundance, with low cost.In today that the problem such as crisis of resource and environmental pollution is day by day serious, reproducible lignin is utilized to prepare CNF significant.
But, lignin molecule is through the unordered 3 D complex structure be polymerized by the benzene oxide monomer of hydroxyl or methoxy substitution, lower and the wider distribution of molecular weight, and containing a large amount of alcoholic extract hydroxyl groups and phenolic hydroxyl group in lignin molecule, there is very strong Hyarogen-bonding, make the spinning moulding of lignin fibre very difficult.
In order to improve the spinnability of lignin, in Chinese patent literature CN200710043185.4, lignin and thermal plastic high polymer polypropylene, polyethylene terephthalate or polybutylene terephthalate (PBT) are carried out physical blending, then carry out melt spinning, then obtain carbon nano-fiber through thermostabilization process.Adopt milipore filter to retain the lignin of relative molecular mass between 5000 ~ 50000 in Chinese patent literature CN201010104518.1, then carry out electrostatic spinning, then obtain carbon nano-fiber through thermostabilization process.But, because lignin is thermal plastic high polymer, there is melting characteristic, easy melting in thermostabilization process, to cause between monofilament and easily occur molten also .Macromol.Mater.Eng.2014 such as (, 299,540-551) Dallmeyer I..Molten and the specific area of final CNF reduces, intensity reduction by causing, and other degradation.
In order to prevent from melting and occur, the thermostabilization process of the precursor utilizing electrostatic spinning to obtain must be carried out under extremely slow heating rate (as 0.05 ~ 0.25 DEG C/min), it is made to change non-fusible structure (.J.Appl.Polym.Sci.2013, the 130:713-728 such as Baker D A.) into.But this will cause the preparation efficiency of CNF extremely low.
Summary of the invention
For the above-mentioned state of the art, the present invention aims to provide a kind of preparation method of lignin-base carbon fiber, the method utilizes electrostatic spinning process that lignin-base spinning solution is made fiber, carbon fiber is made again through thermostabilization process and charing process, effectively can not only avoid molten generation also between carbon fiber, and thermostabilization process can be carried out under heating rate faster, thus effectively improve preparation efficiency.
In order to realize above-mentioned technical purpose, the present inventor adopts the copolymer of lignin and acrylonitrile as spinning solution, i.e. grafted propylene nitrile segments on lignin molecule, makes to form chemical bond between lignin and acrylonitrile segment, then carries out electrostatic spinning and obtain fiber.Because acrylonitrile segment has good heat endurance, its in thermostabilization processing procedure by there is the trapezium structure that cannot not change into molten of cyclization, thus the resistance to meltbility of fiber can be improved, fiber is avoided to occur to melt also in thermostabilization process, and thermostabilization process can be carried out under heating rate faster, improve preparation efficiency.
Namely, the technical solution used in the present invention is: a kind of preparation method of lignin-base carbon nano-fiber, utilize electrostatic spinning process, lignin-base spinning solution is made fiber, carbon fiber is made again through thermostabilization process and charing process, it is characterized in that: described lignin-base spinning solution is the copolymer of lignin and acrylonitrile, i.e. grafted propylene nitrile segments on lignin molecule.
In described electrostatic spinning process, voltage is preferably 5 ~ 50KV, and receiving range is preferably 5 ~ 20cm, and spinning solution extruded velocity is preferably 0.1 ~ 1ml/h.
As preferably, described thermostabilization is treated to: in air atmosphere from room temperature to 200 ~ 300 DEG C, and then constant temperature keeps 10 ~ 60min.Described heating rate is preferably 5 ~ 60 DEG C/min, more preferably 10 ~ 50 DEG C/min.
As preferably, described charing is treated to: in a nitrogen atmosphere with from room temperature to 800 ~ 1500 DEG C, then constant temperature keeps 10 ~ 60min.Described heating rate is preferably the speed of 10 ~ 50 DEG C/min.
In the copolymerization process of lignin and acrylonitrile, the present inventor finds a kind of preferred copolymerization process after long-term great many of experiments is explored, utilize the method can not only form chemical bond between lignin and acrylonitrile segment, realize copolymerization object, and effectively can improve the copolyreaction efficiency of lignin and acrylonitrile, realize the efficiency utilization of lignin.This preferred copolymerization process is as follows:
First by unsaturated acyl chlorides and lignin generation esterification, utilize unsaturated acyl chlorides modified lignin resin, make the hydroxyl in lignin molecule change ester group into, in lignin molecule, introduce unsaturated carbon-carbon double bond simultaneously, obtain esterification lignin; Then this esterification lignin and acrylonitrile monemer are carried out homogeneous phase solution free radical copolymerization, grafted propylene nitrile segments, obtain the copolymer of esterification lignin and acrylonitrile.
In this copolymerization process, the hydroxyl in lignin molecule changes ester group into, has slackened intermolecular Hyarogen-bonding, reduces its obstruction to free radicals copolymerization reaction; Meanwhile, introduce unsaturated carbon-carbon double bond in lignin molecule, for free radicals copolymerization reaction provides avtive spot, therefore this copolymerization process effectively improves the copolyreaction efficiency of lignin and acrylonitrile, achieves the efficiency utilization of lignin.
Described unsaturated acyl chlorides refers to the chloride compounds containing unsaturated carbon-carbon double bond (C=C), includes but not limited to acryloyl chloride, methacrylic chloride etc., is preferably acryloyl chloride.
In described esterification, as 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 not limited to dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide, solder(ing)acid, sodium thiocyanate water solution, red fuming nitric acid (RFNA) etc., and being preferably the strong polar organic solvent such as dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide is reaction medium.
In described homogeneous phase solution free radical copolymerization, preferably adopt initator.Described initator is oil-soluble azo-initiator, preferably adopts the one or more kinds of mixing in azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.
In described homogeneous phase solution free radical copolymerization, reaction temperature is preferably 50 ~ 70 DEG C, and the reaction time is preferably 5 ~ 25h.
After described homogeneous phase solution free radical copolymerization terminates, as preferably, remove the gentle bubble of unreacting propylene nitrile monomer.
In sum, the present invention adopts the copolymer of lignin and acrylonitrile to prepare fiber as spinning solution by electrostatic spinning process, make grafted propylene nitrile segments on lignin molecule, acrylonitrile segment is utilized to have the advantage of good heat endurance, improve the resistance to meltbility of fiber in thermostabilization processing procedure, thus it is molten also to avoid generation between fiber, and it is even higher the heating rate in thermostabilization process can be brought up to 10 ~ 50 DEG C/min, thus effectively improves preparation efficiency.
Accompanying drawing explanation
Fig. 1 is the esterification lignin of acryloyl chloride modification in the embodiment of the present invention 1 and the infrared spectrogram of acrylonitrile copolymer;
Fig. 2 be in the embodiment of the present invention 1 with the esterification lignin of acryloyl chloride modification and acrylonitrile copolymer for spinning solution, make fiber through electrostatic spinning, then the electron scanning micrograph of the carbon nano-fiber made through thermostabilization process, carbonization treatment.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, it is pointed out that the following stated embodiment is intended to be convenient to the understanding of the present invention, and any restriction effect is not play to it.
Embodiment 1:
In the present embodiment, the preparation method of lignin-base carbon nano-fiber comprises the steps:
(1) dimethyl sulfoxide (DMSO), lignin and acryloyl chloride is added successively by weight 100:30:30 in the reactor, esterification 1h is stirred at 25 DEG C, the HCl produced with esterification in a small amount of triethylamine (TEA) is added after reaction terminates, add ether again and make modified lignin deposit, then filter, and with absolute ethanol washing repeatedly, removing TEA hydrochloride, obtains the esterification lignin of acryloyl chloride modification;
(2) esterification lignin, acrylonitrile, the azodiisobutyronitrile of the acryloyl chloride modification that 100:25:25:1 adds dimethyl formamide successively by weight in the reactor, above-mentioned steps (1) obtains, homogeneous phase solution free radical copolymerization is carried out 20 hours under nitrogen protection in 60 DEG C, the unreacting propylene nitrile monomer in polymer fluid is removed under vacuo after reaction terminates, then leave standstill and remove bubble, obtain the copolymer spinning fluid of esterification lignin and acrylonitrile;
The infrared spectrogram of the copolymer spinning fluid of this esterification lignin and acrylonitrile as shown in Figure 1.2243cm in figure
- 1place's absworption peak is the characteristic absorption peak of acrylonitrile cyano group stretching vibration, 1721cm
- 1place's absworption peak is the characteristic absorption peak of esterification lignin carbonylic stretching vibration, in addition, 1410,1510 and 1610cm
- 1there is the characteristic absorption peak of lignin benzene ring structure in place, shows the copolymer successfully obtaining esterification lignin and acrylonitrile.
(3) adopt method of electrostatic spinning, the esterification lignin obtained by above-mentioned steps (2) and acrylonitrile copolymer make electrospinning fibre, and voltage is 15KV, and accepting distance is 10cm, and spinning solution extruded velocity is 0.1ml/h, obtained electrospinning fibre;
(4) electrospinning fibre that step (3) is obtained is risen to 300 DEG C with the speed of 10 DEG C/min from room temperature in air atmosphere, constant temperature keeps 30min to carry out thermostabilization process; Then rise to 1000 DEG C with the speed of 20 DEG C/min from room temperature in a nitrogen atmosphere, constant temperature keeps 10min to carry out charing process, obtained carbon nano-fiber.
Adopt scanning electronic microscope to characterize this carbon nano-fiber, as shown in Figure 2, find not stick together between fiber, the average diameter of carbon nano-fiber is about 250nm in its cross section.
Embodiment 2:
In the present embodiment, the preparation method of lignin-base carbon nano-fiber comprises the steps:
(1) dimethyl sulfoxide (DMSO), lignin and acryloyl chloride is added successively by weight 100:30:20 in the reactor, esterification 1h is stirred at 35 DEG C, the HCl produced with esterification in a small amount of triethylamine (TEA) is added after reaction terminates, add ether again and make modified lignin deposit, then filter, and with absolute ethanol washing repeatedly, removing TEA hydrochloride, obtains the esterification lignin of acryloyl chloride modification;
(2) esterification lignin, acrylonitrile, the azodiisobutyronitrile of the acryloyl chloride modification that 100:30:20:1 adds dimethyl sulfoxide (DMSO) successively by weight in the reactor, above-mentioned steps (1) obtains, homogeneous phase solution free radical copolymerization is carried out 18 hours under nitrogen protection in 65 DEG C, after reaction terminates, remove the unreacting propylene nitrile monomer in polymer fluid under vacuo, then leave standstill and remove bubble, obtain the copolymer spinning fluid of esterification lignin and acrylonitrile;
(3) adopt method of electrostatic spinning, the esterification lignin obtained by above-mentioned steps (2) and acrylonitrile copolymer make electrospinning fibre, and voltage is 25KV, accepting distance is 15cm, spinning solution extruded velocity is 0.3ml/h, obtained electrospinning fibre;
(4) electrospinning fibre that step (3) is obtained is risen to 300 DEG C with the speed of 30 DEG C/min from room temperature in air atmosphere, constant temperature keeps 30min to carry out thermostabilization process; Then rise to 1000 DEG C with the speed of 50 DEG C/min from room temperature in a nitrogen atmosphere, constant temperature keeps 10min to carry out charing process, obtained carbon nano-fiber.
Adopt scanning electronic microscope to characterize this carbon nano-fiber, find not stick together between fiber, the average diameter of carbon nano-fiber is about 640nm.
Embodiment 3:
In the present embodiment, the preparation method of lignin-base carbon nano-fiber comprises the steps:
(1) dimethyl sulfoxide (DMSO), unmodified lignin and acryloyl chloride is added successively by weight 100:30:10 in the reactor, esterification 4h is stirred at 25 DEG C, the HCl produced with esterification in a small amount of triethylamine (TEA) is added after reaction terminates, add ether again and make modified lignin deposit, then filter, and with absolute ethanol washing repeatedly, removing TEA hydrochloride, obtains the esterification lignin of acryloyl chloride modification;
(2) esterification lignin, acrylonitrile, the 2,2'-Azobis(2,4-dimethylvaleronitrile) of the acryloyl chloride modification that 100:30:20:1 adds dimethyl formamide successively by weight in the reactor, above-mentioned steps (1) obtains, homogeneous phase solution free radical copolymerization is carried out 20 hours under nitrogen protection in 65 DEG C, the unreacting propylene nitrile monomer in polymer fluid is removed under vacuo after reaction terminates, then leave standstill and remove bubble, obtain lignin-acrylonitrile copolymer;
(3) adopt method of electrostatic spinning, the esterification lignin obtained by above-mentioned steps (2) and acrylonitrile copolymer make electrospinning fibre, and voltage is 15KV, and accepting distance is 10cm, and spinning solution extruded velocity is 0.1ml/h, obtained electrospinning fibre;
(4) electrospinning fibre that step (3) is obtained is risen to 300 DEG C with the speed of 20 DEG C/min from room temperature in air atmosphere, constant temperature keeps 50min to carry out thermostabilization process; Then rise to 1000 DEG C with the speed of 50 DEG C/min from room temperature in a nitrogen atmosphere, constant temperature keeps 20min to carry out charing process, obtained carbon nano-fiber.
Adopt scanning electronic microscope to characterize this carbon nano-fiber, find not stick together between fiber, the average diameter of carbon nano-fiber is about 530nm.
Embodiment 4:
In the present embodiment, the preparation method of lignin-base carbon nano-fiber comprises the steps:
(1) dimethyl sulfoxide (DMSO), lignin and acryloyl chloride is added successively by weight 100:30:20 in the reactor, esterification 1h is stirred at 25 DEG C, the HCl produced with esterification in a small amount of triethylamine (TEA) is added after reaction terminates, add ether again and make modified lignin deposit, then filter, and with absolute ethanol washing repeatedly, removing TEA hydrochloride, obtains the esterification lignin of acryloyl chloride modification;
(2) esterification lignin, acrylonitrile, the 2,2'-Azobis(2,4-dimethylvaleronitrile) of the acryloyl chloride modification that 100:30:20:1 adds dimethylacetylamide successively by weight in the reactor, above-mentioned steps (1) obtains, homogeneous phase solution free radical copolymerization is carried out 18 hours under nitrogen protection in 58 DEG C, after reaction terminates, remove the unreacting propylene nitrile monomer in polymer fluid under vacuo, then leave standstill and remove bubble, obtain lignin-acrylonitrile copolymer;
(3) adopt method of electrostatic spinning, the esterification lignin obtained by above-mentioned steps (2) and acrylonitrile copolymer make electrospinning fibre, and voltage is 10KV, and accepting distance is 8cm, and spinning solution extruded velocity is 0.1ml/h, obtained electrospinning fibre;
(4) electrospinning fibre that step (3) is obtained is risen to 300 DEG C with the speed of 35 DEG C/min from room temperature in air atmosphere, constant temperature keeps 50min to carry out thermostabilization process; Then rise to 1000 DEG C with the speed of 30 DEG C/min from room temperature in a nitrogen atmosphere, constant temperature keeps 30min to carry out charing process, obtained carbon nano-fiber.
Adopt scanning electronic microscope to characterize this carbon nano-fiber, find not stick together between fiber, the average diameter of carbon nano-fiber is about 700nm.
Embodiment 5:
In the present embodiment, the preparation method of lignin-base carbon nano-fiber comprises the steps:
(1) dimethyl sulfoxide (DMSO), lignin and methacrylic chloride is added successively by weight 100:30:5 in the reactor, esterification 4h is stirred at 25 DEG C, the HCl produced with esterification in a small amount of triethylamine (TEA) is added after reaction terminates, add ether again and make modified lignin deposit, then filter, and with absolute ethanol washing repeatedly, removing TEA hydrochloride, obtains the esterification lignin of acryloyl chloride modification;
(2) esterification lignin, acrylonitrile, the azodiisobutyronitrile of the methacrylic chloride modification that 100:30:20:1 adds dimethyl formamide successively by weight in the reactor, above-mentioned steps (1) obtains.Carry out homogeneous phase solution free radical copolymerization 22 hours in 60 DEG C under nitrogen protection, after reaction terminates, remove the unreacting propylene nitrile monomer in polymer fluid under vacuo, then leave standstill and remove bubble, obtain the copolymer spinning fluid of esterification lignin and acrylonitrile;
(3) adopt method of electrostatic spinning, the esterification lignin obtained by above-mentioned steps (2) and acrylonitrile copolymer make electrospinning fibre, and voltage is 15KV, and accepting distance is 10cm, and spinning solution extruded velocity is 0.1ml/h, obtained electrospinning fibre;
(4) electrospinning fibre that step (3) is obtained is risen to 300 DEG C with the speed of 10 DEG C/min from room temperature in air atmosphere, constant temperature keeps 20min to carry out thermostabilization process; Then rise to 1000 DEG C with the speed of 10 DEG C/min from room temperature in a nitrogen atmosphere, constant temperature keeps 10min to carry out charing process, obtained carbon nano-fiber.
Adopt scanning electronic microscope to characterize this carbon nano-fiber, find not stick together between fiber, the average diameter of carbon nano-fiber is about 380nm.
Embodiment 6:
In the present embodiment, the preparation method of lignin-base carbon nano-fiber comprises the steps:
(1) dimethyl sulfoxide (DMSO), lignin and methacrylic chloride is added successively by weight 100:30:30 in the reactor, esterification 1h is stirred at 25 DEG C, the HCl produced with esterification in a small amount of triethylamine (TEA) is added after reaction terminates, add ether again and make modified lignin deposit, then filter, and with absolute ethanol washing repeatedly, removing TEA hydrochloride, obtains the esterification lignin of methacrylic chloride modification;
(2) esterification lignin, acrylonitrile, the azodiisobutyronitrile of the methacrylic chloride modification that 100:30:20:1 adds dimethylacetylamide successively by weight in the reactor, above-mentioned steps (1) obtains.Carry out homogeneous phase solution free radical copolymerization 18 hours in 65 DEG C under nitrogen protection, after reaction terminates, remove the unreacting propylene nitrile monomer in polymer fluid under vacuo, then leave standstill and remove bubble, obtain the copolymer spinning fluid of esterification lignin and acrylonitrile;
(3) adopt method of electrostatic spinning, by esterification lignin obtained for above-mentioned steps (2) and acrylonitrile copolymer, it makes electrospinning fibre, and voltage is 10KV, and accepting distance is 6cm, and spinning solution extruded velocity is 1ml/h, obtains electrospinning fibre;
(4) electrospinning fibre that step (3) is obtained is risen to 300 DEG C with the speed of 50 DEG C/min from room temperature in air atmosphere, constant temperature keeps 50min to carry out thermostabilization process; Then rise to 1000 DEG C with the speed of 20 DEG C/min from room temperature in a nitrogen atmosphere, constant temperature keeps 10min to carry out charing process, obtained carbon nano-fiber.
Adopt scanning electronic microscope to characterize this carbon nano-fiber, find not stick together between fiber, the average diameter of carbon nano-fiber is about 940nm.
Above-described embodiment has been described in detail technical scheme of the present invention; be understood that and the foregoing is only specific embodiments of the invention; be not limited to the present invention; all make in spirit of the present invention any amendment, supplement or similar fashion substitute etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a lignin-base carbon nano-fiber, utilize electrostatic spinning process, lignin-base spinning solution is made fiber, carbon fiber is made again through thermostabilization process and charing process, it is characterized in that: described lignin-base spinning solution is the copolymer of lignin and acrylonitrile, i.e. grafted propylene nitrile segments on lignin molecule.
2. the preparation method of lignin-base carbon nano-fiber as claimed in claim 1, it is characterized in that: in described electrostatic spinning process, voltage is 5 ~ 50KV, and receiving range is 5 ~ 20cm, 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, is characterized in that: described thermostabilization is treated in air atmosphere from room temperature to 200 DEG C ~ 300 DEG C, and then constant temperature keeps 10 ~ 60min.
4. the preparation method of lignin-base carbon nano-fiber as claimed in claim 3, is characterized in that: described heating rate is 5 ~ 60 DEG C/min, is preferably 10 ~ 50 DEG C/min.
5. the preparation method of lignin-base carbon nano-fiber as claimed in claim 1, is characterized in that: described charing is treated in a nitrogen atmosphere from room temperature to 800 DEG C ~ 1500 DEG C, and then constant temperature keeps 10 ~ 60min; As preferably, described heating rate is 10 ~ 50 DEG C/min.
6. the preparation method of the lignin-base carbon nano-fiber as described in claim arbitrary in claim 1 to 5, is characterized in that: the copolymerization process of described lignin and acrylonitrile is:
First by unsaturated acyl chlorides and lignin generation esterification, make the hydroxyl in lignin molecule change ester group into, in lignin molecule, introduce unsaturated carbon-carbon double bond simultaneously, obtain esterification lignin; Then this esterification lignin and acrylonitrile monemer are carried out homogeneous phase solution free radical copolymerization, grafted propylene nitrile segments, obtain the copolymer of esterification lignin and acrylonitrile.
7. the preparation method of lignin-base carbon nano-fiber as claimed in claim 6, is characterized in that: unsaturated acyl chlorides is acryloyl chloride and/or methacrylic chloride.
8. the preparation method of lignin-base carbon nano-fiber as claimed in claim 6, it is characterized in that: in described esterification, 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.
9. the preparation method of lignin-base carbon nano-fiber as claimed in claim 6, it is characterized in that: in described esterification, reaction temperature is 0 ~ 50 DEG C, and the reaction time is 0.1 ~ 10h;
As preferably, in described homogeneous phase solution free radical copolymerization, reaction temperature is 50 ~ 70 DEG C, and the reaction time is 5 ~ 25h.
10. the preparation method of lignin-base carbon nano-fiber as claimed in claim 6, is characterized in that: in described homogeneous phase solution free radical copolymerization, adopts initator; Described initator is the one or more kinds of mixing in azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510330420.0A CN104947247B (en) | 2015-06-15 | 2015-06-15 | A kind of preparation method of lignin-base carbon nano-fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510330420.0A CN104947247B (en) | 2015-06-15 | 2015-06-15 | A kind of preparation method of lignin-base carbon nano-fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104947247A true CN104947247A (en) | 2015-09-30 |
| CN104947247B CN104947247B (en) | 2017-08-25 |
Family
ID=54162291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510330420.0A Active CN104947247B (en) | 2015-06-15 | 2015-06-15 | A kind of preparation method of lignin-base carbon nano-fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104947247B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109137122A (en) * | 2018-07-25 | 2019-01-04 | 司彩霞 | A kind of preparation method of ion liquid modified heat-resistance polypropylene nitrile fiber |
| CN113527711A (en) * | 2021-08-27 | 2021-10-22 | 西南交通大学 | Method for preparing lignin nanotubes by using agriculture and forestry biomass raw materials |
| CN113604908A (en) * | 2021-09-07 | 2021-11-05 | 宁波瑞耐复合材料有限公司 | Preparation method of carbon nanofiber and nylon composite material reinforced by carbon nanofiber |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080317661A1 (en) * | 2007-06-25 | 2008-12-25 | Weyerhaeuser Co. | Carbon fibers from kraft softwood lignin |
| CN100509891C (en) * | 2005-04-30 | 2009-07-08 | 江苏工业学院 | Process for preparing modified lignocellulose sulfonate graft copolymer |
| CN101768799A (en) * | 2010-01-29 | 2010-07-07 | 华南理工大学 | Lignin carbon nanofiber and preparation method thereof |
| CN102652192A (en) * | 2009-12-09 | 2012-08-29 | 日清纺控股株式会社 | Flexible carbon fiber nonwoven fabric |
| KR20120109227A (en) * | 2011-03-28 | 2012-10-08 | 전남대학교산학협력단 | Method for preparation of carbon fibers using lignin copolymer and the carbon fibers prepared thereby |
-
2015
- 2015-06-15 CN CN201510330420.0A patent/CN104947247B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100509891C (en) * | 2005-04-30 | 2009-07-08 | 江苏工业学院 | Process for preparing modified lignocellulose sulfonate graft copolymer |
| US20080317661A1 (en) * | 2007-06-25 | 2008-12-25 | Weyerhaeuser Co. | Carbon fibers from kraft softwood lignin |
| CN102652192A (en) * | 2009-12-09 | 2012-08-29 | 日清纺控股株式会社 | Flexible carbon fiber nonwoven fabric |
| CN101768799A (en) * | 2010-01-29 | 2010-07-07 | 华南理工大学 | Lignin carbon nanofiber and preparation method thereof |
| KR20120109227A (en) * | 2011-03-28 | 2012-10-08 | 전남대학교산학협력단 | Method for preparation of carbon fibers using lignin copolymer and the carbon fibers prepared thereby |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109137122A (en) * | 2018-07-25 | 2019-01-04 | 司彩霞 | A kind of preparation method of ion liquid modified heat-resistance polypropylene nitrile fiber |
| CN109137122B (en) * | 2018-07-25 | 2020-09-29 | 欧士曼(台州)高分子科技有限公司 | Preparation method of ionic liquid modified heat-resistant polyacrylonitrile fiber |
| CN113527711A (en) * | 2021-08-27 | 2021-10-22 | 西南交通大学 | Method for preparing lignin nanotubes by using agriculture and forestry biomass raw materials |
| CN113604908A (en) * | 2021-09-07 | 2021-11-05 | 宁波瑞耐复合材料有限公司 | Preparation method of carbon nanofiber and nylon composite material reinforced by carbon nanofiber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104947247B (en) | 2017-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108103616B (en) | Preparation method of nitrogen-doped lignin-based carbon fiber composite material | |
| CN102534870B (en) | Preparation method of grapheme-modified acrylonitrile base carbon fiber | |
| CN1194121C (en) | Super high molecular mass polythylene/carbon nano tube composite fiber used in jelly glue spinning and its preparation | |
| CN102586920B (en) | Preparation method of polyacrylonitrile nanometer fibers | |
| CN104945573B (en) | The preparation method of the preparation method and lignin-base carbon fiber of lignin and acrylonitrile copolymer | |
| Sun et al. | Recent advances in lignin-based carbon fibers (LCFs): precursors, fabrications, properties, and applications | |
| KR100623881B1 (en) | Preparation method of polyacrylonitrilePAN/polyimidePI composite nano-fibers by electrospinning, and carbon fibers, activated carbon fibers therefrom | |
| CN107604482B (en) | A kind of N doping porous filamentous nanocarbon and preparation method thereof | |
| CN112251914B (en) | High-temperature-resistant composite nanofiber membrane for preparing piezoelectric material and preparation method thereof | |
| CN108611704B (en) | Nano carbon fiber and preparation method thereof | |
| CN101270198B (en) | Method for electrostatic blending polyacrylonitrile/glycol cellulose nano-fibrous membrane | |
| CN105734724A (en) | Novel method for preparing carbon nanofibers through electrospinning | |
| CN104947247A (en) | Preparation method of lignin-based carbon nanofiber | |
| Hu et al. | Lignin-based/polypyrrole carbon nanofiber electrode with enhanced electrochemical properties by electrospun method | |
| CN103757742B (en) | A kind of preparation method of nuclear shell structure nano fiber of fluorine-contained surface | |
| CN111100603A (en) | High-thermal-conductivity phase-change energy storage material based on electrostatic spinning and preparation method thereof | |
| CN109860485A (en) | A kind of polyimide nano-fiber diaphragm and its manufacturing method | |
| CN112813539B (en) | Preparation method of polyacrylonitrile-based carbon fiber | |
| CN103320902A (en) | Bio-based active carbon fiber filtering material and preparation method thereof | |
| CN108411491A (en) | A kind of preparation method of double cross-linking type electrospun fibers films | |
| CN109082731A (en) | A kind of cross-linked porous carbon nano-fiber and preparation method thereof | |
| CN110468465B (en) | Carbon nano tube/polyimide composite carbonized fiber and production method thereof | |
| CN109629227B (en) | Preparation method of fiber-based carbon nanotube conductive material | |
| Pan et al. | Preparation and characterization of polyacrylonitrile-polyaniline blend nanofibers | |
| CN105869927B (en) | A kind of method that random copolymer prepares high-specific surface area and high specific capacitance carbon fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |