CN105670284A - Method for preparing polypyrrole/inorganic nano composite material - Google Patents

Method for preparing polypyrrole/inorganic nano composite material Download PDF

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CN105670284A
CN105670284A CN201610217943.9A CN201610217943A CN105670284A CN 105670284 A CN105670284 A CN 105670284A CN 201610217943 A CN201610217943 A CN 201610217943A CN 105670284 A CN105670284 A CN 105670284A
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composite material
polypyrrole
inorganic nano
nano composite
inorganic
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CN105670284B (en
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杨飞
燕群
李传宪
孙广宇
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China University of Petroleum East China
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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
    • 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
    • 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
    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

The invention discloses a method for preparing a polypyrrole/inorganic nano composite material.According to the method, the nano composite structure material is generated through an electrochemical in-situ reaction.Inorganic nano particle hydrosol which is evenly dispersed is prepared through a sol-gel method, and then pyrrole monomers are added into the hydrosol for in-situ preparation of the composite material.The preparation method guarantees good dispersity of the inorganic nano particles in a polypyrrole base body, and application performance of the polypyrrole/inorganic nano composite material is remarkably improved.In-situ generation is directly conducted through the electrochemical reaction, the synthesis process is simple, and the composite material is environmentally friendly and free of pollution.Thus, the composite material has good application prospects and economic benefits.

Description

A kind of preparation method of polypyrrole/inorganic nano composite material
Technical field
The preparation method that the present invention relates to a kind of polypyrrole/inorganic nano composite material, belongs to field of material preparation.
Background technology
Polypyrrole is a kind of heterocycle conjugated type conducting polymer, can obtain, through suitable inorganic nano-filler doping, the composite having good electric conductivity, magnetic, heat resistance and mechanical performance concurrently. Such composite is with a wide range of applications in fields such as sensor, ultracapacitor, conducing composite material, solaode, anti-corrosive metal coatings. At present, polypyrrole/inorganic nano composite material is many is prepared by chemical oxidization method in organic solvent. It is generally of higher volatility and physiological-toxicity due to organic solvent, limits the industrialized production of polypyrrole/inorganic nano composite material.
Electrochemical synthesis is a kind of method preparing Preparing Organic-inorganic Nano Hybrid Material that development in recent years is got up. Electrochemical synthesis, also known as electrolytic synthesis, is utilize electrolysis means to carry out electrode reaction at electrode surface thus generating a kind of green synthesis techniques of novel substance. This synthetic method can carry out at normal temperatures and pressures, and can pass through to regulate the state modulator reaction process such as current potential, electric current density, it is simple to automatically controls, simplifies reactions steps, decreases the generation of reactant loss and side reaction. Electrochemical synthesis complies fully with " Atom economy " requirement, and traditional synthetic catalyst and synthesis " medium " are extremely difficult to this requirement. Oxidation in organic solvent method relative to traditional: (1) electrochemical synthesis carries out in aqueous phase, it is not necessary to poisonous or dangerous oxidant, reducing agent and organic solvent, has good economy and hypotoxicity; (2) electrochemical synthetic process is simple, reaction condition is gentle, and required energy consumption and equipment investment are low; (3) electrochemical synthesis product is prone to refining spearation, and the purity of product is high, by-product is few, and environmental pollution can be greatly lowered; (4) composite that electrochemical synthesis obtains is membranaceous, it is possible to be directly used in anti-corrosion of metal, sensor, ultracapacitor, conducing composite material. Therefore, people's growing interest electrochemical synthesis application in Preparing Organic-inorganic Nano Hybrid Material preparation field.
At present, the existing relevant report utilizing electrochemical synthesis to prepare polypyrrole/inorganic nano composite material, mainly use churned mechanically mode to be scattered in aqueous phase by inorganic nanoparticles powder body, be subsequently adding pyrrole monomer and carry out the preparation of composite. Due to mechanical agitation be difficult to ensure inorganic nanoparticles in aqueous phase fully dispersed, cause that in prepared composite, distribution of particles is uneven, and locally lie in particle aggregation phenomenon. It reduce the application performance of polypyrrole/inorganic nano composite material.
Summary of the invention
The technical problem to be solved is to be difficult to ensure inorganic nanoparticles this problem fully dispersed in aqueous phase for existing electrochemical synthesis technology, a kind of new method prepared based on the polypyrrole/inorganic nano composite material of electrochemical synthesis is proposed, to ensure inorganic nanoparticles good dispersion in polypyrrole matrix, and then significantly improve the application performance of polypyrrole/inorganic nano composite material.
The technical problem of the present invention solves by the following technical programs, comprises the following steps:
Step 1, prepare inorganic nanoparticles. Sol-gal process is adopted to prepare at aqueous phase system situ, select the water-disintegrable monomer such as tetraethyl orthosilicate or butyl titanate, according to the concentration of 0.05～0.3mol/L, in the ethanol water of volume ratio water-ethanol=10 1, under room temperature, direct hydrolysis obtains the inorganic nanoparticles such as corresponding nano silicon, nano titanium oxide.
Step 2, mixing. The inorganic nanoparticles hydrosol of step 1 adds the pyrrole monomer after purifying, passes into nitrogen deoxygenation and be uniformly mixed.
Step 3, electrolysis. The liquid of mix homogeneously in step 2 is added electrolyzer, adopts three-electrode system, system is applied the voltage of 0.6～2.0V, with electrochemical synthesis as the motive force reacted.
Step 4, deposition. By electrodeposit reaction, adopting electrochemical operation to stand in electrolytic cell anode deposition polypyrrole/inorganic nano composite material, scanning ten circle, scanning speed is 50mv/s.
Step 5, cleaning, dry. The electrode obtained entirety is alternately cleaned three times with water with ethanol, then drying under reduced pressure 24h, obtain the polypyrrole/inorganic nano composite material after purification.
The invention has the beneficial effects as follows, first prepare inorganic nanoparticles colloidal sol, then in colloidal sol environment, synthesize polypyrrole/inorganic nano composite material by electrochemical method, abandoned the organic solvent that toxicity is bigger. Synthesized polypyrrole/inorganic nano composite material surface is comparatively smooth, polypyrrole Medium Culture even particle distribution, and synthesis step is simple, efficiently, it is easy to prepare in a large number, is suitable for industrialized production. Compared with prior art, the invention have the advantage that
(1) in aqueous phase system, carry out the generation of composite, it is to avoid using organic solvent, building-up process presses close to the requirement of Green Chemistry and low temperature, it is easy to operation, be suitable for industrialized mass production.
(2) by adopting sol-gal process to prepare inorganic nanoparticles at aqueous phase system situ, with simple stirring mixed phase ratio, Granular composite degree is good, is conducive to composite inner granule to be uniformly distributed.
(3) by electrochemistry as the driving force reacted, building-up process energy expenditure is relatively low, more economical.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, embodiments of the invention are described in further detail.
Fig. 1 is polypyrrole/inorganic nanoparticles composite flow process figure prepared by the present invention.
Fig. 2 is the polypyrrole/nanometer silicon dioxide composite material infrared spectrum of the embodiment of the present invention 1 preparation.
Fig. 3～Fig. 5 is the scanning electron microscope spectrogram (SEM) of the polypyrrole/nanometer silicon dioxide composite material of the different silica concentrations of the embodiment of the present invention 1 preparation respectively.
Fig. 6 is the polypyrrole/nanometer titanium dioxide composite material infrared spectrum of the embodiment of the present invention 2 preparation.
Fig. 7～Fig. 9 is the scanning electron microscope spectrogram (SEM) of the polypyrrole/nanometer titanium dioxide composite material of the different titanium dioxide concentration of the embodiment of the present invention 2 preparation.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is further illustrated; the present embodiment is carried out under the premise with technical solution of the present invention; give detailed embodiment and concrete operating procedure, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1: be separately added in 200ml distilled water by 2.08g, 6.24g and 12.48g tetraethyl orthosilicate, is separately added into 20ml straight alcohol, and at 25 DEG C, mechanical agitation hydrolysis 24h, obtains the silica sol of 0.05mol/L, 0.15mol/L and 0.3mol/L successively. After 2.36g pyrroles is purified by the mode of distillation of reducing pressure, join in silica sol system, be continually fed into nitrogen deoxygenation, stir 30min mix homogeneously. The liquid of mix homogeneously is added electrolyzer, using cyclic voltammetry anodic oxidation to generate polypyrrole/nanometer silicon dioxide composite material, scanning current potential is between 0.6～2.0V, between the circulation number of turns is enclosed 50～400, potential scanning speed is 50mv/s, scanning ten circle. Polypyrrole/the nanometer silicon dioxide composite material obtained by anode electrode surface scrapes, and uses ethanol alternately to be cleaned three times by gained composite with water. After drying 24 at 80 DEG C, obtain the polypyrrole/nanometer silicon dioxide composite material of three kinds of different silica concentrations. The infrared spectrum of composite and SEM spectrogram are shown in Fig. 2 and Fig. 3～Fig. 5. Fig. 2 is the infrared spectrum of the polypyrrole/nanometer silicon dioxide composite material of different silica content. From Figure 2 it can be seen that 1384cm-1The absworption peak existed is the absorption vibration peak of pyrrole ring, 784cm-1Be on pyrrole ring=the out-of-plane bending vibration peak of C-H. Outside characteristic absorption peak except above-mentioned PPy, due to PPy-SiO2Containing SiO in rete2So that its infrared spectrum occurs in that SiO2Characteristic peak. Such as: 1100cm-1Absworption peak be antisymmetric stretching vibration peak in Si-O-Si structure; 799cm-1、694cm-1Absworption peak be Si-O symmetrical stretching vibration absworption peak. Infrared analysis shows, has synthesized PPy-SiO by cyclic voltammetry2Composite. Fig. 3～Fig. 5 is the SEM spectrogram of the polypyrrole/nanometer silicon dioxide composite material of different silica concentration (0.05mol/L, 0.15mol/L and 0.3mol/L) successively. It is distributed by surface particles, it is possible to directly find out polypyrrole/nanometer silicon dioxide composite material even particle size distribution, and have comparatively homogeneous apparent condition.
Embodiment 2: be separately added in 200ml distilled water by 2.5g, 7.5g, 15g butyl titanate, is separately added into 20ml straight alcohol, obtains the titanium oxide sol of 0.05mol/L, 0.15mol/L and 0.3mol/L successively. After 2.36g pyrroles is purified by the mode of distillation of reducing pressure, join in titanium oxide sol system, be continually fed into nitrogen deoxygenation, by stirring mixing 30min. The liquid of mix homogeneously being added electrolyzer, uses cyclic voltammetry anodic oxidation to generate polypyrrole/nanometer titanium dioxide composite material, scanning current potential is between 0.6～2.0V, and scanning speed is 50mv/s, scanning ten circle. Polypyrrole/the nanometer titanium dioxide composite material that obtains of anode electrode surface is scraped, uses ethanol alternately to be cleaned three times by gained composite with water. After drying 24 at 80 DEG C, obtain product. The infrared spectrum of composite and SEM spectrogram are shown in Fig. 6 and Fig. 7～Fig. 9. Fig. 6 is the infrared spectrum of polypyrrole/nanometer titanium dioxide composite material. As seen from Figure 6,3000～2800cm-1Between strong absworption peak corresponding to the C-H symmetric and anti-symmetric stretching vibration of methyl in alkyl chain and methylene, 1300～1500cm-1The absorption at place is then caused by the bending vibration of c h bond, 400～1000cm-1Between absorption then corresponding to the vibration of Ti-O key, 750cm-1It it is the characteristic absorption peak of Ti-O-Ti key.Infrared analysis shows, has synthesized polypyrrole/nanometer titanium dioxide composite material by cyclic voltammetry. Fig. 7～Fig. 9 is the SEM spectrogram of the polypyrrole/nanometer titanium dioxide composite material of different titanium oxide concentration (0.05mol/L, 0.15mol/L and 0.3mol/L) successively, it can be seen directly that polypyrrole/nanometer titanium dioxide composite material even particle size distribution, and there is comparatively homogeneous apparent condition.
Embodiments above; it is the goal in research to the present invention, technology path, the further illustrating of effect of optimization; it is not limiting as other embodiments of the present invention; all within the spirit and principles in the present invention; any amendment, the optimization made design, are equal to replacement etc., all should within protection scope of the present invention.

Claims (1)

1. the preparation method of polypyrrole/inorganic nano composite material, it is characterised in that comprise the following steps:
(1) inorganic nanoparticles is prepared, sol-gal process is adopted to prepare at aqueous phase system situ, select tetraethyl orthosilicate or butyl titanate, according to the concentration of 0.05～0.3mol/L, in the ethanol water of volume ratio water-ethanol=10 1, under room temperature, direct hydrolysis obtains corresponding nanometer silicon dioxide particle or titanium dioxide nanoparticle;
(2) according to mol ratio pyrrole monomer inorganic nanoparticles=3 1～10 1, the above-mentioned machine nano-particle hydrosol adds the pyrrole monomer after purifying, passes into nitrogen deoxygenation and be uniformly mixed;
(3) liquid of mix homogeneously in (2nd) step is added electrolyzer, adopt three-electrode system, system is applied the voltage of 0.6～2.0V, with electrochemical synthesis as the motive force reacted;
(4) by electrodeposit reaction, adopting electrochemical operation to stand in electrolytic cell anode deposition polypyrrole/inorganic nano composite material, scanning ten circle, scanning speed is 50mv/s;
(5) with water, the material entirety scraped from electrode is alternately cleaned three times with ethanol, at 80 DEG C of dry 24h, obtain the polypyrrole/inorganic nano composite material after purification.
CN201610217943.9A 2016-04-08 2016-04-08 A kind of preparation method of polypyrrole/inorganic nano composite material Expired - Fee Related CN105670284B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108250559A (en) * 2018-03-05 2018-07-06 象山杰尔德智能科技有限公司 A kind of high-performance rotational moulding type urea box and preparation method thereof
CN108410168A (en) * 2018-03-08 2018-08-17 查公祥 A kind of intercalation polypyrrole nano material and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101789513A (en) * 2010-03-30 2010-07-28 上海交通大学 Composite proton conducting membrane added with proton conducting polymer and preparation method thereof

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
CN101789513A (en) * 2010-03-30 2010-07-28 上海交通大学 Composite proton conducting membrane added with proton conducting polymer and preparation method thereof

Non-Patent Citations (3)

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MITSUYOSHI ONODA ET AL.: "Conducting Polypyrrole-Silica Glass Composite Films Prepared by Electrochemical Polymerization", 《JPN.J.APPL.PHYS PART 1》 *
王黔平 等: "《Al2O3系复合微滤膜制备研究》", 30 November 2010 *
陈剑松: "多巴胺修饰的二氧化钛纳米粒子-导电聚合物纳米复合膜的制备、表征及其光电转换性质", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108250559A (en) * 2018-03-05 2018-07-06 象山杰尔德智能科技有限公司 A kind of high-performance rotational moulding type urea box and preparation method thereof
CN108410168A (en) * 2018-03-08 2018-08-17 查公祥 A kind of intercalation polypyrrole nano material and preparation method thereof

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