CN109943920A - A kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber - Google Patents
A kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber Download PDFInfo
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Abstract
The present invention discloses a kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber; the lignin and polyacrylonitrile handled first with acetylation and graft modification is configured to polyacrylonitrile/lignin mixed solution; then the above-mentioned mixed liquor of electrostatic spinning prepares polyacrylonitrile/lignin nano fibrous membrane, finally carries out pre-oxidation to the nano fibrous membrane of preparation and carbonization treatment obtains polyacrylonitrile/lignin carbon nano-fiber.Lignin is after acetylation and graft modification processing in the method for the present invention; there is preferable compatibility with polyacrylonitrile; improve polyacrylonitrile/lignin mixed solution spinnability; polyacrylonitrile/lignin nanofiber diameter of preparation reaches 200nm~350nm simultaneously; thermodynamic property is also improved, and is successfully prepared for the good carbon nano-fiber of structural behaviour using polyacrylonitrile/lignin after pre-oxidation and carbonization treatment.
Description
Technical field
The present invention relates to the technical field of carbon nano-fiber preparation, in particular to a kind of electrostatic blended spinning polyacrylonitrile/wooden
The method that element prepares carbon nano-fiber.
Background technique
Carbon fiber has low-density, high intensity, high-modulus, high temperature resistant and the excellent performances such as corrosion-resistant, is widely used in
The fields such as space flight and aviation, biologic medical, sports equipment and auto parts and components, the preparation and application of carbon fiber also push section's technical economy
The development of Ji.Nanoscale carbon fiber assigns the biggish porosity of carbon fiber and specific surface area, application range are more extensive.
The common technique for preparing carbon nano-fiber mainly has pulling method, self-assembly method, vapour deposition process, templated synthesis
Method, method of electrostatic spinning etc..Wherein pulling method has higher requirement, the yield of self-assembly method and vapour deposition process to the viscosity of solution
Not high, template synthesis method not can be carried out continuous production, and method of electrostatic spinning is in the side such as spinning technology parameter and nanofibers of dimensions
There is preferable controllability in face, more superior compared with other methods in terms of efficiency and yield.
Electrostatic spinning prepares the raw material of carbon fiber there are commonly polyacrylonitrile (PAN) fiber, with carbon fiber demand not
The problem of disconnected increase, the PAN consumption as petroleum derivative is increasing, higher cost is also more and more prominent, finds one kind
It is also more more and more urgent that lower cost materials as carbon fiber prepare raw material.Lignin abundance, phosphorus content is high, can be used as carbon fiber
A kind of bio-based materials of raw material, but its molecular structure is complicated, is not easy spinning moulding.Rationally to utilize lignin, to lignin
Carrying out chemical modification and mix electrospinning with the preferable high molecular material of other spinnabilitys will be as the effective ways using lignin.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of electrostatic blended spinning polyacrylonitrile/lignin systems
The method of standby carbon nano-fiber, this method are prepared by being modified to lignin using electrostatic blended spinning polyacrylonitrile/lignin
Carbon fibre precursor improves the spinnability of lignin, is prepared for the fiber precursor of preferable thermodynamic property with being not only simple, and
Pre-oxidation is carried out to fiber precursor again and carbonization treatment obtains the carbon nano-fiber of compact structure.
The technical solution of the present invention is as follows: a kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber, packet
Include following steps:
(1) lignosulfonates are pre-processed, obtains lignin；
(2) step (1) resulting lignin is first subjected to acetic anhydride acetylation process, then carried out at acrylonitrile graft modification
Reason；
(3) it will be mixed by the lignin of step (2) processing with polyacrylonitrile, gained mixture is dissolved in organic solvent
In, it is configured to polyacrylonitrile/lignin mixed solution that Solute mass fraction is 8~16%；
(4) electrostatic spinning molding is carried out to the polyacrylonitrile prepared in step (3)/lignin mixed solution, prepares poly- third
Alkene nitrile/lignin nano fibrous membrane；When electrostatic spinning forms, voltage is 10~20kv, and receiving distance is 12~20cm, and flow pushes away
Speed is 0.2~2ml/h；
(5) polyacrylonitrile/lignin nano fibrous membrane prepared in step (4) is pre-oxidized in air, is pre-oxidized
Temperature is 200~280 DEG C, and preoxidation time is 0.5~2h, and polyacrylonitrile/lignin nano fibrous membrane after pre-oxidation is in nitrogen
700~1000 DEG C of 2~8h of carbonization are warming up under gas shielded.
In the step (1), the preprocess method of lignosulfonates are as follows: add lignosulfonates in NaOH solution
Heat of solution, after filtering removes impurity, simultaneously the concentrated sulfuric acid is added dropwise in quick agitating solution, adjusts the pH value of solution to 2~4, centrifugation is dry
Dry solution, obtains lignin.
In the step (2), the acetic anhydride acetylation process method of lignin are as follows: by lignin obtained in step (1)
It is dissolved in dimethyl sulfoxide, adds triethylamine, then acetic anhydride is slowly added dropwise and is stirred continuously, 2~8h is reacted under room temperature, instead
It answers product to be placed in ether to precipitate, filter, then the solid being obtained by filtration with ethanol washing is obtained through 50~80 DEG C of vacuum dryings
Acetylation lignin.
In the step (2), the acrylonitrile graft modification processing method of lignin are as follows: by acrylonitrile, azodiisobutyronitrile
It is mixed with dimethyl sulfoxide, is warming up to 60~90 DEG C, is slowly stirred under nitrogen protection, mixing time is no more than 2h, is mixed
Close solution；Lignin Jing Guo acetic anhydride acetylation process is mixed with mixed solution, adds CaCl2And H2O2, protected in nitrogen
It is stirred to react 14 under shield~for 24 hours.
In the step (3), the mass ratio of lignin and polyacrylonitrile (PAN) are 5:5~1:9.
In the step (3), organic solvent uses dimethyl formamide solution, dimethyl sulphoxide solution or dimethyl formyl
Amine/dimethyl sulfoxide mixed solution, the Solute mass fraction of organic solvent are 8%~16%.
In the step (4), the environment temperature of electrostatic spinning is 10~30 DEG C, and ambient humidity is 20%~70%.
In the step (4), the needle diameter of electrostatic spinning is 0.1~1mm.
In the preoxidation process of the step (5), unidirectional is applied to polyacrylonitrile/lignin nano fibrous membrane
Power.
In the preoxidation process of the step (5), heating rate is 5~20 DEG C/min.
The present invention compared with the existing technology, has the advantages that
The method that this electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber, is received using lignin as carbon is prepared
Rice one of fibrous raw material, lignin abundance and safe and non-toxic reduce use cost.
The method that this electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber has carried out acetyl to lignin in advance
Change and graft modification is handled, improves the compatibility and spinnability of lignin and high molecular material.
The method that this electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber, it is quiet using polyacrylonitrile and lignin
Electricity is blended to prepare nano fibrous membrane, and polyacrylonitrile/lignin nano fibrous membrane fibre diameter of preparation is smaller, it can reach 200~
350nm, thermodynamic property are preferable；The present invention be successfully prepared the polyacrylonitrile with preferable shape characteristic and carbonizing degree/
Lignin carbon nano-fiber.
Detailed description of the invention
Fig. 1 is the polyacrylonitrile/lignin nanofiber Electronic Speculum shape appearance figure prepared by 1 method of embodiment.
Fig. 2 is the polyacrylonitrile/lignin carbon nano-fiber Raman spectrogram prepared by 2 method of embodiment.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
A kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber of the present embodiment, as shown in Figure 1, tool
Body the following steps are included:
(1) it takes 20g lignosulfonates to be dissolved in the NaOH solution of the 0.5mol/L of 2000ml, stirs to completely molten
Solution, will wherein contaminant filter fall, the concentrated sulfuric acid is slowly added dropwise into obtained filtrate and is stirred continuously, and adjust its pH value to 3, heat
To 85 DEG C of stirring a period of times, centrifugation is precipitated after cooling, centrifugal drying is repeated several times, last drying and grinding obtains lignin powder
End.
(2) the lignin powder that 2g step (1) obtains is dissolved in the dimethyl sulfoxide (DMSO) of 40ml, dissolution is completed
After cool down, then be added 2ml triethylamine (TEA), be slow added into 20ml acetic anhydride and be stirred continuously, react 6h under room temperature；On
It states reaction product to precipitate in ether, be centrifuged, ethanol washing, 60 DEG C of vacuum drying obtain acetylation lignin；By 5g acrylonitrile
(AN) it is added in the three neck round bottom flask of the dimethyl sulfoxide equipped with 20ml (DMSO) with 10mg azodiisobutyronitrile (AIBN),
It is slowly stirred dissolution acrylonitrile and azodiisobutyronitrile, 70 DEG C is warming up to, stirs 2h under nitrogen protection；40ml bis- will be dissolved in
The 2g acetylation lignin of methyl sulfoxide pours into round-bottomed flask, and the H of 2gCacl2 and 2ml30% is then added2O2, in nitrogen protection
It is stirred to react for 24 hours.
(3) modified lignin is mixed with polyacrylonitrile 3:7 in mass ratio, dissolution is dispersed in 5ml dimethyl formyl
It is 12% polyacrylonitrile/lignin mixed solution that mass fraction is configured in amine (DMF), as electrostatic spinning liquid；Using electrostatic
Spinning voltage is 15kv, and it is 18cm that electrostatic spinning, which receives distance, and electrostatic spinning flow pushes away process conditions that speed is 0.5ml/h to matching
The electrostatic spinning liquid of system carries out electrostatic spinning molding, prepares polyacrylonitrile/lignin nano fibrous membrane.
(4) obtained polyacrylonitrile/lignin nano fibrous membrane is placed in Muffle furnace, in air atmosphere with 5 DEG C/
Min is warming up to 250 DEG C of heat preservations and is pre-oxidized for 2 hours, then sets the polyacrylonitrile after pre-oxidation/lignin nano fibrous membrane
In vacuum tube furnace, 900 DEG C of carbonizations are warming up to 5 DEG C/min under nitrogen protection, keep the temperature 2h, obtain polyacrylonitrile/wooden
Plain carbon nano-fiber.
Embodiment 2
A kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber of the present embodiment, specifically includes following
Step:
(1) it takes 20g lignosulfonates to be dissolved in the NaOH solution of the 0.5mol/L of 2000ml, stirs to completely molten
Solution, will wherein contaminant filter fall, the concentrated sulfuric acid is slowly added dropwise into obtained filtrate and is stirred continuously, and adjust its pH value to 3, heat
To 85 DEG C of stirring a period of times, centrifugation is precipitated after cooling, centrifugal drying is repeated several times, last drying and grinding obtains lignin powder
End.
(2) the lignin powder that 2g step (1) obtains is dissolved in the dimethyl sulfoxide (DMSO) of 40ml, dissolution is completed
After cool down, then be added 2ml triethylamine (TEA), be slow added into 30ml acetic anhydride and be stirred continuously, react 4h at 30 DEG C；On
It states reaction product to precipitate in ether, be centrifuged, ethanol washing, 60 DEG C of vacuum drying obtain acetylation lignin；By 5g acrylonitrile
(AN) it is added in the three neck round bottom flask of the dimethyl sulfoxide equipped with 20ml (DMSO) with 10mg azodiisobutyronitrile (AIBN),
It is slowly stirred dissolution acrylonitrile and azodiisobutyronitrile, 70 DEG C is warming up to, stirs 2h under nitrogen protection；40ml bis- will be dissolved in
The 2g acetylation lignin of methyl sulfoxide pours into round-bottomed flask, and the H of 2gCacl2 and 2ml30% is then added2O2, in nitrogen protection
It is stirred to react for 24 hours.
(3) modified lignin is mixed with polyacrylonitrile 2:8 in mass ratio, dissolution is dispersed in 5ml dimethyl formyl
It is 12% polyacrylonitrile/lignin mixed solution that mass fraction is configured in amine (DMF), as electrostatic spinning liquid；Using electrostatic
Spinning voltage is 12kv, and it is 16cm that electrostatic spinning, which receives distance, and electrostatic spinning flow pushes away the fast process conditions for being 1ml/h to preparation
Electrostatic spinning liquid carry out electrostatic spinning molding, prepare polyacrylonitrile/lignin nano fibrous membrane.
(4) obtained polyacrylonitrile/lignin nano fibrous membrane is placed in Muffle furnace, in air atmosphere with 5 DEG C/
Min is warming up to 230 DEG C of heat preservations and is pre-oxidized for 2 hours, then sets the polyacrylonitrile after pre-oxidation/lignin nano fibrous membrane
In vacuum tube furnace, 900 DEG C of carbonizations are warming up to 5 DEG C/min under nitrogen protection, keep the temperature 2h, obtain polyacrylonitrile/wooden
Plain carbon nano-fiber.
As shown in Fig. 2, being polyacrylonitrile manufactured in the present embodiment/lignin carbon nano-fiber Raman spectrogram；In figure,
1355cm-1The peak at place is known as the peak D, indicates the unordered and defect situation occurred during carbon fibre carbonizing, 1589cm-1Locate
The existing peak peak position G, indicates the integrity degree of carbon fiber structural.R=D/G measures the carbonizing degree and structural integrity of fiber,
The compound carbon fiber R value of polyacrylonitrile/lignin is 0.95, and fibers carbonization degree is higher, and 2894cm-1The peak of appearance is known as ' G
' peak, this peak can only occur in the higher carbon fiber of carbonizing degree.
Embodiment 3
A kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber of the present embodiment, specifically includes following
Step:
(1) it takes 20g lignosulfonates to be dissolved in the NaOH solution of the 0.5mol/L of 2000ml, stirs to completely molten
Solution, will wherein contaminant filter fall, the concentrated sulfuric acid is slowly added dropwise into obtained filtrate and is stirred continuously, and adjust its pH value to 3, heat
To 85 DEG C of stirring a period of times, centrifugation is precipitated after cooling, centrifugal drying is repeated several times, last drying and grinding obtains lignin powder
End.
(2) the lignin powder that 2g step (1) obtains is dissolved in the dimethyl sulfoxide (DMSO) of 40ml, dissolution is completed
After cool down, then be added 2ml triethylamine (TEA), be slow added into 40ml acetic anhydride and be stirred continuously, react 2h under room temperature；On
It states reaction product to precipitate in ether, be centrifuged, ethanol washing, 60 DEG C of vacuum drying obtain acetylation lignin；By 5g acrylonitrile
(AN) it is added in the three neck round bottom flask of the dimethyl sulfoxide equipped with 20ml (DMSO) with 10mg azodiisobutyronitrile (AIBN),
It is slowly stirred dissolution acrylonitrile and azodiisobutyronitrile, 70 DEG C is warming up to, stirs 2h under nitrogen protection；40ml bis- will be dissolved in
The 2g acetylation lignin of methyl sulfoxide pours into round-bottomed flask, and the H of 2gCacl2 and 2ml30% is then added2O2, in nitrogen protection
It is stirred to react for 24 hours.
(3) modified lignin is mixed with polyacrylonitrile 1:9 in mass ratio, dissolution is dispersed in 5ml dimethyl formyl
It is 12% polyacrylonitrile/lignin mixed solution that mass fraction is configured in amine (DMF), as electrostatic spinning liquid；Using electrostatic
Spinning voltage is 12kv, and it is 16cm that electrostatic spinning, which receives distance, and electrostatic spinning flow pushes away the fast process conditions for being 2ml/h to preparation
Electrostatic spinning liquid carry out electrostatic spinning molding, prepare polyacrylonitrile/lignin nano fibrous membrane.
(4) obtained polyacrylonitrile/lignin nano fibrous membrane is placed in Muffle furnace, in air atmosphere with 5 DEG C/
Min is warming up to 280 DEG C of heat preservations and is pre-oxidized for 2 hours, then sets the polyacrylonitrile after pre-oxidation/lignin nano fibrous membrane
In vacuum tube furnace, 900 DEG C of carbonizations are warming up to 5 DEG C/min under nitrogen protection, keep the temperature 2h, obtain polyacrylonitrile/wooden
Plain carbon nano-fiber.
As described above, the present invention can be better realized, above-described embodiment is only presently preferred embodiments of the present invention, is not used
To limit practical range of the invention；It is i.e. all according to equivalent changes and modifications made by the content of present invention, all wanted for right of the present invention
Range claimed is asked to be covered.
Claims (10)
1. a kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber, which is characterized in that including following step
It is rapid:
(1) lignosulfonates are pre-processed, obtains lignin；
(2) step (1) resulting lignin is first subjected to acetic anhydride acetylation process, then carries out acrylonitrile graft modification processing；
(3) it will be mixed by the lignin of step (2) processing with polyacrylonitrile, gained mixture dissolves in organic solvent, matches
Polyacrylonitrile/lignin mixed solution that Solute mass fraction is 8~16% is made；
(4) electrostatic spinning molding is carried out to the polyacrylonitrile prepared in step (3)/lignin mixed solution, prepare polyacrylonitrile/
Lignin nano fibrous membrane；When electrostatic spinning forms, voltage is 10~20kv, and receiving distance is 12~20cm, and flow pushes away speed and is
0.2~2ml/h；
(5) polyacrylonitrile/lignin nano fibrous membrane prepared in step (4) is pre-oxidized in air, Pre oxidation
It is 200~280 DEG C, preoxidation time is 0.5~2h, and polyacrylonitrile/lignin nano fibrous membrane after pre-oxidation is protected in nitrogen
700~1000 DEG C of 2~8h of carbonization are warming up under shield.
2. a kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber according to claim 1, feature
It is, in the step (1), the preprocess method of lignosulfonates are as follows: heat lignosulfonates in NaOH solution
Dissolution, after filtering removal impurity, simultaneously the concentrated sulfuric acid is added dropwise in quick agitating solution, adjusts the pH value of solution to 2~4, centrifugal drying
Solution obtains lignin.
3. a kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber according to claim 1, feature
It is, in the step (2), the acetic anhydride acetylation process method of lignin are as follows: by lignin dissolution obtained in step (1)
In dimethyl sulfoxide, triethylamine is added, then acetic anhydride is slowly added dropwise and is stirred continuously, 2~8h is reacted under room temperature, reaction produces
Object is placed in ether and precipitates, and filtering, then the solid being obtained by filtration with ethanol washing obtain acetyl through 50~80 DEG C of vacuum dryings
Change lignin.
4. a kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber according to claim 1, feature
It is, in the step (2), the acrylonitrile graft modification processing method of lignin are as follows: by acrylonitrile, azodiisobutyronitrile and two
Methyl sulfoxide mixing, is warming up to 60~90 DEG C, is slowly stirred under nitrogen protection, and mixing time is no more than 2h, obtains mixing molten
Liquid；Lignin Jing Guo acetic anhydride acetylation process is mixed with mixed solution, adds CaCl2And H2O2, under nitrogen protection
It is stirred to react 14~for 24 hours.
5. a kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber according to claim 1, feature
It is, in the step (3), the mass ratio of lignin and polyacrylonitrile (PAN) are 5:5~1:9.
6. a kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber according to claim 1, feature
Be, in the step (3), organic solvent using dimethyl formamide solution, dimethyl sulphoxide solution or dimethylformamide/
Dimethyl sulfoxide mixed solution, the Solute mass fraction of organic solvent are 8%~16%.
7. a kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber according to claim 1, feature
It is, in the step (4), the environment temperature of electrostatic spinning is 10~30 DEG C, and ambient humidity is 20%~70%.
8. a kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber according to claim 1, feature
It is, in the step (4), the needle diameter of electrostatic spinning is 0.1~1mm.
9. a kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber according to claim 1, feature
It is, in the step (5), in preoxidation process, unidirectional is applied to polyacrylonitrile/lignin nano fibrous membrane
Power.
10. a kind of method that electrostatic blended spinning polyacrylonitrile/lignin prepares carbon nano-fiber according to claim 1, special
Sign is, in the step (5), in preoxidation process, heating rate is 5~20 DEG C/min.
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| CN116375392A (en) * | 2023-04-07 | 2023-07-04 | 广东长鑫环保科技有限公司 | Preparation process of material using nano carbonized plant modification and activation technology |
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