CN108866821A - A kind of preparation method of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base - Google Patents

A kind of preparation method of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base Download PDF

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CN108866821A
CN108866821A CN201810840101.8A CN201810840101A CN108866821A CN 108866821 A CN108866821 A CN 108866821A CN 201810840101 A CN201810840101 A CN 201810840101A CN 108866821 A CN108866821 A CN 108866821A
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cardanol
ortho position
modified
thermosetting phenolic
activated carbon
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CN108866821B (en
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曹健
张彩云
杨凯
刘淑萍
魏朋
何建新
拱荣华
李洁
任东雪
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Zhongyuan University of Technology
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4391—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C7/00—Heating or cooling textile fabrics
    • D06C7/04—Carbonising or oxidising

Abstract

The invention discloses a kind of preparation methods of high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base, include the following steps：Phenols, aldehyde compound, anacardol are reacted under the action of catalyst, high ortho position Cardanol Modified PF Resin is made in decompression dehydration；It is dissolved in alcohols and is reacted under the action of catalyst with aldehyde compound, high ortho position modified by cardanol thermosetting phenolic resin is made；As carbon precursor solution, using coaxial electrostatic spinning, it is heating and curing to obtain the high ortho position thermosetting phenolic tunica fibrosa of high ortho position modified by cardanol of skin-core structure partially compatible；Then in N2It is carbonized and is activated under protection, obtain the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base.Compared with prior art, the advantages of this method is simple and easy, environmental-friendly, degree of hollowness is controllable, solidification is efficient, high mechanical properties.

Description

A kind of high hollow nanometer gradient active carbon fibre of ortho position modified by cardanol thermosetting phenolic base Tie up the preparation method of film
Technical field
The invention belongs to the preparation fields of extraordinary Carbon Materials, and in particular to a kind of to obtain high ortho position modified by cardanol thermosetting property phenol The preparation method of the hollow nanometer gradient activated carbon fiber film of aldehyde radical.
Background technique
Phenolic resin has lot of advantages as carbon matrix precursor, but its heat resistance is relatively poor, and wherein thermoplastic phenolic is solid The change period is long, process is more, with high costs and pollution environment, and thermosetting phenolic molecular weight is low, and the problem of spinnability difference always can not It avoids.It for the heat resistance for improving phenolic fibre, generallys use chemical method and resin is modified, anacardol primary structure is benzene Phenol meta position replaces the monoene or diolefin long-chain of 15 carbon, therefore it not only only has the characteristic of phenolic compound, and there are also rouge The flexibility of fat compounds of group, this phenol-formaldehyde resin modified can be obviously improved the heat resistance of material, and its C15Side chain can be bright The aobvious toughness for improving material.Wherein Luo Jun（Application number 201410763432.8, a kind of preparation side of Cardanol Modified PF Resin Method）Phenolic resin is modified by anacardol, increases the toughness of phenolic resin, reduces its high temperature red brittleness.And method Easy to operate, environmental-friendly, production cost is low.
The method for preparing the hollow activated carbon fibre of phenolic aldehyde base at present has semi-solid preparation-leaching, profile spinneret spin processes, but The fiber that it is prepared is thicker, prepares cumbersome, with high costs, environmental pollution weight and is difficult to large-area applications.Coaxial electrostatic spinning method The above problem is just can solve, although coaxial electrostatic spinning method has been widely used in various polymer matrix micro-nanos at present In the preparation and production of rice doughnut, but without being applied in the spinning of high ortho position thermosetting phenolic resin.Simultaneously Either conventional spinning method or electrostatic spinning, obtained hollow activated carbon fibre even aperture distribution, on fiber inside and outside wall Hole size it is constant, affect the absorption property of absorbent charcoal material.There is provided herein a kind of coaxial electrostatic spinning methods to prepare high neighbour The preparation method of the position hollow nanometer gradient activated carbon fiber film of thermosetting phenolic base, simplifies preparation step, improves solidification effect Rate, while absorption property, mechanical property, chemical property and heat-proof quality can be further increased etc., keep it industrial in hydrogen storage, The fields such as environmental protection, Water warfare and electrochemistry are widely used.
Summary of the invention
The present invention changes in view of the above problems, obtaining high ortho position anacardol by addition anacardol in phenolic resin synthesis process Property phenolic resin, and react to obtain high ortho position modified by cardanol thermosetting phenolic resin with aldehydes, pass through coaxial electrostatic spinning method It is prepared for a kind of continuous, flexible, the hollow activated carbon nano fiber of high ortho position modified by cardanol thermosetting phenolic base of high Residual carbon Preparation method.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of preparation method of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base, including with Lower step：
（1）By anacardol, phenols and aldehyde compound under the first catalyst action boiling reaction 2-6h, then be added dropwise acidity urge Agent continues boiling reaction 0.5-4h, and decompression dehydration is to slowly warm up to 105-165 DEG C after being cooled to 40 DEG C, and the reaction was continued 0.1-4h obtains high ortho position Cardanol Modified PF Resin；
（2）High ortho position Cardanol Modified PF Resin is dissolved in alcohol compound, aldehyde compound and the second catalyst is added, 3-7h is reacted under conditions of 45-85 DEG C, is down to room temperature, pH is adjusted to make pH=5-8.0, is filtered, removes impurity, then decompression dehydration, Decompression dehydration final temperature is 50-90 DEG C, and the decompression dehydration time is 0.5-3h, and high ortho position modified by cardanol thermosetting phenolic is made Resin；
（3）High ortho position modified by cardanol thermosetting phenolic resin and Linear Polymer polymer are dissolved in solvent, shell liquid are made, Linear Polymer polymer is dissolved in solvent obtained core liquid to be heating and curing to obtain skin-core structure portion using coaxial electrostatic spinning The high ortho position thermosetting phenolic tunica fibrosa of high ortho position modified by cardanol that split-phase is held；Then in N2It is carbonized and is activated under protection, Obtain the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base.
The step（1）In, phenolic compound is phenol, p-cresol or xylenol；Aldehyde compound is formaldehyde, acetaldehyde Or furfural, the first catalyst are zinc acetate, cadmium acetate or zinc oxide；Acid catalyst is phosphoric acid, nitric acid, mass fraction 98% Sulfuric acid or mass fraction be 37% hydrochloric acid；Wherein the molar ratio of phenols and aldehydes is 1:（0.6-2）, phenolic compound and The mass ratio of one catalyst is 100:（0.8-3）, the mass ratio of phenolic compound and acid catalyst is 100:（0.2-2）；Phenol The mass ratio of class and anacardol is 100:（5-35）.
The step（2）In, alcohol compound is methanol or ethyl alcohol；Aldehyde compound be formaldehyde, acetaldehyde, in furfural extremely Few one kind, the second catalyst are triethanolamine, barium carbonate or barium acetate；Adjusting acid used in pH is that hydrochloric acid, oxalic acid or mass fraction are One of 98% sulfuric acid；Wherein the mass ratio of high ortho position Cardanol Modified PF Resin and alcohols is 1:1-3, high ortho position waist The molar ratio of fruit phenol phenol-formaldehyde resin modified and aldehydes is 1:1-10, high ortho position Cardanol Modified PF Resin and the second catalyst Mass ratio is 100:1-5.
The step（3）In, Linear Polymer polymer is PVB, PVA or PVP, and solvent is ethyl alcohol, methanol, tetrahydro furan It mutters, at least one of distilled water, N.N- dimethylformamide, wherein the mass fraction ratio of shell liquid each component is high ortho position cashew nut Phenol modified thermosetting phenolic resin:Linear Polymer polymer:Solvent=（18-75）:（15-0）:（67-25）, core liquid each component Mass fraction ratio be macromolecule linear polymer:Solvent=（1-15）:（99-85）.
The step（3）In, coaxial electrostatic spinning parameter is T=15-30 DEG C of temperature, relative humidity RH=35-70%, is received Distance d=12-25cm, spinning voltage U=13-28kV, interior outer shaft spinning speed Vin:Vout=1:1-3.
The step（3）In, the temperature that is heating and curing is 120-200 DEG C, curing time 0.5-3h, and Curing environment is sky One of gas, nitrogen, vacuum.
The step（3）In, activator is vapor, CO2、KOH、ZnCl2, one of KCl.
The step（3）In, when a step activates, the quality of solid activating agent and high ortho position modified by cardanol phenolic fibre film Than for 0.5-8:1；First when carbonization, post activation, solid activating agent and the hollow nanometer of high ortho position modified by cardanol thermosetting phenolic base The mass ratio of gradient carbon-fiber film is 0.5-8:1；The flow of gas activation agent is 10-30ml/min.
The step（3）In, carbonization and activation heating rate are 1-10 DEG C/min, and carburizing temperature is 400-1100 DEG C, carbon Change time 0.5-2.5h, activation temperature is 400-1000 DEG C, activation time 0.1-2h, obtains high ortho position modified by cardanol thermosetting The property hollow nanometer gradient activated carbon fiber film of phenolic aldehyde base.
Beneficial effects of the present invention：1, high ortho position modified by cardanol thermosetting phenolic resin prepared by the present invention, due to waist Fruit phenol primary structure is the monoene or diolefin long-chain that phenol meta position replaces 15 carbon, so that high ortho position anacardol changes Property thermosetting phenolic fiber membrane and ablation resistance, thermal stability, the mechanical property of activated carbon fiber film etc. are all mentioned In addition height uses natural anacardol, so that production process is more environmentally-friendly, cost is substantially reduced, and the processing is simple；It has higher Contraposition activity, be conducive to further react with formaldehyde and generate high ortho position thermosetting phenolic resin, while remaining align also can The faster response in as-spun fibre solidification, improves reflection efficiency, reduces energy consumption, have the characteristics that green high-efficient；2, this hair When the high ortho position thermosetting phenolic resin of bright synthesis, use triethanolamine, barium carbonate and barium acetate as catalyst, in adjustment pH value When, be conducive to the removal of catalyst（Precipitating or volatilization）, catalyst/reaction product content in resin is reduced, improving resin makes Stability in；The high ortho position thermosetting phenolic resin of preparation had both had thermoplastic phenolic resin molecular weight high, and spinnability is high The characteristics of, have both thermosetting phenolic resin only and need to simply be heating and curing can direct carbonization the characteristics of, solve thermosetting phenolic aldehyde point The problem of son amount is low, and spinnability difference and thermoplastic phenolic cure time are long, curing process is more, with high costs and pollution environment；3, originally The high hollow nanometer gradient active carbon fibre of ortho position modified by cardanol thermosetting phenolic base that invention is prepared using coaxial electrostatic spinning method Tieing up film has the features such as preparation process is simple, environmentally protective, low energy consumption, controlled diameter, and degree of hollowness can design；Due to heat cure Cheng Zhong, core-skin layer phase counterdiffusion, produces phenolic aldehyde concentration gradient from surface to center, to produce phenolic aldehyde aperture after activation Gradient, remoter from surface, macropore increases.4, the present invention is compared with common phenolic resin based activated carbon fiber, due to hollow ladder Structure is spent, thus there is higher specific surface area, better toughness, therefore its absorption property and chemical property greatly improve, and Because being enclosed with a large amount of still air in its internal hollow cavity, so its heat-proof quality is also greatly enhanced.With it is common The hollow activated carbon fibre of phenolic aldehyde base is compared, and with the micro-or nano size that doughnut is uniform, and cortex bore diameter gradient is distributed, together When make it have complete continuous hollow structure, be greatly promoted the development of micro-nano hollow Gradient Materials preparation.
Specific embodiment
Combined with specific embodiments below, the present invention will be further described.It should be understood that following embodiment is merely to illustrate this The person skilled in the art of the range of invention and is not intended to limit the present invention, the field can make one according to the content of foregoing invention A little nonessential modifications and adaptations.
Embodiment 1
The preparation method of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base of the present embodiment, Steps are as follows：
（1）By phenol, formaldehyde, anacardol under the action of zinc acetate boiling reaction 2h, the concentrated sulfuric acid the reaction was continued 0.5h is added dropwise, subtracts Press-dehydrating is cooled to 40 DEG C, is to slowly warm up to 105 DEG C, isothermal reaction 0.1h, obtains high ortho position Cardanol Modified PF Resin, Wherein phenol:The molar ratio of formaldehyde is 1:0.7, phenol:Zinc acetate:The mass ratio of the concentrated sulfuric acid is 100:0.8:0.2, phenol:Waist The mass ratio of fruit phenol is 100:5；
（2）The high ortho position Cardanol Modified PF Resin obtained is dissolved in methanol, and formaldehyde is then added under the action of triethanolamine In 45 DEG C of reaction 3h, it is down to room temperature, hydrochloric acid tune pH=5 is added dropwise and filters.Decompression dehydration, is warming up to 45 DEG C, and constant temperature 0.5h obtains height Ortho position modified by cardanol thermosetting phenolic resin；Wherein high ortho position Cardanol Modified PF Resin:The mass ratio of methanol is 1:1, High ortho position Cardanol Modified PF Resin:The molar ratio of formaldehyde is 1:1, high adjacent position phenolic resin:The mass ratio of triethanolamine is 100:1；
（3）Using coaxial electrostatic spinning, it is heating and curing to obtain the high ortho position modified by cardanol thermosetting property of skin-core structure partially compatible Phenolic fibre film；Wherein the mass fraction ratio of shell liquid is:High ortho position modified by cardanol thermosetting phenolic resin:Ethyl alcohol=75:25, The mass fraction ratio of core liquid is PVB:Ethyl alcohol=1:99, coaxial electrostatic spinning parameter be T=15 DEG C, RH=35%, d=12cm, U= 13kV,Vin:Vout=1:1.And in 120 DEG C of air set 0.5h；It is heated up under nitrogen protection with the heating rate of 1 DEG C/min To 400 DEG C, carbonization 0.5h, being passed through vapor flow is 30ml/min, obtains high ortho position modified by cardanol heat after activating 0.1h The hollow nanometer gradient activated carbon fiber film of solidity phenolic aldehyde base.
The Residual carbon of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base obtained is 85%, activated carbon fibre diameter distribution 690-1900nm, internal diameter 290-1120nm, thermal coefficient 141W/mK compare table Area is 2400m2/ g, iodine number 179mg/g, average micro-pore diameter 0.7nm, internal mesopore diameter are 5nm, and gradient occurs in aperture Distribution.Specific capacitance is 298F/g in the Et4NBF4/PC electrolyte of 1mol/ L, and current density increases to 10A/g by 50mA/g Afterwards, specific capacitance is still able to maintain 279F/g.
Embodiment 2
The preparation method of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base of the present embodiment, Steps are as follows：
（1）By phenol, acetaldehyde, anacardol under the action of chromium acetate boiling reaction 2.5h, hydrochloric acid the reaction was continued 1h, decompression is added dropwise Dehydration, is cooled to 40 DEG C, is to slowly warm up to 115 DEG C, isothermal reaction 0.5h, obtain high ortho position modified by cardanol thermoplastic phenolic resin Rouge.Wherein phenol:The molar ratio of acetaldehyde is 1:0.8, phenol:Chromium acetate:The mass ratio of hydrochloric acid is 100:1:0.5, phenol:Cashew nut The mass ratio of phenol is 100:8；
（2）The high ortho position Cardanol Modified PF Resin obtained is dissolved in ethyl alcohol, and acetaldehyde is then added in the work of catalyst acetic acid barium In 50 DEG C of reaction 4h under, it is down to room temperature, sulfuric acid, which is added dropwise, makes pH=5.5, filters.Decompression dehydration is warming up to 55 DEG C, and constant temperature 1h is obtained To high ortho position modified by cardanol thermosetting phenolic resin；Wherein high ortho position Cardanol Modified PF Resin:The mass ratio of ethyl alcohol is 1:1.5, high ortho position Cardanol Modified PF Resin:The molar ratio of acetaldehyde is 1:2, high ortho position Cardanol Modified PF Resin:Second The mass ratio of sour barium is 100:5；
（3）Using coaxial electrostatic spinning, it is heating and curing to obtain the high ortho position modified by cardanol thermosetting property of skin-core structure partially compatible Phenolic fibre film；Wherein the mass fraction ratio of shell liquid is:High ortho position modified by cardanol thermosetting phenolic resin:PVB:Ethyl alcohol=70: 0.05:29.95, the mass fraction ratio of core liquid is PVB:Ethyl alcohol=2:98, coaxial electrostatic spinning parameter be T=20 DEG C, RH=40%, d= 16cm,U=15kV,Vin:Vout=1:1.And solidify 1h in 140 DEG C of nitrogen；Under nitrogen protection with the heating speed of 2 DEG C/min Rate is warming up to 600 DEG C, is carbonized after 0.7h, is passed through CO2Flow is 20ml/min, obtains high ortho position anacardol after activation 0.3h and changes The property hollow nanometer gradient activated carbon fiber film of thermosetting phenolic base.
The Residual carbon of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base obtained is 85%, activated carbon fibre diameter distribution is 500-940nm, and internal diameter 245-510nm, thermal coefficient 132W/mK compare table Area is 2698m2/ g, iodine number 199mg/g, average micro-pore diameter 1.7nm, internal mesopore diameter are 15nm, and ladder occurs in aperture Degree distribution.Specific capacitance is 355F/g in the Et4NBF4/PC electrolyte of 1mol/ L, and current density increases to 10A/ by 50mA/g After g, specific capacitance is still able to maintain 334F/g.
Embodiment 3
The preparation method of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base of the present embodiment, Steps are as follows：
（1）By phenol, furfural, anacardol under the action of zinc oxide boiling reaction 3h, phosphoric acid the reaction was continued 1.5h, decompression is added dropwise Dehydration, is cooled to 40 DEG C, is to slowly warm up to 125 DEG C, isothermal reaction 1h, obtain high ortho position modified by cardanol thermoplastic phenolic resin Rouge, wherein phenol:The molar ratio of furfural is 1:0.8, phenol:Zinc oxide:The mass ratio of phosphoric acid is 100:1.5:0.7, phenol: The mass ratio of anacardol is 100:10；
（2）The high ortho position Cardanol Modified PF Resin obtained is dissolved in methanol, and furfural is then added in the work of catalyst barium carbonate In 55 DEG C of reaction 5h under, it is down to room temperature, oxalic acid, which is added dropwise, makes pH=6, filters.Decompression dehydration, is warming up to 60 DEG C, and constant temperature 1.5h is obtained To high ortho position modified by cardanol thermosetting phenolic resin；Wherein high ortho position Cardanol Modified PF Resin:The mass ratio of methanol is 1:2, high ortho position Cardanol Modified PF Resin:The molar ratio of furfural is 1:3, high ortho position Cardanol Modified PF Resin:Carbonic acid The mass ratio of barium is 100:2；
（3）Using coaxial electrostatic spinning, it is heating and curing to obtain the high ortho position modified by cardanol thermosetting property of skin-core structure partially compatible Phenolic fibre film；Wherein the mass fraction ratio of shell liquid is:High ortho position modified by cardanol thermosetting phenolic resin:PVB:Methanol=50: 0.1:49.9, the mass fraction ratio of core liquid is PVB:Methanol=3:97, coaxial electrostatic spinning parameter be T=25 DEG C, RH=45%, d= 19cm,U=20kV,Vin:Vout=1:1.2.And solidify 1.5h under 160 DEG C of vacuum conditions；Under nitrogen protection with 3 DEG C/min Heating rate be warming up to 700 DEG C, carbonization 0.9h after, obtain the hollow nanometer gradient of high ortho position modified by cardanol thermosetting phenolic base Carbon-fiber film weighs the hollow nanometer gradient carbon-fiber film of high ortho position modified by cardanol thermosetting phenolic base and KOH, wherein the two matter Amount is than being 1:0.5, after adding distilled water immersion 1h and drying, 700 are warming up to the heating rate of 3 DEG C/min under nitrogen protection DEG C, activation 0.5h after, obtain the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base.
The Residual carbon of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base obtained is 76%, activated carbon fibre diameter distribution is 290-710nm, and internal diameter 101-320nm, thermal coefficient 113W/mK compare table Area is 2890m2/ g, iodine number 291mg/g, average micro-pore diameter 1.2nm, internal mesopore diameter are 25nm, and ladder occurs in aperture Degree distribution.Specific capacitance is 384F/g in the Et4NBF4/PC electrolyte of 1mol/ L, and current density increases to 10A/ by 50mA/g After g, specific capacitance is still able to maintain 343F/g.
Embodiment 4
The preparation method of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base of the present embodiment, Steps are as follows：
（1）By phenol, formaldehyde, anacardol under the action of zinc acetate boiling reaction 3.3h, nitric acid the reaction was continued 2h, decompression is added dropwise Dehydration, is cooled to 40 DEG C, is to slowly warm up to 135 DEG C, isothermal reaction 2h, obtain high ortho position modified by cardanol thermoplastic phenolic resin Rouge, wherein phenol:The molar ratio of formaldehyde is 1:1, phenol:Zinc acetate:The mass ratio of nitric acid is 100:1.8:0.9, phenol:Waist The mass ratio of fruit phenol is 100:12；
（2）The high ortho position Cardanol Modified PF Resin obtained is dissolved in ethyl alcohol, and formaldehyde and acetaldehyde is then added in three second of catalyst In 60 DEG C of reaction 5.5h under the action of hydramine, it is down to room temperature, hydrochloric acid, which is added dropwise, makes pH=6.5, filters.Decompression dehydration is warming up to 65 DEG C, constant temperature 2h obtains high ortho position modified by cardanol thermosetting phenolic resin；Wherein high ortho position Cardanol Modified PF Resin:Second The mass ratio of alcohol is 1:2.5, high ortho position Cardanol Modified PF Resin:Formaldehyde:The molar ratio of acetaldehyde is 1:3:2, high ortho position waist Fruit phenol phenol-formaldehyde resin modified:The mass ratio of triethanolamine is 100:3.5；
（3）Using coaxial electrostatic spinning, it is heating and curing to obtain the high ortho position modified by cardanol thermosetting property of skin-core structure partially compatible Phenolic fibre film；Wherein the mass fraction ratio of shell liquid is:High ortho position modified by cardanol thermosetting phenolic resin:PVB:Tetrahydrofuran =30:0.5:69.5, the mass fraction ratio of core liquid is PVB:Tetrahydrofuran=4:96, coaxial electrostatic spinning parameter be T=30 DEG C, RH= 50%, d=21cm, U=23kV, Vin:Vout=1:1.6, and solidify 2h in 180 DEG C of nitrogen, under nitrogen protection with 4 DEG C/min Heating rate be warming up to 800 DEG C, carbonization 1h after, obtain the high hollow nanometer gradient carbon of ortho position modified by cardanol thermosetting phenolic base Tunica fibrosa weighs the hollow nanometer gradient carbon-fiber film of high ortho position modified by cardanol thermosetting phenolic base and ZnCl2, wherein the two matter Amount is than being 1:2, after adding distilled water immersion 3h and drying, under nitrogen protection with the heating rate of 4 DEG C/min be warming up to 800 DEG C, After activating 0.7h, the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base is obtained.
The Residual carbon of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base obtained is 65%, activated carbon fibre diameter distribution is 183-450nm, internal diameter 69-156nm, thermal coefficient 101W/mK, specific surface Product is 3750m2/ g, iodine number 351mg/g, average micro-pore diameter 1.4nm, internal mesopore diameter are 32nm, and gradient occurs in aperture Distribution.Specific capacitance is 398F/g in the Et4NBF4/PC electrolyte of 1mol/ L, and current density increases to 10A/g by 50mA/g Afterwards, specific capacitance is still able to maintain 364F/g.
Embodiment 5
The preparation method of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base of the present embodiment, Steps are as follows：
（1）By metacresol, formaldehyde, anacardol under zinc acetate effect boiling reaction 4h, the concentrated sulfuric acid is added dropwise, the reaction was continued 2h subtracts Press-dehydrating is cooled to 40 DEG C, is to slowly warm up to 145 DEG C, isothermal reaction 2.5h, obtains high ortho position modified by cardanol thermoplastic phenolic Resin, wherein metacresol:The molar ratio of formaldehyde is 1:1.2, metacresol:Zinc acetate:The mass ratio of the concentrated sulfuric acid is 100:1.8: 1.1, metacresol:The mass ratio of anacardol is 100:15；
（2）The high ortho position Cardanol Modified PF Resin obtained is dissolved in methanol, and formaldehyde is then added in the work of catalyst barium carbonate In 70 DEG C of reaction 6h under, it is down to room temperature, sulfuric acid, which is added dropwise, makes pH=7, filters.Decompression dehydration, is warming up to 70 DEG C, and constant temperature 2h is obtained High ortho position modified by cardanol thermosetting phenolic resin；Wherein high ortho position Cardanol Modified PF Resin:The mass ratio of methanol is 1: 2.5, high ortho position Cardanol Modified PF Resin:The molar ratio of formaldehyde is 1:7, high ortho position Cardanol Modified PF Resin:Carbonic acid The mass ratio of barium is 100:4；
（3）Using coaxial electrostatic spinning, it is heating and curing to obtain the high ortho position modified by cardanol thermosetting property of skin-core structure partially compatible Phenolic fibre film；Wherein the mass fraction ratio of shell liquid is:High ortho position modified by cardanol thermosetting phenolic resin:PVB:Ethyl alcohol:Four Hydrogen furans=20:1:16:63, the mass fraction ratio of core liquid is PVB:Ethyl alcohol:Tetrahydrofuran=5: 76:19, coaxial electrostatic spinning Parameter is T=30 DEG C, RH=55%, d=23cm, U=25kV, Vin:Vout=1:2, and solidify 2.5h in 200 DEG C of vacuum, in nitrogen 900 DEG C are warming up to the heating rate of 5 DEG C/min under protection, after the 1.2h that is carbonized, obtain high ortho position modified by cardanol thermosetting property phenol The hollow nanometer gradient carbon-fiber film of aldehyde radical weighs the high hollow nanometer gradient carbon-fiber film of ortho position modified by cardanol thermosetting phenolic base KCl2, wherein the two mass ratio is 1:3, after adding distilled water immersion 5h and drying, under nitrogen protection with the heating speed of 5 DEG C/min After rate is warming up to 900 DEG C, activates 0.8h, the high hollow nanometer gradient active carbon fibre of ortho position modified by cardanol thermosetting phenolic base is obtained Tie up film.
The Residual carbon of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base obtained is 55%, activated carbon fibre diameter distribution is 93-210nm, internal diameter 41-112nm, thermal coefficient 102W/mK, specific surface Product is 3735m2/ g, iodine number 596mg/g, average micro-pore diameter 1.4nm, internal mesopore diameter are 32nm, and gradient occurs in aperture Distribution.Specific capacitance is 409F/g in the Et4NBF4/PC electrolyte of 1mol/ L, and current density increases to 10A/g by 50mA/g Afterwards, specific capacitance is still able to maintain 464F/g.
Embodiment 6
The preparation method of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base of the present embodiment, Steps are as follows：
（1）By metacresol, furfural, anacardol under the action of zinc oxide boiling reaction 4.5h, be added dropwise the concentrated sulfuric acid, the reaction was continued 2.5h, decompression dehydration cool the temperature to 40 DEG C, are to slowly warm up to 150 DEG C, isothermal reaction 3h, obtain high ortho position modified by cardanol Thermoplastic phenolic resin, wherein metacresol:The molar ratio of furfural is 1:4, metacresol:Zinc oxide:The mass ratio of the concentrated sulfuric acid is 100:2:1.3, metacresol:The mass ratio of anacardol is 100:20；
（2）The high ortho position Cardanol Modified PF Resin obtained is dissolved in ethyl alcohol, and acetaldehyde is then added in catalyst triethanolamine In 80 DEG C of reaction 6.5h under effect, it is down to room temperature, oxalic acid, which is added dropwise, makes pH=7.5, filters.Decompression dehydration is warming up to 80 DEG C, constant temperature 2.5h obtains high ortho position modified by cardanol thermosetting phenolic resin；Wherein high ortho position Cardanol Modified PF Resin:The matter of ethyl alcohol Amount is than being 1:3, high ortho position Cardanol Modified PF Resin:The molar ratio of acetaldehyde is 1:8, high ortho position modified by cardanol phenolic aldehyde tree Rouge:The mass ratio of triethanolamine is 100: 5；
（3）Using coaxial electrostatic spinning, it is heating and curing to obtain the high ortho position modified by cardanol thermosetting property of skin-core structure partially compatible Phenolic fibre film；Wherein the mass fraction ratio of shell liquid is:High ortho position modified by cardanol thermosetting phenolic resin:PVB:Methanol:Four Hydrogen furans=18:2:70:10, the mass fraction ratio of core liquid is PVB:Methanol:Tetrahydrofuran=4:76.8:19.2 coaxial electrostatic spinning Silk parameter is T=15 DEG C, RH=60%, d=25cm, U=28kV, Vin:Vout=1:2.3, and in 160 DEG C of air set 3h, in nitrogen 1100 DEG C are warming up to the heating rate of 6 DEG C/min under gas shielded, after the 1.5h that is carbonized, obtain high ortho position modified by cardanol thermosetting property The hollow nanometer gradient carbon-fiber film of phenolic aldehyde base weighs the high hollow nanometer gradient carbon fiber of ortho position modified by cardanol thermosetting phenolic base Film and KOH, the mass ratio of the two are 1:4, after adding distilled water immersion 7h and drying, under nitrogen protection with the heating of 6 DEG C/min After rate is warming up to 1000 DEG C, activates 1h, the high hollow nanometer gradient active carbon of ortho position modified by cardanol thermosetting phenolic base is obtained Tunica fibrosa.
The Residual carbon of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base obtained is 53%, activated carbon fibre diameter distribution is 87-154nm, internal diameter 40-51nm, thermal coefficient 97W/mK, specific surface area For 4245m2/ g, iodine number 819mg/g, average micro-pore diameter 1.6nm, internal mesopore diameter are 38nm, and gradient point occurs in aperture Cloth.Specific capacitance is 418F/g in the Et4NBF4/PC electrolyte of 1mol/ L, after current density increases to 10A/g by 50mA/g, Specific capacitance is still able to maintain 383F/g.
Embodiment 7
The preparation method of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base of the present embodiment, Steps are as follows：
（1）By metacresol, acetaldehyde, the concentrated sulfuric acid is added dropwise in anacardol boiling reaction 5h under cadmium acetate effect, the reaction was continued 3h, is subtracted Press-dehydrating is down to 40 DEG C, is to slowly warm up to 155 DEG C, isothermal reaction 3h, obtains high ortho position modified by cardanol thermoplastic phenolic resin Rouge.Wherein metacresol:The molar ratio of acetaldehyde is 1:1.6, metacresol:Zinc oxide:The mass ratio of the concentrated sulfuric acid is 100:2:1.5, Cresols:The mass ratio of anacardol is 100:25；
（2）The high ortho position Cardanol Modified PF Resin obtained is dissolved in methanol, and formaldehyde is then added in the work of catalyst barium carbonate In 85 DEG C of reaction 7h under, it is down to room temperature, hydrochloric acid, which is added dropwise, makes pH=8, filters.Decompression dehydration, is warming up to 85 DEG C, and constant temperature 3h is obtained High ortho position modified by cardanol thermosetting phenolic resin；Wherein high ortho position Cardanol Modified PF Resin:The mass ratio of methanol is 1: 2.5, high ortho position Cardanol Modified PF Resin:The molar ratio of formaldehyde is 1:10, high ortho position Cardanol Modified PF Resin:Carbonic acid The mass ratio of barium is 100:5；
（3）Using coaxial electrostatic spinning, it is heating and curing to obtain the high ortho position modified by cardanol thermosetting property of skin-core structure partially compatible Phenolic fibre film；Wherein the mass fraction ratio of shell liquid is:High ortho position modified by cardanol thermosetting phenolic resin:PVA:Ethyl alcohol=60: 5:The mass fraction ratio of 35 core liquid is PVA:Ethyl alcohol=5:95, coaxial electrostatic spinning parameter be T=15 DEG C, RH=35%, d=14cm, U= 16kV,Vin:Vout=1:1.2, and in 120 DEG C of air set 0.5h, under nitrogen protection with the heating rate liter of 7 DEG C/min After temperature to 500 DEG C, carbonization 2h, being passed through vapor flow is 15ml/min, obtains high ortho position modified by cardanol thermosetting after activating 2h The property hollow nanometer gradient activated carbon fiber film of phenolic aldehyde base.
The Residual carbon of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base obtained is 79%, activated carbon fibre diameter distribution is 242-330nm, internal diameter 82-120nm, thermal coefficient 90W/mK, specific surface Product is 3810m2/ g, iodine number 373mg/g, average micro-pore diameter 1nm, internal mesopore diameter are 22nm, and gradient point occurs in aperture Cloth.Specific capacitance is 459F/g in the Et4NBF4/PC electrolyte of 1mol/ L, after current density increases to 10A/g by 50mA/g, Specific capacitance is still able to maintain 398F/g.
Embodiment 8
The preparation method of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base of the present embodiment, Steps are as follows：
（1）By xylenol, formaldehyde, anacardol is heated to boiling reaction 5h under zinc acetate effect, strong sulfuric acid response is added dropwise 3.5h, decompression dehydration are cooled to 40 DEG C, are to slowly warm up to 160 DEG C, isothermal reaction 3.5h, obtain high ortho position modified by cardanol heat Plastic phenolic resin, wherein xylenol:The molar ratio of formaldehyde is 1:1.8, xylenol:Zinc acetate:The mass ratio of the concentrated sulfuric acid is 100:2.5:1.7, xylenol:The mass ratio of anacardol is 100:30；
（2）The high ortho position Cardanol Modified PF Resin obtained is dissolved in ethyl alcohol, and acetaldehyde is then added in catalyst triethanolamine In 80 DEG C of reaction 6.5h under effect, it is down to room temperature, oxalic acid, which is added dropwise, makes pH=7.5, filters.Decompression dehydration is warming up to 80 DEG C, constant temperature 2.5h obtains high ortho position modified by cardanol thermosetting phenolic resin；Wherein high ortho position Cardanol Modified PF Resin:The matter of ethyl alcohol Amount is than being 1:3, high ortho position Cardanol Modified PF Resin:The molar ratio of acetaldehyde is 1:8, high ortho position modified by cardanol phenolic aldehyde tree Rouge:The mass ratio of triethanolamine is 100:5；
（3）Using coaxial electrostatic spinning, it is heating and curing to obtain the high ortho position thermosetting phenolic tunica fibrosa of skin-core structure partially compatible； Wherein the mass fraction ratio of shell liquid is:High ortho position thermosetting phenolic resin:PVA:Distilled water=50:7:The mass fraction of 43 core liquid Than for PVA:Distilled water=12:88, coaxial electrostatic spinning parameter is T=30 DEG C, RH=35%, d=25cm, U=18kV, Vin:Vout= 1:1.4.And solidify 1h in 140 DEG C of nitrogen, 600 DEG C, carbonization are warming up to the heating rate of 8 DEG C/min under nitrogen protection After 2.5h, it is passed through CO2Flow is 10ml/min, and it is hollow to obtain high ortho position modified by cardanol thermosetting phenolic base after activation 0.8h Nanometer gradient activated carbon fiber film.
The Residual carbon of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base obtained is 70%, activated carbon fibre diameter distribution is 132-290nm, internal diameter 110-132nm, thermal coefficient 78W/mK, specific surface Product is 4970m2/ g, iodine number 587mg/g, average micro-pore diameter 1.8nm, internal mesopore diameter are 36nm, and gradient occurs in aperture Distribution.Specific capacitance is 468F/g in the Et4NBF4/PC electrolyte of 1mol/ L, and current density increases to 10A/g by 50mA/g Afterwards, specific capacitance is still able to maintain 429F/g.
Embodiment 9
The preparation method of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base of the present embodiment, Steps are as follows：
（1）Boiling reaction 6h, the dropwise addition concentrated sulfuric acid, the reaction was continued 4h, decompression under zinc acetate effect by phenol, formaldehyde, anacardol Dehydration, is cooled to 40 DEG C, is to slowly warm up to 165 DEG C, isothermal reaction 4h, obtain high ortho position modified by cardanol thermoplastic phenolic resin Rouge.Wherein phenol:The molar ratio of formaldehyde is 1:2, phenol:Zinc acetate:The mass ratio of the concentrated sulfuric acid is 100:3:2, phenol:Cashew nut The mass ratio of phenol is 100:12；
（2）The high ortho position Cardanol Modified PF Resin obtained is dissolved in methanol, and formaldehyde is then added in the work of catalyst barium carbonate In 85 DEG C of reaction 7h under, it is down to room temperature, hydrochloric acid, which is added dropwise, makes pH=8, filters.Decompression dehydration, is warming up to 85 DEG C, and constant temperature 3h is obtained High ortho position modified by cardanol thermosetting phenolic resin；Wherein high ortho position Cardanol Modified PF Resin:The mass ratio of methanol is 1: 2.5, high ortho position Cardanol Modified PF Resin:The molar ratio of formaldehyde is 1:10, high ortho position Cardanol Modified PF Resin:Carbonic acid The mass ratio of barium is 100:5；
（3）Using coaxial electrostatic spinning, it is heating and curing to obtain the high ortho position modified by cardanol thermosetting property of skin-core structure partially compatible Phenolic fibre film；Wherein the mass fraction ratio of shell liquid is:High ortho position modified by cardanol thermosetting phenolic resin:PVA:N.N- diformazan Base formamide=28:12:The mass fraction ratio of 60 core liquid is PVA:Dimethylformamide=15 N.N-:85, coaxial electrostatic spinning ginseng Number is T=25 DEG C, RH=70%, d=25cm, U=28kV, Vin:Vout=1:3, and solidify 1.5h in 160 DEG C of vacuum, it is protected in nitrogen 700 DEG C are warming up to the heating rate of 10 DEG C/min under shield, after the 1.2h that is carbonized, obtain high ortho position modified by cardanol thermosetting phenolic The hollow nanometer gradient carbon-fiber film of base weighs the high hollow nanometer gradient carbon-fiber film of ortho position modified by cardanol thermosetting phenolic base KOH, wherein the two mass ratio is 1:8, after adding distilled water immersion 9h and drying, under nitrogen protection with the heating speed of 9 DEG C/min After rate is warming up to 700 DEG C, activates 0.5h, the high hollow nanometer gradient active carbon fibre of ortho position modified by cardanol thermosetting phenolic base is obtained Tie up film.
The Residual carbon of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base obtained is 65%, activated carbon fibre diameter distribution is 32-65nm, internal diameter 20-32nm, thermal coefficient 66W/mK, and specific surface area is 4460m2/ g, iodine number 590mg/g, average micro-pore diameter 1.4nm, internal mesopore diameter are 38nm, and gradient distribution occurs in aperture. Specific capacitance is 467F/g in the Et4NBF4/PC electrolyte of 1mol/ L, after current density increases to 10A/g by 50mA/g, than Capacitor is still able to maintain 389F/g.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and Its equivalent thereof.

Claims (9)

1. a kind of preparation method of the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base, special Sign is to include the following steps：
（1）By anacardol, phenols and aldehyde compound under the first catalyst action boiling reaction 2-6h, then be added dropwise acidity urge Agent continues boiling reaction 0.5-4h, and decompression dehydration is to slowly warm up to 105-165 DEG C after being cooled to 40 DEG C, and the reaction was continued 0.1-4h obtains high ortho position Cardanol Modified PF Resin；
（2）High ortho position Cardanol Modified PF Resin is dissolved in alcohol compound, aldehyde compound and the second catalyst is added, 3-7h is reacted under conditions of 45-85 DEG C, is down to room temperature, pH is adjusted to make pH=5-8.0, is filtered, removes impurity, then decompression dehydration, Decompression dehydration final temperature is 50-90 DEG C, and the decompression dehydration time is 0.5-3h, and high ortho position modified by cardanol thermosetting phenolic is made Resin；
（3）High ortho position modified by cardanol thermosetting phenolic resin and Linear Polymer polymer are dissolved in solvent, shell liquid are made, Linear Polymer polymer is dissolved in solvent obtained core liquid to be heating and curing to obtain skin-core structure portion using coaxial electrostatic spinning The high ortho position thermosetting phenolic tunica fibrosa of high ortho position modified by cardanol that split-phase is held；Then in N2It is carbonized and is activated under protection, Obtain the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base.
2. the high hollow nanometer gradient activated carbon fibre of ortho position modified by cardanol thermosetting phenolic base according to claim 1 The preparation method of film, it is characterised in that：The step（1）In, phenolic compound is phenol, p-cresol or xylenol；Aldehydes Compound is formaldehyde, acetaldehyde or furfural, and the first catalyst is zinc acetate, cadmium acetate or zinc oxide；Acid catalyst is phosphoric acid, nitre The hydrochloric acid that the sulfuric acid or mass fraction that acid, mass fraction are 98% are 37%；Wherein the molar ratio of phenols and aldehydes is 1:（0.6- 2）, the mass ratio of phenolic compound and the first catalyst is 100:（0.8-3）, the mass ratio of phenolic compound and acid catalyst It is 100:（0.2-2）；The mass ratio of phenols and anacardol is 100:（5-35）.
3. the high hollow nanometer gradient activated carbon fibre of ortho position modified by cardanol thermosetting phenolic base according to claim 1 The preparation method of film, it is characterised in that：The step（2）In, alcohol compound is methanol or ethyl alcohol；Aldehyde compound is first At least one of aldehyde, acetaldehyde, furfural, the second catalyst are triethanolamine, barium carbonate or barium acetate；Adjusting acid used in pH is salt One of the sulfuric acid that acid, oxalic acid or mass fraction are 98%；The wherein quality of high ortho position Cardanol Modified PF Resin and alcohols Than being 1:（1-3）, the molar ratio of high ortho position Cardanol Modified PF Resin and aldehydes is 1:（1-10）, high ortho position modified by cardanol The mass ratio of phenolic resin and the second catalyst is 100:（1-5）.
4. the high hollow nanometer gradient activated carbon fibre of ortho position modified by cardanol thermosetting phenolic base according to claim 1 The preparation method of film, it is characterised in that：The step（3）In, Linear Polymer polymer is PVB, PVA or PVP, and solvent is second At least one of alcohol, methanol, tetrahydrofuran, distilled water, N.N- dimethylformamide, the wherein mass fraction of shell liquid each component Than for high ortho position modified by cardanol thermosetting phenolic resin:Linear Polymer polymer:Solvent=（18-75）:（15-0）:（67- 25）, the mass fraction ratio of core liquid each component is macromolecule linear polymer:Solvent=（1-15）:（99-85）.
5. the high hollow nanometer gradient activated carbon fibre of ortho position modified by cardanol thermosetting phenolic base according to claim 1 The preparation method of film, it is characterised in that：The step（3）In, coaxial electrostatic spinning parameter is T=15-30 DEG C of temperature, relatively wet RH=35-70% is spent, distance d=12-25cm, spinning voltage U=13-28kV, interior outer shaft spinning speed Vin are received:Vout=1:1-3.
6. the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base according to claim 1 Preparation method, it is characterised in that：The step（3）In, the temperature that is heating and curing is 120-200 DEG C, curing time 0.5-3h, Curing environment is one of air, nitrogen, vacuum.
7. the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base according to claim 1 Preparation method, it is characterised in that：The step（3）In, activator is vapor, CO2、KOH、ZnCl2, one of KCl.
8. the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base according to claim 1 Preparation method, it is characterised in that：The step（3）In, when a step activates, solid activating agent and high ortho position modified by cardanol phenol The mass ratio of aldehyde tunica fibrosa is 0.5-8:1；First when carbonization, post activation, solid activating agent and high ortho position modified by cardanol thermosetting property The mass ratio of the hollow nanometer gradient carbon-fiber film of phenolic aldehyde base is 0.5-8:1；The flow of gas activation agent is 10-30ml/min.
9. the high hollow nanometer gradient activated carbon fiber film of ortho position modified by cardanol thermosetting phenolic base according to claim 1 Preparation method, it is characterised in that：The step（3）In, carbonization and activation heating rate are 1-10 DEG C/min, and carburizing temperature is 400-1100 DEG C, carbonization time 0.5-2.5h, activation temperature is 400-1000 DEG C, activation time 0.1-2h, obtains high ortho position The hollow nanometer gradient activated carbon fiber film of modified by cardanol thermosetting phenolic base.
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