CN105670284B - A kind of preparation method of polypyrrole/inorganic nano composite material - Google Patents
A kind of preparation method of polypyrrole/inorganic nano composite material Download PDFInfo
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- CN105670284B CN105670284B CN201610217943.9A CN201610217943A CN105670284B CN 105670284 B CN105670284 B CN 105670284B CN 201610217943 A CN201610217943 A CN 201610217943A CN 105670284 B CN105670284 B CN 105670284B
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- polypyrrole
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- 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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/024—Anodisation under pulsed or modulated current or potential
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a kind of preparation methods of polypyrrole/inorganic nano composite material.It is a kind of preparation method for reacting generated nano composite structural material by electrochemical in-situ.The present invention first passes through sol-gel processing and prepares the finely dispersed inorganic nanoparticles hydrosol, and pyrrole monomer is then added in the hydrosol carries out being prepared in situ for composite material.Above-mentioned preparation method has ensured good dispersion of the inorganic nanoparticles in polypyrrole matrix, and then significantly improves the application performance of polypyrrole/inorganic nano composite material.And generated by electrochemical reaction direct in-situ, building-up process is simple, green non-pollution.Therefore the composite material has preferable application prospect and economic benefit.
Description
Technical field
The present invention relates to a kind of preparation methods of polypyrrole/inorganic nano composite material, belong to field of material preparation.
Background technology
Polypyrrole is a kind of heterocycle conjugated type conducting polymer, can be obtained by inorganic nano-filler appropriate doping simultaneous
Has the composite material of good electric conductivity, magnetism, heat resistance and mechanical performance.Such composite material is in sensor, super capacitor
The fields such as device, conducing composite material, solar cell, anti-corrosive metal coating are with a wide range of applications.Currently, polypyrrole/
Inorganic nano composite material is mostly prepared by chemical oxidization method in organic solvent.Since organic solvent usually has higher wave
Hair property and physiological-toxicity, limit the industrialized production of polypyrrole/inorganic nano composite material.
Electrochemical synthesis is a kind of method preparing Preparing Organic-inorganic Nano Hybrid Material developed in recent years.
Electrochemistry formated is also known as electrosynthesis glyoxal, is to carry out electrode reaction in electrode surface to generate the one of novel substance using electrolysis means
Kind green synthesis techniques.The synthetic method can carry out at normal temperatures and pressures, and can be by adjusting the parameters controls such as current potential, current density
Reaction process processed simplifies reaction step convenient for automatically controlling, and reduces the generation of reactant loss and side reaction.Electrochemistry
Synthesis complies fully with " Atom economy " requirement, and traditional synthetic catalyst and synthesis " medium " are extremely difficult to this requirement.
Relative to traditional oxidation in organic solvent method：(1) electrochemistry formated carries out in water phase, without toxic or dangerous oxidation
Agent, reducing agent and organic solvent have good economy and hypotoxicity；(2) electrochemical synthetic process is simple, reaction condition temperature
With required energy consumption and equipment investment are low；(3) electrochemistry formated product is easy to refining spearation, purity height, the by-product of product
It is few, environmental pollution can be greatly lowered；(4) composite material that electrochemistry formated obtains is in membranaceous, and it is anti-to be used directly for metal
Corruption, sensor, ultracapacitor, conducing composite material.Therefore, people's growing interest electrochemical synthesis is in polymer/inorganic
Application in nanocomposite preparation field.
Currently, the existing relevant report that polypyrrole/inorganic nano composite material is prepared using electrochemical synthesis, mainly
Inorganic nanoparticles powder is scattered in water phase using churned mechanically mode, pyrrole monomer is then added and carries out composite material
Preparation.Since mechanical agitation is difficult to ensure that inorganic nanoparticles are fully dispersed in water phase, lead to prepared composite material
Middle distribution of particles is uneven, and locally lies in particle aggregation phenomenon.It reduce polypyrrole/inorganic nano composite materials
Application performance.
Invention content
The technical problem to be solved by the present invention is to be directed to existing electrochemistry formated technology to be difficult to ensure inorganic nanoparticles
This fully dispersed problem in water phase proposes prepared by a kind of polypyrrole based on electrochemistry formated/inorganic nano composite material
New method, to ensure good dispersion of the inorganic nanoparticles in polypyrrole matrix, and then significantly improve polypyrrole/inorganic
The application performance of nanocomposite.
The technical problem of the present invention solves by the following technical programs, includes the following steps：
Step 1 prepares inorganic nanoparticles.It is prepared in situ in aqueous phase system using sol-gel processing, selects positive silicon
The water-disintegrable monomer such as acetoacetic ester or butyl titanate, according to the concentration of 0.05~0.3mol/L, in the ︰ 1 of volume ratio Shui ︰ ethyl alcohol=10
Ethanol water at room temperature direct hydrolysis obtain the inorganic nanos such as corresponding nano silicon dioxide, nano-titanium dioxide
Grain.
Step 2, mixing.The pyrrole monomer after purification is added in the inorganic nanoparticles hydrosol of step 1, is passed through nitrogen
Deoxygenation is simultaneously uniformly mixed.
Step 3, electrolysis.Electrolytic cell is added in the liquid being uniformly mixed in step 2 to apply system using three-electrode system
The voltage for adding 0.6~2.0V uses electrochemistry formated as the motive force of reaction.
Step 4, deposition.By electrodeposit reaction, polypyrrole/inorganic is deposited in electrolytic cell anode using electrochemical workstation
Nanocomposite, ten circle of scanning, sweep speed 50mv/s.
Step 5, cleaning, drying.The electrode obtained is integrally replaced into cleaning three times with water with ethyl alcohol, then is dried under reduced pressure for 24 hours, is obtained
To polypyrrole/inorganic nano composite material after purification.
The invention has the advantages that preparing inorganic nanoparticles colloidal sol first, then pass through electrification in colloidal sol environment
Method synthesizes polypyrrole/inorganic nano composite material, has abandoned the organic solvent being more toxic.Synthesized polypyrrole/nothing
Machine nanocomposite surface is more smooth, and polypyrrole Medium Culture even particle distribution, synthesis step is simple, efficiently, is easy to big
Prepared by amount, be suitable for industrialized production.Compared with prior art, it is an advantage of the invention that：
(1) generation that composite material is carried out in aqueous phase system avoids using organic solvent, and building-up process is close to greenization
Requirement, and low temperature, it is easily operated, it is suitble to industrialized mass production.
(2) inorganic nanoparticles are prepared in situ in aqueous phase system by using sol-gel processing, with simple stirring
Mixed phase ratio, particle degree of scatter is good, is conducive to composite inner particle and is uniformly distributed.
(3) it is used as the driving force of reaction by electrochemistry, building-up process energy expenditure is relatively low, more economical.
Description of the drawings
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is polypyrrole/inorganic nanoparticles composite material flow figure prepared by the present invention.
Fig. 2 is polypyrrole/nanometer silicon dioxide composite material infrared spectrum prepared by the embodiment of the present invention 1.
Fig. 3~Fig. 5 is polypyrrole/nanometer titanium dioxide of different silica concentrations prepared by the embodiment of the present invention 1 respectively
The scanning electron microscope spectrogram (SEM) of silicon composite.
Fig. 6 is polypyrrole/nanometer titanium dioxide composite material infrared spectrum prepared by the embodiment of the present invention 2.
Fig. 7~Fig. 9 is that polypyrrole/nano-titanium dioxide of different titanium dioxide concentrations prepared by the embodiment of the present invention 2 is multiple
The scanning electron microscope spectrogram (SEM) of condensation material.
Specific implementation mode
The present invention is further illustrated with reference to the accompanying drawings and examples, and the present embodiment is with technical solution of the present invention
Under the premise of implemented, give detailed embodiment and specific operating procedure, but protection scope of the present invention is unlimited
In following embodiments.
Embodiment 1：2.08g, 6.24g and 12.48g ethyl orthosilicate are separately added into 200ml distilled water, are separately added into
20ml straight alcohols, at 25 DEG C mechanical agitation hydrolysis for 24 hours, obtain the oxidation of 0.05mol/L, 0.15mol/L and 0.3mol/L successively
Ludox.After 2.36g pyrroles is purified by way of vacuum distillation, it is added in silica sol system, is continually fed into nitrogen
Gas deoxygenation, stirring 30min are uniformly mixed.Electrolytic cell is added in uniformly mixed liquid, uses cyclic voltammetry anodic oxygen metaplasia
At polypyrrole/nanometer silicon dioxide composite material, scanning current potential is between 0.6~2.0V, and the cycle number of turns is in 50~400 circles
Between, potential scanning speed 50mv/s, ten circle of scanning.Polypyrrole/nano silicon dioxide that anode electrode surface is obtained is compound
Material scrapes, and gained composite material is replaced cleaning three times with water using ethyl alcohol.To get three kinds of differences after dry 24 at 80 DEG C
Polypyrrole/nanometer silicon dioxide composite material of silica concentration.The infrared spectrum of composite material is shown in Fig. 2 and Fig. 3 with SEM spectrograms
~Fig. 5.Fig. 2 is the infrared spectrum of polypyrrole/nanometer silicon dioxide composite material of different silica contents.From Figure 2 it can be seen that
1384cm-1Existing absorption peak is the absorption vibration peak of pyrrole ring, 784cm-1Be on pyrrole ring=out-of-plane bending of C-H shakes
Dynamic peak.Outside characteristic absorption peak except above-mentioned PPy, due to PPy-SiO2Contain SiO in film layer2So that occur in its infrared spectrum
SiO2Characteristic peak.Such as：1100cm-1Absorption peak be antisymmetric stretching vibration peak in Si-O-Si structures；799cm-1、
694cm-1Absorption peak be Si-O symmetrical stretching vibration absorption peaks.Infrared analysis shows to have synthesized PPy- by cyclic voltammetry
SiO2Composite material.Fig. 3~Fig. 5 is the poly- of different silica concentrations (0.05mol/L, 0.15mol/L and 0.3mol/L) successively
The SEM spectrograms of pyrroles/nanometer silicon dioxide composite material.It is distributed by surface particles, it can be seen directly that polypyrrole/nanometer two
Silica composite material even particle size distribution, and have more uniform surface state.
Embodiment 2：2.5g, 7.5g, 15g butyl titanate are separately added into 200ml distilled water, it is pure to be separately added into 20ml
Ethyl alcohol obtains the titanium oxide sol of 0.05mol/L, 0.15mol/L and 0.3mol/L successively.2.36g pyrroles is steamed by depressurizing
It after the mode evaporated purifies, is added in titanium oxide sol system, is continually fed into nitrogen deoxygenation, mixes by stirring 30min.It will mix
It closes uniform liquid and electrolytic cell is added, polypyrrole/nanometer titanium dioxide composite material is generated using cyclic voltammetry anodic oxidation,
Current potential is scanned between 0.6~2.0V, sweep speed 50mv/s, ten circle of scanning.By anode electrode surface obtain polypyrrole/
Nanometer titanium dioxide composite material scrapes, and gained composite material is replaced cleaning three times with water using ethyl alcohol.It is dry at 80 DEG C
To get product after 24.The infrared spectrum of composite material is shown in Fig. 6 and Fig. 7~Fig. 9 with SEM spectrograms.Fig. 6 is polypyrrole/nano-silica
Change the infrared spectrum of titanium composite material.As seen from Figure 6,3000~2800cm-1Between strong absworption peak correspond to alkyl chain in methyl
With the C-H symmetric and anti-symmetric stretching vibrations of methylene, 1300~1500cm-1The absorption at place is then drawn by the bending vibration of c h bond
It rises, 400~1000cm-1Between absorb then correspond to Ti-O keys vibration, 750cm-1It is the characteristic absorption peak of Ti-O-Ti keys.
Infrared analysis shows to have synthesized polypyrrole/nanometer titanium dioxide composite material by cyclic voltammetry.Fig. 7~Fig. 9 is not successively
With the SEM of polypyrrole/nanometer titanium dioxide composite material of titanium oxide concentration (0.05mol/L, 0.15mol/L and 0.3mol/L)
Spectrogram, it can be seen directly that polypyrrole/nanometer titanium dioxide composite material even particle size distribution, and have more uniform surface
State.
Embodiments above is the further explanation to the goal in research, technology path, effect of optimization of the present invention, and
The other embodiment of the present invention is not limited, and all within the spirits and principles of the present invention, any modification, the optimization made are set
Meter, equivalent replacement etc., all should be within protection scope of the present invention.
Claims (1)
1. a kind of preparation method of polypyrrole/inorganic nano composite material, which is characterized in that include the following steps：
(1) inorganic nanoparticles are prepared, are prepared in situ in aqueous phase system using sol-gel processing, butyl titanate is selected,
According to the concentration of 0.15mol/L, direct hydrolysis obtains accordingly at room temperature in the ethanol water of the ︰ 1 of volume ratio Shui ︰ ethyl alcohol=10
Titanium dioxide nanoparticle；
(2) ︰ 1 of Dan Ti ︰ inorganic nanoparticles=3 is coughed up according to molar ratio Bi, purification is added in above-mentioned titanium dioxide nanoparticle
Pyrrole monomer afterwards is passed through nitrogen deoxygenation and is uniformly mixed；
(3) electrolytic cell is added in the liquid being uniformly mixed in (2) step, using three-electrode system, applies the electricity of 2.0V to system
Pressure uses electrochemistry formated as the motive force of reaction；
(4) by electrodeposit reaction, polypyrrole/inorganic nano combined material is deposited in electrolytic cell anode using electrochemical workstation
Material, ten circle of scanning, sweep speed 50mv/s；
(5) material scraped from electrode is integrally replaced into cleaning three times with ethyl alcohol with water, drying for 24 hours, is purified at 80 DEG C
Polypyrrole/inorganic nano composite material afterwards.
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