阅读说明：本技术 一种聚苯胺/聚吡咯复合纳米纤维的连续化制备装置和方法 (A kind of the serialization preparation facilities and method of polyaniline/polypyrrole composite nano fiber ) 是由 梁浜雷 司建鑫 郭心欣 赵海鹏 赵亚奇 张艳花 冯巧 李辉 郭静怡 于 2019-08-30 设计创作，主要内容包括：本发明提供了一种聚苯胺/聚吡咯复合纳米纤维的制备装置及方法,将含有掺杂剂的苯胺单体溶液和引发剂溶液分别注入到第一容器和第二容器中,并以一定的速度在第一反应管内流动聚合,生成聚苯胺纳米纤维；将吡咯单体和引发剂分别溶解在含有掺杂剂的第三容器和第四容器中,将两溶液以一定的速度持续注入到第二反应管中,在流经第一反应管末端时与聚苯胺纳米纤维接触,并在其表面进行氧化聚合；聚吡咯不断在聚苯胺纳米纤维表面进行包覆,最终汇集到收集容器中；洗涤、抽滤和干燥,得到聚苯胺/聚吡咯复合纳米纤维。本发明操作简单、反应可控、不需要使用任何有机溶剂和模板、重复性高,整个聚合过程在反应管内完成,极大地提高了生产效率。(The present invention provides a kind of preparation facilities of polyaniline/polypyrrole composite nano fiber and methods, aniline monomer solution containing dopant and initiator solution are injected separately into the first container and second container, and polymerization is flowed in the first reaction tube with certain speed, generate polyaniline nano fiber；Pyrrole monomer and initiator are dissolved in respectively in the third container and the 4th container containing dopant, two solution are persistently injected into the second reaction tube with certain speed, it is contacted when flowing through the first reaction pipe end with polyaniline nano fiber, and carries out oxidation polymerization on its surface；Polypyrrole is constantly coated on polyaniline nano fiber surface, is finally pooled in collection vessel；Washing, suction filtration and drying, obtain polyaniline/polypyrrole composite nano fiber.Operation of the present invention is simple, reaction is controllable, it is high using any organic solvent and template, repeatability not need, and entire polymerization process is completed in reaction tube, greatly improves production efficiency.)

1. a kind of serialization preparation facilities of polyaniline/polypyrrole composite nano fiber, it is characterised in that: including the first container (1), second container (2), agitating device (3), third container (4), the 4th container (5), current velocity controller (6), the first reaction Manage (7), the second reaction tube (8) and collection vessel (9)；First reaction tube (7) feed end connection the first container (1) and Second container (2), the discharge end of the first reaction tube extend into second via the feed end of the second reaction tube (8) in coaxial fashion In reaction tube (8), agitating device (3) are equipped in the first reaction tube (7)；The feed end of second reaction tube (8) connects third The discharge end of container (4) and the 4th container (5), the second reaction tube (8) connects collection vessel (9)；The third container (4) and Four containers (5) are connected separately with current velocity controller (6).

2. a kind of serialization preparation facilities of polyaniline/polypyrrole composite nano fiber according to claim 1, feature It is:

The length of first reaction tube is 2 ~ 8 m, and internal diameter is 10 ~ 100 mm；The length of second reaction tube be 2 ~ 20 m, internal diameter are 50 ~ 300 mm；The length of first reaction tube and the second reaction tube ratio be 1:(0.5 ~ 10), diameter ratio be 1:(1 ~ 10), the feed end of the second reaction tube is equipped with convex-concave region, of length no more than the first reaction tube length protruded into the second reaction tube Degree.

3. a kind of serialization preparation facilities of polyaniline/polypyrrole composite nano fiber according to claim 1, feature Be: the current velocity controller (6) is driving pump, flow injection device or peristaltic pump, the driving pump or flow injection device It is internal to be separately positioned on third container (4) and the 4th container (5), the peristaltic pump setting is in third container, the 4th container and the On connecting line between two reaction tubes.

4. preparing polyaniline/polypyrrole composite nano fiber using any serialization preparation facilities of claim 1-3 Method, it is characterised in that steps are as follows:

(1) the aniline monomer solution containing dopant is injected into the first container, the aniline monomer containing dopant is caused Agent solution is injected into second container, and aniline monomer solution and initiator solution flow into the first reaction tube under gravity In, aniline monomer solution and initiator solution are mixed and with certain speed in the first reaction tube by the rotation of agitating device Interior flowing polymerization, generates polyaniline nano fiber；

(2) pyrrole monomer and pyrrole monomer initiator are dissolved in respectively in the third container and the 4th container containing dopant, Two solution are persistently injected into the second reaction tube with certain speed by current velocity controller, by the second reaction tube beginning Convex-concave region mix them thoroughly, contacted when flowing through the first reaction pipe end with polyaniline nano fiber, and in polyaniline Nanofiber surface carries out oxidation polymerization；With constant flow polymerization of the reaction solution in the second reaction tube, polypyrrole constantly exists Polyaniline nano fiber surface is coated, and is finally pooled in collection vessel；

(3) by reaction product washing, suction filtration and the drying in collection vessel, polyaniline/polypyrrole composite nano fiber is obtained eventually.

5. according to the method described in claim 4, it is characterized by: solution flow velocity in the step (1) in the first reaction tube It is controlled by the revolving speed of agitating device, the revolving speed of agitating device is 50 ~ 2000 r/min.

6. according to the method described in claim 4, it is characterized by: solution flow velocity in the step (2) in the second reaction tube For 10 ~ 1000 mL/h.

7. according to the method described in claim 4, it is characterized by: mole of the aniline monomer solution and pyrrole monomer solution Concentration is 0.005~5.0 mol/L, and molar ratio is 1:(0.1 ~ 10.0).

8. according to the method described in claim 4, it is characterized by: the aniline monomer initiator is ammonium persulfate, tri-chlorination At least one of iron, bichromate, hydrogen peroxide or peroxidating formyl, the pyrrole monomer initiator are ferric trichloride, mistake At least one of ammonium sulfate or hydrogen peroxide, the molar ratio of aniline monomer and aniline monomer initiator be 1:(0.01~ 10.0), the molar ratio of pyrrole monomer and pyrrole monomer initiator is 1:(0.01~10.0).

9. according to the method described in claim 4, it is characterized by: the dopant be hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, Phosphoric acid, fluoboric acid, acetic acid, sulfosalicylic acid, saturated fatty acid, helianthic acid, how sulfonic acid, camphorsulfonic acid or detergent alkylate At least one of sulfonic acid, the molar concentration of dopant are 0.1 ~ 6.0 mol/L.

10. a kind of serialization preparation facilities of polyaniline/polypyrrole composite nano fiber according to claim 1, special Sign is: the material of the production agitating device and reaction tube is polyflon, phenolic resin or organic silicon monomer The material of the acid and alkali-resistances such as resin.

Technical field

The invention belongs to the preparation field of nanocomposite, in particular to a kind of polyaniline/polypyrrole composite Nano is fine Tie up preparation facilities and preparation method.

Background technique

The exploitation of the energy and the core subject using always human development.It is steady in the effective use and development for pursuing the energy Under the background of fixed, efficient energy storing technology, the appearance of supercapacitor has great realistic meaning.Relative to other storages Energy device, supercapacitor have quick charging and discharging capabilities, the cyclical stability of overlength, the service performance of safety and environment friend The advantages that good.Key components of the electrode material as supercapacitor are the important indicators for determining its performance, wherein polymerizeing Object electrode material is due to having obtained extensive concern the characteristics of itself.Studies have shown that the energy storage row of conductive polymer nanometer fiber To be substantially better than unordered conducting polymer, reason can be attributed to its aggregated structure high-sequential, to greatly improve Its carrier mobility.In numerous polymer, polyaniline and polypyrrole are conductive high, cheap, convieniently synthesized The advantages that.However, all have the defects that for the polyaniline of one-component or polypyrrole it is certain, as polyaniline be suitable for acidity Electrolyte, and polypyrrole is suitable for neutral electrolyte and alkaline electrolyte.Therefore, polyaniline and polypyrrole compound preparation is carried out to gather Aniline/polypyrrole composite nano fiber realizes that the organic integration of the two excellent performance is significant.

Currently, the method for synthesizing one-dimensional polyaniline/polypyrrole composite material is broadly divided into chemical oxidization method and electrochemistry is poly- It is legal, as Donghua University Qin Zongyi et al. has invented a kind of preparation side of polyaniline/polypyrrole composite nano fiber electrode materials Method, first by being quickly mixed with out polyaniline nano fiber, then by the in situ chemical oxidative polymerization of pyrroles by poly- pyrrole It coughs up and is coated on polyaniline nano fiber surface, synthesize the polyaniline/polypyrrole composite nano fiber with core-shell structure [CN101892530A]；Yao Chao of Changzhou Aotena New Material Technology Co., Ltd. et al. proposes a kind of polyaniline/polypyrrole two The preparation method of first composite nano tube is added pore creating material and handles it, then first using rodlike silicate clay as nucleome Aniline is added and pyrrole monomer carries out oxidative polymerization, prepares silicate clay/polyaniline/polypyrrole composite material, finally Rodlike silicate clay template is removed with nitration mixture dissolution, is made polyaniline/polypyrrole composite nano tube [CN103224704A]；Liu Blog article is using nano-cellulose as nucleome and hard template, using methyl orange and neopelex as soft template, using in situ poly- Polypyrrole and polyaniline in legal cladding are prepared nano-cellulose/polypyrrole/polyaniline composite nano fiber, are finally used Ionic liquid dissolves nano-cellulose, obtains polypyrrole/polyaniline composite nanometer tube [CN108250744A]；In addition, grinding Study carefully and show to prepare one-dimensional polyaniline (or polypyrrole) first using electrochemical polymerization method, then passes through electrification using it as template It learns deposition or chemical oxidising polymerisation and polypyrrole (or polyaniline) is subjected to surface cladding, finally prepare one-dimensional polyaniline/poly- pyrrole Cough up composite material.

However, current these preparation methods all have some limitations, as electrochemical polymerization method is needed by instrument Equipment, yield are primarily limited to electrode area；It is to be combined using template and situ aggregation method mostly in chemical oxidization method, makes Standby polyaniline/polypyrrole composite nano fiber generally requires substep and carries out, and preparation process is complex, and need it is cumbersome after Treatment process is made a return journey removing template, and scale application potentiality are weakened；Although there is researcher to replace template using quick mixing method Method synthesized polyaniline nanofiber seed, but quickly mixing method due to polymerization process it is more difficult to control, and monomer concentration is not high so that The quality of the polyaniline/polypyrrole nanofiber finally prepared is not high, and yield is relatively low.Based on this, the present invention constructs a kind of poly- Aniline/polypyrrole composite nano fiber preparation facilities, proposes a kind of continuous preparation method, by adding in reaction tube Agitating device makes aniline and initiator is uniformly mixed and constant flow, and polymerization is generated during steady flow, generates poly- Aniline nano-fiber；Then pyrroles and initiator are introduced in flow process, by polypyrrole poly- under lasting flow regime Aniline nano-fiber surface is coated, and is finally realized high regularity, is had excellent performance polyaniline/polypyrrole composite nano fiber Serialization preparation；Meanwhile composite nano fiber is made to carry out molecularly oriented using flow driving power.The present invention do not need using appoint What organic solvent and template, without cumbersome postprocessing working procedures, low in cost, easy to operate, reaction is controllable, repeatability is high, whole A polymerization process is completed in reaction tube, high production efficiency, is to realize high-quality polyaniline/polypyrrole composite nano fiber scale Change a kind of effective way of quantity-produced.

Summary of the invention

Aiming at the problems existing in the prior art, the present invention provides a kind of company of polyaniline/polypyrrole composite nano fiber Continuousization preparation facilities and method, first by being uniformly mixed aniline and initiator solution in reaction tube by agitating device, And provide and continue, stable flow driving power, it realizes the flowing polymerization of aniline, obtains polyaniline nano fiber；Then pass through stream Pyrrole monomer and initiator solution are constantly introduced into current system by velocity control device, and pyrroles exists under lasting flow regime Polyaniline nano fiber surface carries out chemical oxidising polymerisation, realizes and carries out surface cladding to polyaniline nano fiber, final to prepare The polyaniline/polypyrrole composite nano fiber that regularity is high out, has excellent performance.

In order to solve the above-mentioned technical problem, the invention adopts the following technical scheme:

A kind of serialization preparation facilities of polyaniline/polypyrrole composite nano fiber, including the first container, second container, stirring Device, third container, the 4th container, current velocity controller, the first reaction tube, the second reaction tube and collection vessel；Described The feed end connection the first container and second container of one reaction tube, the discharge end of the first reaction tube is in coaxial fashion via second The feed end of reaction tube is extend into the second reaction tube, and agitating device is equipped in the first reaction tube；Second reaction tube into Expect that end connection third container and the 4th container, the discharge end of the second reaction tube connect collection vessel；The third container and the 4th Container is connected separately with current velocity controller.

Further, the length of first reaction tube is 2 ~ 8 m, and internal diameter is 10 ~ 100 mm；The agitating device Diameter of propeller blade is depending on the inner diameter size of the first reaction tube；The length of second reaction tube be 2 ~ 20 m, internal diameter be 50 ~ 300 mm；The length of first reaction tube and the second reaction tube ratio is 1:(0.5 ~ 10), diameter ratio is 1:(1 ~ 10), the second reaction tube Feed end be equipped with convex-concave region, of length no more than the first tube length of reaction tube protruded into the second reaction tube.

The material of the production agitating device and reaction tube is polyflon, phenolic resin or organic silicon monomer The material of the acid and alkali-resistances such as resin.

The current velocity controller is driving pump, flow injection device or peristaltic pump, the driving pump or flow injection device It is separately positioned on inside third container and the 4th container, the peristaltic pump setting is reacted in third container, the 4th container with second On connecting line between pipe.

The method for preparing polyaniline/polypyrrole composite nano fiber using the serialization preparation facilities, steps are as follows:

(1) the aniline monomer solution containing dopant is injected into the first container, the aniline monomer containing dopant is caused Agent solution is injected into second container, and aniline monomer solution and initiator solution flow into the first reaction tube under gravity In, aniline monomer solution and initiator solution are mixed and with certain speed in the first reaction tube by the rotation of agitating device Interior flowing polymerization, generates polyaniline nano fiber；

(2) pyrrole monomer and pyrrole monomer initiator are dissolved in respectively in the third container and the 4th container containing dopant, Two solution are persistently injected into the second reaction tube with certain speed by current velocity controller, by the second reaction tube beginning Convex-concave region mix them thoroughly, contacted when flowing through the first reaction pipe end with polyaniline nano fiber, and in polyaniline Nanofiber surface carries out oxidation polymerization；With constant flow polymerization of the reaction solution in the second reaction tube, polypyrrole constantly exists Polyaniline nano fiber surface is coated, and is finally pooled in collection vessel；

(3) by reaction product washing, suction filtration and the drying in collection vessel, polyaniline/polypyrrole composite nano fiber is obtained eventually.

Further, the solution flow velocity in the step (1) in the first reaction tube is controlled by the revolving speed of agitating device, The revolving speed of agitating device is 50 ~ 2000 r/min.

Further, the solution flow velocity in the step (2) in the second reaction tube is 10 ~ 1000 mL/h；Pyrrole monomer solution It can also be respectively controlled with the relative velocity of initiator solution.

Further, the molar concentration of the aniline monomer solution and pyrrole monomer solution is 0.005~5.0 mol/L, is rubbed You are than being 1:(0.1 ~ 10.0).

Further, the aniline monomer initiator is ammonium persulfate, ferric trichloride, bichromate, hydrogen peroxide or mistake Aoxidizing at least one of formyl, pyrrole monomer initiator is at least one of ferric trichloride, ammonium persulfate or hydrogen peroxide, The molar ratio of monomer and initiator is 1:0.01~10.0.

Further, the dopant is hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, fluoboric acid, acetic acid, sulfosalisylic Acid, saturated fatty acid, helianthic acid, how at least one of sulfonic acid, camphorsulfonic acid or dodecyl benzene sulfonic acid, dopant Molar concentration is 0.1 ~ 6.0 mol/L.

Synthesis mechanism of the invention: present invention proposition synthesizes polyaniline nano fiber first under flow regime, then Polypyrrole is coated on polyaniline nano fiber surface by the in situ chemical oxidative polymerization of pyrroles during same flowing, is realized It is prepared by the serialization of polyaniline/polypyrrole composite nano fiber；The inducing molecule chain orientation by way of flowing, and then prepare Pattern is uniform, compound with regular structure, well dispersed high-quality polyaniline/polypyrrole composite nano fiber.The invention is low in cost, grasps Work is simple, reaction is controllable, without using any organic solvent and template, repeatability height, and entire polymerization process is complete in reaction tube At, greatly improve production efficiency, be suitable for scale consecutive production.

Beneficial effects of the present invention: (1) preparation method of the present invention and existing polyaniline/polypyrrole composite nano fiber Compared to outstanding feature, the synthesis which overcomes existing polyaniline/polypyrrole composite nano fiber preparation method is imitated Rate is low, is difficult to the disadvantages such as mass production, preparation process is cumbersome, feed stock conversion is low, for the first time by polyaniline and polypyrrole Synthesis carries out one-step method and integrates, and proposes the continuity Composite process of polyaniline and polypyrrole；By adding agitating device energy Reaction solution mixing uniformity is enough greatly improved, and then effectively increases yield and preparation efficiency, in addition, by current velocity controller Can Effective Regulation flow velocity, ensured the flow stability of reaction solution, and then the orientation of effectively inducing molecule chain, final continuous system Standby compound with regular structure out is had excellent performance, well dispersed high-quality polyaniline/polypyrrole composite nano fiber.

(2) present invention is low in cost, easy to operate, reaction is controllable, does not need using any organic solvent and template, is not necessarily to Cumbersome postprocessing working procedures, entire polymerization process are completed in reaction tube, substantially increase industrial applications potentiality；Reaction solution is mixed It closes uniformity coefficient and flowing polymerization stability is high, effectively contained the generation of clogging, and without in timely process container Reaction product, further ensure the polyaniline/polypyrrole composite nano fiber size and structure of different time sections preparation Homogeneity, repeatability are high；The invention is continuously controllable, and combined coefficient is high, convenient to grow to polyaniline/polypyrrole composite nano fiber Process is monitored now, facilitates relevant polymerization mechanism study.

(3) compound with regular structure prepared by the present invention, the high-quality polyaniline/polypyrrole composite nano fiber haveing excellent performance, It can be applied to many necks such as energy storage and converting material, conductive material, anti-static material, anti-corrosion material and sensing material Domain.

Detailed description of the invention

Fig. 1 is the structural schematic diagram of the serialization preparation facilities of polyaniline/polypyrrole composite nano fiber；

Fig. 2 is the transmission electron microscope picture of polyaniline/polypyrrole composite nano fiber synthesized by the embodiment of the present invention 1；

Fig. 3 is electric in neutrality for the electrode prepared using polyaniline/polypyrrole composite nano fiber synthesized by the embodiment of the present invention 2 Solve the electrochemistry cyclic voltammetry curve in liquid；

Fig. 4 is the scanning electron microscope (SEM) photograph of polyaniline/polypyrrole composite nano fiber synthesized by the embodiment of the present invention 3；

Fig. 5 is the gas sensor that is prepared using polyaniline/polypyrrole composite nano fiber synthesized by the embodiment of the present invention 4 to first The response curve of alcohol；

Fig. 6 is the electrode that is prepared using polyaniline/polypyrrole composite nano fiber synthesized by the embodiment of the present invention 5 in Neutral Electrolysis Constant current charge-discharge curve in liquid.

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 shown in Figure 1, the serialization preparation facilities of polyaniline/polypyrrole composite nano fiber of the invention include the first container 1, Second container 2, agitating device 3, third container 4, the 4th container 5, current velocity controller 6, the first reaction tube 7, the second reaction tube 8 With collection vessel 9；The beginning of first reaction tube 7 is connected to the first container 1 and second container 2, and end is with coaxial Mode is extend into the second reaction tube 8, internal that agitating device 3 is arranged；The beginning of second reaction tube is connected to third Container 4, the 4th container 5 and the first reaction tube 7, and it is equipped with convex-concave region.The length of first reaction tube is 2 m, interior Diameter is 20 mm, and the diameter of the agitating device is 18 mm, and the length of second reaction tube is 2 m, internal diameter 50 mm；The first container 1 and second container 2 fills aniline solution and aniline initiator solution, the third container 4 respectively Chromium solution and pyrroles's initiator solution are filled respectively with the 4th container 5, and collection vessel 9 collects final product.

The method for preparing polyaniline/polypyrrole composite nano fiber using above-mentioned apparatus is as follows:

(1) 93.2 g(1mol are accurately weighed) aniline and 11.4 g(0.05mol) ammonium persulfate, it is dissolved in the 0.1 of 1 L respectively In mol/L hydrochloric acid solution and it is injected into the first container and second container；Accurately weigh 67.1 g(1mol) pyrroles and 11.4 g (0.05) ammonium persulfate is dissolved in the 0.1 mol/L hydrochloric acid solution of 1 L respectively and is injected separately into third container and the 4th and holds In device.

(2) 50.0 r/min are set by the revolving speed of agitating device, makes the solution of the first container and second container constantly The first reaction tube is introduced, is uniformly mixed reaction solution by the rotation of agitating device, steady flow and polymerization obtain polyaniline and receive Rice fiber, polyaniline nano fiber flow into the second reaction tube with solution；By the solution in third container and the 4th container It is sustainedly and stably injected into the second reaction tube by current velocity controller, flow velocity is set as 10 mL/h, by the second reaction tube The convex-concave region of feed end mixes them thoroughly, and converges when flowing through the first reaction tube discharge end with polyaniline nano fiber, with Constant flow polymerization of the reaction solution in the second reaction tube, polypyrrole constantly coated on polyaniline nano fiber surface, Finally it is pooled to (see figure 1) in the collection vessel 9 for fill deionized water.

(3) after wait flow, after reaction product is washed repeatedly, filtered and is dried, obtain diameter between 30~ 40 nm, length between 200~600 nm polyaniline/polypyrrole composite nano fiber (as shown in Figure 2).