CN110354794A - A kind of device and method that moving boundary polymerization continuously prepares polyaniline nano fiber - Google Patents

A kind of device and method that moving boundary polymerization continuously prepares polyaniline nano fiber Download PDF

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CN110354794A
CN110354794A CN201910814639.6A CN201910814639A CN110354794A CN 110354794 A CN110354794 A CN 110354794A CN 201910814639 A CN201910814639 A CN 201910814639A CN 110354794 A CN110354794 A CN 110354794A
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container
nano fiber
polyaniline nano
agitating device
reaction tube
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CN110354794B (en
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梁浜雷
司建鑫
赵海鹏
郭心欣
张艳花
赵亚奇
冯巧
李翔
史向阳
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Henan University of Urban Construction
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
    • B01F27/90—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with paddles or arms 
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/80—Mixing plants; Combinations of mixers
    • B01F33/81—Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles
    • B01F33/813—Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles mixing simultaneously in two or more mixing receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/2425—Tubular reactors in parallel
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products

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  • Organic Chemistry (AREA)
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Abstract

The present invention provides the device and method that a kind of polymerization of moving boundary continuously prepares polyaniline nano fiber, aniline monomer and organic solvent are persistently mainly injected into the first container, it is agitated to be mixed to form organic phase solution, the acidic aqueous solution of initiator and dopant persistently injects in second container, agitated to be mixed to form aqueous phase solution；Two solution difference is after mixing, open valve, by the centrifugal force provided by agitating device make two solution with certain speed it is continual and steady flow through two reaction tubes, and moving boundary is formed in reaction tube, aniline monomer polymerize in moving boundary region, after flowing polymerization, finally it is pooled in two collection vessels；Product in collection vessel is washed, filtered, is dried, polyaniline nano fiber can be obtained.Operation of the present invention is easy, low in cost, reaction is controllable, repeatability is high, is to realize a kind of effective way of high-quality polyaniline nano fiber scale quantity-produced.

Description

A kind of device and method that moving boundary polymerization continuously prepares polyaniline nano fiber
Technical field
The invention belongs to the preparation field of nano-fiber material, in particular to a kind of preparation side of polyaniline nano fiber Method.
Background technique
Polyaniline is always the research hotspot of conductive polymer material, not only have raw material it is cheap and easy to get, it is convieniently synthesized, The advantages that conductivity is higher, environmental stability is preferable, but also there is unique mechanism of doping effect, it can be formed in conjunction with other materials The composite material of unique energy.In numerous polyaniline micro nano structures, polyaniline nano fiber is with higher to compare table Area, high porosity and unique conductive channel are passed in supercapacitor, stealth material, nano photoelectric device, chemistry and biology The fields such as sensor show biggish application potential.The synthetic method of polyaniline nano fiber is in addition to electrostatic spinning It, can also be using electrification outside the physical methods such as [CN101973713A, CN101967279A, CN100360725C], mechanical stretching Method and chemical oxidization method synthesize.
Electrochemical process is to need to borrow by the way that monomer is dissolved in electrolyte and polymerization reaction directly occurs on inert electrode With expensive instrument and equipment, the requirement to electrode and current potential is relatively high, and yield is limited to electrode area, is unfavorable for extensive Processing.Chemical oxidization method mainly includes hard template method, soft template method and template-free method.Wherein, hard template method and soft template method be all Template is needed to be induced [CN101284908A, CN100586987C] the growth of polyaniline nano fiber, and major part needs Relatively complicated last handling process is wanted to remove removing template, this can cause certain destruction to the micro nano structure of polyaniline.
The birth of template-free method effectively compensates for this defect, mainly include emulsion polymerization [CN102060993A, CN102050947A], ultrasound polymerization method [CN1323199C] and interfacial polymerization [CN101016660A, CN101710541A, CN101037504A] etc..Since, frequently with a large amount of emulsifier, last handling process is cumbersome during emulsion polymerization；It is super Sound polymerization is needed by expensive instrument and equipment, and is difficult to realize the finely regulating to polyaniline micro nano structure, so that The practical extension aspect of both methods is restricted.Interfacial polymerization is that current synthesized polyaniline nanofiber is more common Method, aniline monomer polymerization occurs at organic phase/aqueous phase interface generates polyaniline in this method, is then expanded to water phase It dissipates, effectively prevents the diauxic growth of polyaniline, substantially increase product quality, prepare high-quality polyaniline nano fiber Effective ways.
However, the yield of traditional interface polymerization is limited to interfacial area, and is difficult to realize high-volume continuous production, because This its combined coefficient is extremely limited.Meanwhile pattern, ordered structure and the performance of gained polyaniline nano fiber need further It improves.
Based on this, the present invention is specifically proposed.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention proposes that a kind of novel moving boundary polymerization continuously prepares polyphenyl The device and method of amine nanofiber utilize the centrifugal force of agitating device rotation offer by constructing flowing polymerization reaction configuration Promote solute in container to be sufficiently mixed with solvent, and continues to push in solution injection reaction tube and carry out steady flow；It is reacting Organic phase/water phase moving boundary is created in pipe, aniline monomer polymerization generates polyaniline nano fiber in interface, and passes through flowing Driving force effectively facilitates the oriented growth of polyaniline nano fiber, and then high-quality polyaniline nano fiber is prepared in serialization.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of continuous device for preparing polyaniline nano fiber of moving boundary polymerization, including the first container and second container, first It is equipped with the first agitating device in container, the second agitating device is equipped in second container, the first container bottom passes through the first connecting tube It is connected to the feed end of reaction tube, second container bottom is connected to by the second connecting tube with the feed end of reaction tube, reaction tube Discharge end is connected to collection vessel, is equipped with valve in first connecting tube and the second connecting tube.
Preferably, number n >=1 of first connecting tube, number n >=1 of the second connecting tube, the number n of reaction tube >= 1, and the number of the first connecting tube=second connecting tube number=reaction tube number.
Preferably, number n=2 of first connecting tube, number n=2 of the second connecting tube, number n=2 of reaction tube.
Preferably, the internal diameter of the first container and second container is 10 ~ 500 mm；First agitating device and second The diameter of agitating device is 5 ~ 480 mm；The length of the reaction tube is 0.5 ~ 20 m, and internal diameter is 1 ~ 50 mm.
The method for preparing polyaniline nano fiber using the device, comprising the following steps:
(1) aniline monomer and organic solvent are persistently injected into the first container, it is agitated to be mixed to form organic phase solution, it will draw Hair agent and the aqueous solution containing dopant are persistently injected into second container, agitated to be mixed to form aqueous phase solution；
(2) valve is opened, organic phase solution and aqueous phase solution pass through the first agitating device respectively and the second agitating device provides Centrifugal force flows it in reaction tube with certain speed, and forms moving boundary, and aniline monomer occurs on moving boundary Polymerization, is finally pooled in collection vessel；
(3) by reaction product washing, suction filtration, the drying in collection vessel, polyaniline nano fiber is obtained.
Preferably, the revolving speed of first agitating device is 1 ~ 5000 r/min, the revolving speed of the second agitating device is 1 ~ 5000 r/min, and the rotating ratio of the first agitating device and the second agitating device is 1:(0.1 ~ 10).
Preferably, the organic solvent in the step (1) is carbon tetrachloride, benzene,toluene,xylene, carbon disulfide or chlorine At least one of imitate；The molar concentration of aniline monomer in organic solvent in the step (1) is 0.005~5.0 mol/ L。
Preferably, the dopant in the aqueous solution containing dopant in the step (1) includes hydrochloric acid, sulfuric acid, nitric acid, height Chloric acid, phosphoric acid, fluoboric acid, acetic acid, sulfosalicylic acid, saturated fatty acid, helianthic acid, how sulfonic acid, camphorsulfonic acid or 12 At least one of alkyl benzene sulphonate；The molar concentration of dopant is 0.2~5.0 mol/L.
Preferably, the initiator in the step (1) is ferric trichloride, bichromate, hydrogen peroxide, ammonium persulfate or mistake Aoxidize at least one of formyl.
Preferably, the molar ratio of the aniline monomer in the step (1) and initiator is 1:(0.01~10).
Preferably, after the valve opening, the solution in the first container and second container flows into reaction tube, and valve is not required to It to open repeatedly, during persistently feeding intake, agitating device can be achieved at the same time the mixing of solute and solvent and provide flowing The double action of driving force；Organic phase and aqueous phase solution can be by valve regulated relative discharges, and then control in moving boundary The relative amount of organic phase liquid compatible with water.
Preferably, the material of the described production agitating device and reaction tube be polyflon, it is phenolic resin, organic The acidproof base material such as silicon monomer resin.
Preferably, the organic phase and aqueous phase solution form moving boundary in reaction tube, in interface aniline monomer Polymerization generates polyaniline nano fiber, is then dissolved in aqueous phase solution, can effectively avoid polyaniline from occurring in interface secondary Growth, and realize serialization preparation process；Flowing polymerization can promote polyaniline streamwise that oriented growth occurs, and obtain height Quality polyaniline nano fiber.
Preferably, the relative amount of the organic phase and aqueous phase solution in reaction tube can pass through valve and agitating device Adjusting carry out 0 ~ 100% regulation.
The present invention proposes continuously to prepare polyaniline nano fiber by moving boundary polymerization, rotates and provide by agitating device Centrifugal force realize the mixed preparing of reaction solution and continue driving a reaction liquid and carry out steady flow in reaction tube, and create organic Phase/water phase moving boundary the zone of convergency induces polyaniline nano fiber to be held in reaction tube by regulation flow driving power Continuous oriented growth, and then continuously prepare uniform pattern, compound with regular structure, the high-quality polyaniline that well dispersed, the degree of orientation is high Nanofiber.
Beneficial effects of the present invention:
(1) present invention has distinguishing feature compared with the preparation method of existing electrically conductive polyaniline nano fiber, and the present invention mentions for the first time Go out in the method for moving boundary polymerization continuously preparing poly aniline nano-fiber, it is conductive to overcome existing interfacial polymerization preparation Polyaniline nano fiber combined coefficient is low, the shortcomings such as low that are difficult to continuous batch production, feed stock conversion.Pass through stirring The centrifugal force that device rotation provides promotes each reaction solution uniformly to mix and the steady flow in reaction tube of driving a reaction liquid；It is flowing In the process, organic phase and aqueous phase solution form stable moving boundary region in reaction tube, the aniline list at the moving boundary Body polymerization generates polyaniline nano fiber, and spreads in time into water phase, and then contains the diauxic growth of polyaniline；Flow driving Power effectively facilitates polyaniline nano fiber streamwise and carries out continuing oriented growth, while the moving boundary that unit volume generates Long-range and traditional interface polymerization, the effective contact area of organic phase/water phase increase, and monomer utilization ratio is improved, adds The design of two-way flow configuration, substantially increases combined coefficient.
(2) preparation facilities of the invention and method it is simple and easy to operate, it is low in cost, without carry out reaction solution preparation from Line step does not need by any template, reacts controllable, repeatability height, and entire polymerization process is completed in reaction tube, Neng Gouyou Effect improves the preparation efficiency of polyaniline nano fiber；It is complete in reaction tube that the present invention can satisfy being grown in for polyaniline nano fiber At the postprocessing working procedures for needing further to stand because aggregation growth is insufficient being avoided, simultaneously because polymerization reaction only occurs In moving boundary region, therefore also avoid generating a large amount of products in a short time because rate of polymerization is too fast and causing in reaction tube The phenomenon that blocking；Only by control agitating device revolving speed, solute can either be conveniently promoted to mix with the uniform of solvent, again Energy Effective Regulation flow driving power, and then effectively control the oriented growth of polyaniline nano fiber；The present invention is continuously controllable, convenient The growth course of polyaniline nano fiber is monitored now, facilitates relevant polymerization mechanism and micro nano structure evolution mechanism Research.
(3) polyaniline that present invention gained topography uniformity is good, compound with regular structure, well dispersed, the degree of orientation is high, has excellent performance Nanofiber, can be applied to energy storage and converting material, adsorbent material, conductive material, anti-static material, anti-corrosion material, The numerous areas such as sensing material, electromagnetic shielding material.
Detailed description of the invention
Fig. 1 is the preparation facilities structural schematic diagram of polyaniline nano fiber；
Fig. 2 is the side view of the preparation facilities of polyaniline nano fiber in Fig. 1；
Fig. 3 is the scanning electron microscope (SEM) photograph of polyaniline nano fiber synthesized by the embodiment of the present invention 1；
Fig. 4 is the electrification of the electrode that is prepared using polyaniline nano fiber synthesized by the embodiment of the present invention 2 in an acidic solution Learn cyclic voltammetry curve；
Fig. 5 is the scanning electron microscope (SEM) photograph of polyaniline nano fiber synthesized by the embodiment of the present invention 3；
Fig. 6 is that the response of the gas sensor PARA FORMALDEHYDE PRILLS(91,95) prepared using polyaniline nano fiber synthesized by the embodiment of the present invention 4 is bent Line；
Fig. 7 is the scanning electron microscope (SEM) photograph of polyaniline nano fiber synthesized by the embodiment of the present invention 5.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.
Embodiment 1
As illustrated in fig. 1 and 2, the moving boundary polymerization of the present embodiment continuously prepares the device of polyaniline nano fiber, including first Container 11 and second container 12, the first container 11 is interior to be equipped with the first agitating device 21, and the second stirring is equipped in second container 12 and is filled 22 are set, is uniformly mixed solution in container by agitating device, and provide flow driving power for it.11 bottom of the first container passes through First connecting tube 31 is connected to the feed end of reaction tube, the charging that 12 bottom of second container passes through the second connecting tube 32 and reaction tube End connection, the discharge end of reaction tube are connected to collection vessel, are equipped with valve in first connecting tube 31 and the second connecting tube 32 Door 4.
Preferably, the number of first connecting tube of the present embodiment=second connecting tube number=reaction tube number=collection Number=2 of container.I.e. the bottom of the first container and second container connects two groups of reaction tubes simultaneously, can effectively improve Production efficiency.Specifically, the collection vessel includes left collection vessel 61 and right collection vessel 62, the reaction tube includes left anti- Should pipe 51 and right reaction tube 52,11 bottom of the first container is separately connected left reaction tube 51 and the right side is anti-by two group of first connecting tube 31 Should pipe 52 feed end, 12 bottom of second container is separately connected left reaction tube 51 and right reaction tube by two group of second connecting tube 32 The discharge end of 52 feed end, left reaction tube 51 and right reaction tube 52 is separately connected left collection vessel 61 and right collection vessel 62.
The internal diameter of the first container 11 and second container 12 is 10.1 mm, first agitating device and the second stirring The diameter of device (stirrer paddle) is 10.0 mm；The length of the reaction tube is 2.0 m, and internal diameter is 1.0 mm；Described One container 11 fills aniline monomer and organic solvent, and second container 12 fills the aqueous solution of initiator and dopant；The left receipts Collect container 61 and right collection vessel 62 collects final product.
The polyaniline nano fiber of the present embodiment the preparation method is as follows:
(1) 931.3 g aniline monomers and 22.8 g ammonium persulfates are accurately weighed, aniline monomer is added to and fills carbon tetrachloride In the first container, ammonium persulfate is added in the second container for filling 0.1 mol/L hydrochloric acid solution；
(2) setting the rotating ratio of 50 r/min(organic phases and water phase for the revolving speed of organic phase agitating device is 1:1), to abundant It after dissolution, opens valve (organic phase/water phase pipeline valve opening degree is identical), the solution in the first container and second container It is gently introduced into reaction tube, forms moving boundary and steady flow in reaction tube, reaction solution is final to flow after flowing polymerization Enter (see figure 2) in the collection vessel equipped with water；
(3) reaction product washed repeatedly, filtered, dried, obtain diameter between 20~40 nm, length between 200~ The polyaniline nano fiber (as shown in Figure 3) of 600 nm.
Embodiment 2
The moving boundary polymerization of the present embodiment continuously prepares the first container 11 and second container in the device of polyaniline nano fiber 12 internal diameter is 50.2 mm, and the diameter of the first agitating device and the second agitating device is 50.0 mm；The length of the reaction tube Degree is 5.0 m, and internal diameter is 8.0 mm；Other embodiments are the same as embodiment 1.
The polyaniline nano fiber of the present embodiment the preparation method is as follows:
(1) 372.5 g aniline monomers and 650.0 g ferric trichlorides are accurately weighed, aniline monomer is added to and fills dimethylbenzene In the first container, ferric trichloride is added in the second container for filling 0.5 mol/L doping acid solution, wherein mixing and doping agent It is made of phosphoric acid and perchloric acid, the molar ratio of phosphoric acid and perchloric acid is 1:2；
(2) setting the rotating ratio of 500 r/min(organic phases and water phase for the revolving speed of organic phase agitating device is 1:0.5), to After completely dissolution, it opens valve (the valve opening degree of organic phase pipeline be water phase 2 times), in the first container and second container Solution be gently introduced into reaction tube, moving boundary and steady flow are formed in reaction tube, reaction solution after flowing polymerization, Finally flow into (see figure 2) in the collection vessel equipped with water；
(3) reaction product washed repeatedly, filtered, dried, obtain diameter between 20~50 nm, length between 200~ The polyaniline nano fiber of 570 nm.Fig. 4 gives the cyclic voltammetry curve of the electrode in 0.5 mol/L sulfuric acid solution.
Embodiment 3
The moving boundary polymerization of the present embodiment continuously prepares the first container 11 and second container in the device of polyaniline nano fiber 12 internal diameter is 100.0 mm, and the diameter of the first agitating device and the second agitating device is 95.0 mm；The length of the reaction tube Degree is 10.0 m, and internal diameter is 15.0 mm；Other embodiments are the same as embodiment 1.
The polyaniline nano fiber of the present embodiment the preparation method is as follows:
(1) 46.6 g aniline monomers, 1210.0 g benzoyl peroxides are accurately weighed, aniline monomer is added to and fills chloroform In the first container, benzoyl peroxide is added in the second container for filling 1 mol/L sulfuric acid solution；
(2) setting the rotating ratio of 1000 r/min(organic phases and water phase for the revolving speed of organic phase agitating device is 1:2), wait fill After point dissolution, open valve (the valve opening degree of water phase pipeline be organic phase 2 times), in the first container and second container Solution is gently introduced into reaction tube, moving boundary and steady flow is formed in reaction tube, reaction solution is after flowing polymerization, most (see figure 2) in the collection vessel equipped with water is flowed into eventually.
(3) reaction product washed repeatedly, filtered, dried, obtain diameter between 20~35 nm, length between 200 The polyaniline nano fiber (as shown in Figure 5) of~550 nm.
Embodiment 4
The moving boundary polymerization of the present embodiment continuously prepares the first container 11 and second container in the device of polyaniline nano fiber 12 internal diameter is 300.0 mm, and the diameter of first agitating device and the second agitating device is 290.0 mm；The reaction The length of pipe is 15.0 m, and internal diameter is 20.0 mm；Other embodiments are the same as embodiment 1.
The polyaniline nano fiber of the present embodiment the preparation method is as follows:
(1) 465.7 g aniline monomers, 745.0 g sodium dichromates, 570.5 g ammonium persulfates are accurately weighed, aniline monomer is added Into the first container for filling carbon disulfide, compounding initiator is added to and fills the second of 2 mol/L sulfosalisylic acid solutions In container；
(2) setting the rotating ratio of 500 r/min(organic phases and water phase for the revolving speed of organic phase agitating device is 1:8), wait fill After dividing dissolution, open valve (organic phase/water phase pipeline valve opening degree is identical), it is molten in the first container and second container Liquid is gently introduced into reaction tube, moving boundary and steady flow is formed in reaction tube, reaction solution is after flowing polymerization, finally Flow into (see figure 2) in the collection vessel equipped with water；
(3) reaction product washed repeatedly, filtered, dried, obtain diameter between 20~50 nm, length between 150~ The polyaniline nano fiber of 500 nm.
Gas sensor is made in prepared polyaniline nano fiber, Fig. 6 gives the gas sensor PARA FORMALDEHYDE PRILLS(91,95) gas The response curve of body.
Embodiment 5
The moving boundary polymerization of the present embodiment continuously prepares the first container 11 and second container in the device of polyaniline nano fiber 12 internal diameter is 500.0 mm, and the diameter of first agitating device and the second agitating device is 460.0 mm；The reaction The length of pipe is 20.0 m, and internal diameter is 35.0 mm；Other embodiments are the same as embodiment 1.
The polyaniline nano fiber of the present embodiment the preparation method is as follows:
(1) 931.3 g aniline monomers and 22820.0 g ammonium persulfates are accurately weighed, aniline monomer is added to and fills benzene and two In the first container of toluene mixed organic solvents, the molar ratio of benzene and toluene is 1:1, and ammonium persulfate is added to and contains 4 mol/L In the second container of dodecylbenzenesulfonic acid solution；
(2) setting the rotating ratio of 4500 r/min(organic phases and water phase for the revolving speed of organic phase agitating device is 1:1), wait fill After dividing dissolution, open valve (organic phase/water phase pipeline valve opening degree is identical), it is molten in the first container and second container Liquid is gently introduced into reaction tube, moving boundary and steady flow is formed in reaction tube, reaction solution is after flowing polymerization, finally Flow into (see figure 2) in the collection vessel equipped with water；
(3) reaction product washed repeatedly, filtered, dried, obtain diameter between 20~35 nm, length between 150~ The polyaniline nano fiber (as shown in Figure 7) of 450 nm.
The present invention adds agitating device in the first container and second container, the centrifugation provided by agitating device rotation Making every effort to promote is sufficiently mixed solute in two containers with solvent, and the flowing for pushing solution continual and steady into two reaction tubes simultaneously； In flow process, organic phase and aqueous phase solution form stable moving boundary in reaction tube；It is poly- in interface aniline monomer Symphysis is spread into water phase in time at polyaniline nano fiber, and then contains the diauxic growth of polyaniline.Realizing lasting stream While dynamic, flow driving power can effectively facilitate polyaniline nano fiber streamwise and carry out oriented growth, while unit The moving boundary that volume generates is long-range and traditional interface polymerization, monomer utilization ratio are improved, and adds two-way flow configuration Design, combined coefficient is substantially increased, and the off-line step without carrying out reaction solution preparation, without any mould Plate, easy to operate, low in cost, reaction is controllable, combined coefficient is high, repeatability is high, and whole process is carried out in reaction tube, is not necessarily to Cumbersome postprocessing working procedures, therefore the present invention is a kind of effective way of high efficiency continuously preparation high-quality polyaniline nano fiber Diameter, and the scale for being suitable for other one-dimensional Polymers materials is continuously prepared.

Claims (10)

1. the device that a kind of moving boundary polymerization continuously prepares polyaniline nano fiber, it is characterised in that: including the first container (11) and second container (12) the first agitating device (21), are equipped in the first container (11), second is equipped in second container (12) Agitating device (22), the first container (11) bottom are connected to by the first connecting tube (31) with the feed end of reaction tube, second container (12) bottom is connected to by the second connecting tube (32) with the feed end of reaction tube, and the discharge end of reaction tube is connected to collection vessel, Valve (4) are equipped on first connecting tube (31) and the second connecting tube (32).
2. the device that moving boundary polymerization according to claim 1 continuously prepares polyaniline nano fiber, it is characterised in that: Number n >=1 of first connecting tube, number n >=1 of the second connecting tube, number n >=1 of reaction tube, and the first connecting tube Number=second connecting tube number=reaction tube number.
3. the device that moving boundary polymerization according to claim 1 continuously prepares polyaniline nano fiber, it is characterised in that: Number n=2 of first connecting tube, number n=2 of the second connecting tube, number n=2 of reaction tube.
4. the device that moving boundary polymerization according to claim 1 continuously prepares polyaniline nano fiber, it is characterised in that: The internal diameter of the first container and second container is 10 ~ 500 mm；The diameter of first agitating device and the second agitating device For 5 ~ 480 mm；The length of the reaction tube is 0.5 ~ 20 m, and internal diameter is 1 ~ 50 mm.
5. the method for preparing polyaniline nano fiber using any device of claim 1-4, it is characterised in that including with Lower step:
(1) aniline monomer and organic solvent are persistently injected into the first container (11), it is agitated to be mixed to form organic phase solution, Initiator and the aqueous solution containing dopant are persistently injected into second container (12), it is agitated to be mixed to form aqueous phase solution；
(2) valve (4) are opened, organic phase solution and aqueous phase solution pass through the first agitating device (21) and the second agitating device respectively (22) centrifugal force provided flows it in reaction tube with certain speed, and forms moving boundary, and aniline monomer is in movement It polymerize on interface, is finally pooled in collection vessel；
(3) by reaction product washing, suction filtration, the drying in collection vessel, polyaniline nano fiber is obtained.
6. according to the method described in claim 5, it is characterized by: the revolving speed of first agitating device (21) is 1 ~ 5000 R/min, the revolving speed of the second agitating device (22) are 1 ~ 5000 r/min, and the first agitating device (21) and the second agitating device (22) rotating ratio is 1:(0.1 ~ 10).
7. according to the method described in claim 5, it is characterized by: organic solvent in the step (1) be carbon tetrachloride, At least one of benzene,toluene,xylene, carbon disulfide or chloroform；Aniline monomer in the step (1) is in organic solvent Molar concentration be 0.005~5.0 mol/L.
8. according to the method described in claim 5, it is characterized by: in the aqueous solution containing dopant in the step (1) Dopant includes hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, fluoboric acid, acetic acid, sulfosalicylic acid, saturated fatty acid, azobenzene Sulfonic acid, how at least one of sulfonic acid, camphorsulfonic acid or dodecyl benzene sulfonic acid；The molar concentration of dopant is 0.2~5.0 mol/L。
9. according to the method described in claim 5, it is characterized by: the initiator in the step (1) is ferric trichloride, weight chromium At least one of hydrochlorate, hydrogen peroxide, ammonium persulfate or peroxidating formyl.
10. according to the method described in claim 5, it is characterized by: aniline monomer and initiator in the step (1) rubs You are than being 1:(0.01~10).
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CN103408754A (en) * 2013-07-11 2013-11-27 东华大学 Preparation method of polyaniline nanometer fiber
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CN108774335A (en) * 2018-07-05 2018-11-09 深圳大学 A method of polyether-ether-ketone surface is modified using polyaniline nano fiber
CN109942733A (en) * 2018-10-26 2019-06-28 复旦大学 A kind of method that continuous flow moves synthetic polymer

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CN103408754A (en) * 2013-07-11 2013-11-27 东华大学 Preparation method of polyaniline nanometer fiber
CN104630917A (en) * 2015-02-13 2015-05-20 东华大学 Preparation device and method for polyaniline nanofibers
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