CN1314760C - Montmorillonite/Ce(OH)3, Pr2O3/ polyaniline nano-rod three phase composite material and its preparation method - Google Patents
Montmorillonite/Ce(OH)3, Pr2O3/ polyaniline nano-rod three phase composite material and its preparation method Download PDFInfo
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Abstract
The present invention discloses montmorillonite / Ce (OH) 3, Pr2O3 / polyaniline nanometer rod three-phase composite material and a preparation method thereof. The present invention uses mixed rare earth salt of aniline monomers, montmorillonite, PrCl3 and CeCl3 as raw material and uses an emulsion intercalation onestep polymerization method to prepare the montmorillonite / Ce (OH) 3, Pr2O3 / polyaniline nanometer rod three-phase composite material which is uniformly dispersed; the length of the polyaniline nanometer rods is from 70 to 90 nm, the diameters of the nanometer rods are about from 15 to 25 nm, the thickness of a scouring layer is about 10 to 20 nm, and the average particle diameters of rare earth nanometer particles are about from 10 to 15 nm. the synergistic effect of the present invention exceeds the synergistic effect of composite material prepared by the traditional technique, and particularly, the heat resistance and the conductivity of the present invention are greatly increased; simultaneously, the montmorillonite and the mischmetal nanometer particles are used for greatly increasing the heat stability of the material; simultaneously, the electrochemical performance of the composite material is greatly increased.
Description
Technical Field
The invention relates to a nano composite material using polyaniline as a main body, in particular to a three-phase nano composite material consisting of polyaniline, montmorillonite and rare earth nanoparticles, belonging to the polymer composite material technology.
Background
Polyaniline is a novel functional polymer material, has unique chemical, electrical, optical and thermal properties, has wide application prospect in the fields of energy, electromagnetic shielding, corrosion prevention, electrochromism and the like, and is a conductive polymer which is expected to be widely applied. Polyaniline is a macromolecule with strong interaction and conjugated big pi bonds, the processing performance is poor, and the polymer loses conductivity due to dedoping. Because the montmorillonite has the functions of lamellar structure, heat conduction, self lubrication and the like, the electric conduction percolation threshold can be reduced after the montmorillonite is compounded with the lamellar polymer. The two-phase composite material prepared by the montmorillonite and the aniline through polymerization can improve the surface structure of the montmorillonite, play the synergistic effect of the polyaniline and the montmorillonite and provide good filler for preparing the filled conductive polymer composite material.
Montmorillonite is widely used as a filler for heat-resistant polymer composites and conductive polymer composites due to the particularity of montmorillonite. The higher the filler content in a certain range, the better the performance of the composite material, but the mechanical properties of the material are reduced, and particularly the toughness of the material is obviously reduced. One effective way to improve the performance of the composite material is to uniformly fill inorganic particles into the polymer in a nanometer level, so that the thermal property, the electrical property and the mechanical property of the polymer can be improved, but the traditional method is difficult to uniformly disperse the filler on a nanometer level; because the chemical structures and physical forms of the filler and the polymer are greatly different, the interface modification technology is difficult to completely change the interface between the filler and the polymer matrix to reduce the interfacial tension and realize the nanoscale uniform dispersion and the interfacial adhesion at present. Therefore, the composite material cannot reach the molecular dispersion level, but only belongs to a micro-mixed material, and the improvement of the toughness, rigidity, heat resistance and electrical property of the material is influenced. Another improved approach is to polymerize polymer monomers between layers of montmorillonite to form a composite. However, since the interlayer spacing of montmorillonite is less than a few nanometers, oily polymer monomers are difficult to penetrate into the interlayer of the water-based montmorillonite, and the performance of the formed composite material is also not improved ideally.
The emulsion intercalation one-step polymerization method is that emulsion self-assembly is formed by relying on a surfactant to prepare rare earth nanoparticles, a polymer monomer is used as an oil phase, a mixed rare earth ion aqueous solution is used as a water phase to form reverse micelle microemulsion, the rare earth particles are uniformly dispersed in the oil phase to form a thermodynamically stable emulsion system, then the emulsion is intercalated between the lamella layers of organic montmorillonite (O-MMT), an initiator polymer monomer is added to directly carry out in-situ polymerization to prepare the polyaniline/montmorillonite/rare earth nanoparticle ternary nanocomposite, and a novel preparation method is provided for the ternary nanocomposite. The method has the advantages of simple preparation process, short preparation time, high production efficiency and low cost, and the prepared composite material has good mechanical property, electrical property and thermal stability, and also has good processability of organic polymers, so the method has a very wide application prospect.
Disclosure of Invention
The invention aims to provide a method for preparing montmorillonite/Ce (OH) by adopting an emulsion intercalation method3，Pr2O3A method for preparing polyaniline nano-rod three-phase composite material.
The invention prepares montmorillonite/Ce (OH)3，Pr2O3The method for preparing the polyaniline nanorod three-phase composite material comprises the steps of dissolving 100 parts of aniline monomer, 10-50 parts of dopant and 15-25 parts of surfactant in 800-1200 parts of dispersion medium, uniformly stirring, and adding 10-25 parts of PrCl3With CeCl3Mixing the aqueous solution of the rare earth salt, stirring, and ultrasonically dispersing for 30-60 minutes at room temperature to form reverse micelle emulsion; then in N2Adding the reverse micelle emulsion into aqueous dispersion containing 5-20 parts of organic montmorillonite dropwise under protection, adjusting the temperature to 60-80 ℃, dispersing intercalation for 2-3 hours by magnetic stirring, then cooling to 0-5 ℃, adding initiator aqueous solution with the same mole as aniline monomer to initiate polymerization of polymer monomer, adding precipitator of rare earth nanoparticles after reaction for 24-30 hours to completely precipitate rare earth particles, filtering and washing to obtain montmorillonite/Ce (OH)3，Pr2O3Polyaniline nano-rod three-phase composite material.
The dopant is any one of sulfosalicylic acid, polystyrene sulfonic acid, dodecyl sulfuric acid, p-toluenesulfonic acid and hydrochloric acid.
The surfactant is an anionic surfactant, a cationic surfactant or a nonionic surfactant, wherein the anionic surfactant is sodium dodecyl sulfate or sodium stearate or stearic acid; the cationic surfactant is hexadecyl trimethyl ammonium chloride; the nonionic surfactant is alkylphenol polyoxyethylene.
The dispersion medium is water.
The initiator is ammonium persulfate or ferric p-toluenesulfonate.
PrCl in the mixed rare earth salt3With CeCl3The weight ratio of the components is as follows: PrCl 320％-50％，CeCl 380％～50％。
The precipitant of the rare earth nano particles is NaOH solution.
The preparation process of organic montmorillonite includes ① setting modifier in water, adding hydrochloric acid to regulate protonating solution, ② setting purified montmorillonite in water,stirring and heating in a constant-temperature water bath at 40-60 ℃ for 30-60 min, standing to form a montmorillonite aqueous dispersion, ③ dropwise adding the protonated solution into the montmorillonite aqueous dispersion, vibrating with ultrasonic waves for 3-4 hours, filtering, washing with water to remove bromide ions and chloride ions, ④ finally, drying in vacuum at 70-90 ℃, grinding and sieving to obtain the organic montmorillonite, wherein the sheets of the organic montmorillonite are uniformly dispersed in an organic modifier matrix, the thickness of the sheets is 40-50 nm, the distance between the sheets is 3-15 nm, and the special structure of the organic montmorillonite is used for preparing montmorillonite/Ce (OH)3，Pr2O3The nanometer characteristics of the polyaniline nanometer rod three-phase composite material provide the basis.
The reaction principle of the rare earth nano-ions is as follows:
montmorillonite/Ce (OH) prepared by the invention3，Pr2O3In the polyaniline nano-rod three-phase composite material, montmorillonite and rare earth nano-particle Ce(OH)3，Pr2O3Closely combined with polyaniline nano-rods and uniformly dispersed in aniline monomer in nano-scale.
montmorillonite/Ce (OH) prepared by the invention3，Pr2O3In the polyaniline nano-rod three-phase composite material, the montmorillonite and the rare earth nano-particle Ce (OH)3，Pr2O3And the polyaniline nano-rod comprises the following components in parts by mass: rare earth nanoparticles Ce (OH)3，Pr2O310-25 parts of aniline, 100 parts of montmorillonite and 5-20 parts of montmorillonite.
montmorillonite/Ce (B) prepared by the inventionOH)3，Pr2O3In the polyaniline nano-rod three-phase composite material, the montmorillonite and the rare earth nano-particle Ce (OH)3Rare earth nano particle Pr2O3And the polyaniline nano-rod comprises the following components in parts by mass: rare earth nanoparticles Ce (OH)35-20 parts of rare earth nano particle Pr2O32-12.5 parts of aniline, 100 parts of montmorillonite and 5-20 parts of montmorillonite.
montmorillonite/Ce (OH) prepared by the invention3，Pr2O3The polyaniline nanorod three-phase composite material has the advantages that the length of a polyaniline nanorod is 70-90 nm, the diameter of the nanorod is about 15-25 nm, the thickness of a soil removal lamella is about 10-20 nm, the stripping phenomenon of expanded montmorillonite can be obviously seen, a uniform nanorod composite material is formed, the average particle size of rare earth nanoparticles is about 10-15 nm, the rare earth nanoparticles have a very large interface area, the interface of a water phase and a polymer matrix has ideal bonding performance, the problems of mismatching and incompatibility of thermal expansion coefficients of water phase and oil phase substances can be solved, the inherent excellent mechanical property and high heat resistance of an inorganic substance and the inherent toughness of a polymer are fully exerted, and the physical and chemical properties of the composite material are well improved.
The invention provides montmorillonite/Ce (OH)3，Pr2O3The reinforcing effect of the polyaniline nano-rod three-phase composite material is superior to that of the composite material prepared by the traditional process, and particularly, the heat resistance and the conductivity are greatly improved. Meanwhile, montmorillonite and mixed rare earth metal nanoparticles are introduced, so that the thermal stability of the material is greatly improved, and the electrochemical performance of the composite material is greatly improved.
The preparation method has the advantages of simple preparation process, convenient operation, low cost and convenient industrial production.
Drawings
FIG. 1 shows montmorillonite/Ce (OH)3，Pr2O3Schematic diagram for forming polyaniline nanorod three-phase composite material
FIG. 2 shows montmorillonite/Ce (OH)3，Pr2O3TEM photograph of polyaniline nano-rod three-phase composite material
FIG. 3 shows montmorillonite/Ce (OH)3，Pr2O3SEM photograph of polyaniline nanorod three-phase composite material
FIG. 4 shows montmorillonite/Ce (OH)3，Pr2O3Polyaniline nanorod three-phase composite material infrared spectrum (FT-IR) diagram
FIG. 5 shows montmorillonite/Ce (OH)3，Pr2O3TG curve of polyaniline nanorod three-phase composite material
Detailed Description
Example 1100 parts of a phenylamine monomer, 10 parts of sulfosalicylic acid and 15 parts of sodium lauryl sulfate were dissolved in 800 parts of water and stirred uniformly, and 10 parts of PrCl was added thereto3With CeCl3Mixed rare earth salts (PrCl)3With CeCl 320% and 80%) of the aqueous solution, and ultrasonically dispersing the aqueous solution at room temperature for 30 minutes to form a reverse micelle emulsion; then in N2Adding the reverse micelle emulsion into aqueous dispersion containing 5 parts of organic montmorillonite dropwise under protection, heating to 80 ℃, dispersing intercalation for 2 hours by magnetic stirring, then cooling, transferring reactants into ice water bath at about 0 ℃, adding ammonium persulfate initiator aqueous solution which is equal to molar quantity of aniline monomer dropwise to initiate polymerization of aniline monomer, adding 0.1mol/L NaOH solution after reaction for 30 hours, adjusting pH to 8-9 to completely precipitate rare earth particles, filtering and washing to obtain uniformly dispersed nano-scale montmorillonite/Ce (OH)3，Pr2O3Polyaniline nano-rod three-phase composite material. Montmorillonite and rare earth nano-particle Ce (OH) in the composite material3Rare earth nano particle Pr2O3And the polyaniline nano-rod comprises the following components in parts by mass: rare earth nanoparticles Ce (OH)38 parts of rare earth nano particle Pr2O32 parts of aniline 100 parts and montmorillonite 5 parts.
Example 2 100 parts of aniline monomer, 20 parts of polystyrenesulfonic acid and 18 parts of sodium stearate were dissolved in 1000 parts of water and stirred uniformly, and then the solution was addedAdding 15 parts of PrCl3With CeCl3Mixed rare earth salts (PrCl)3With CeCl3Mixing the water solution with the mixing ratio of 30% to 70%), stirring, and performing ultrasonic dispersion for 40 minutes at room temperature to form reverse micelle emulsion; then in N2Adding the reverse micelle emulsion into aqueous dispersion containing 10 parts of organic montmorillonite dropwise under protection, heating to 75 ℃, carrying out magnetic stirring to disperse intercalation for 2 hours, then cooling, transferring the reactant into an ice water bath at about 1 ℃, adding ammonium persulfate initiator aqueous solution which is equal to molar amount of aniline monomer dropwise to initiate polymerization of aniline monomer, adding 0.1mol/L NaOH solution after 28 hours of reaction, adjusting the pH to 8-9 to completely precipitate rare earth particles, filtering and washing to obtain uniformly dispersed nano-scale montmorillonite/Ce (OH)3，Pr2O3Polyaniline nano-rod three-phase composite material. Montmorillonite and rare earth nano-particle Ce (OH) in the composite material3Rare earth nano particle Pr2O3And the polyaniline nano-rod comprises the following components in parts by mass: rare earth elementNanoparticles Ce (OH)310.5 parts of rare earth nano particle Pr2O34.5 parts of aniline 100 parts and montmorillonite 10 parts.
Example 3 100 parts of aniline monomer, 30 parts of dodecylsulfuric acid and 20 parts of stearic acid were dissolved in 1100 parts of water and stirred uniformly, and 20 parts of PrCl was added thereto3With CeCl3Mixed rare earth salts (PrCl)3With CeCl340-60 percent respectively), and ultrasonically dispersing for 50 minutes at room temperature to form reverse micelle emulsion; then in N2Adding the reverse micelle emulsion into aqueous dispersion containing 15 parts of organic montmorillonite dropwise under protection, heating to 70 ℃, carrying out magnetic stirring to disperse intercalation for 2.5 hours, then cooling, transferring the reactant into an ice water bath at about 3 ℃, adding ammonium persulfate initiator aqueous solution which is equal to molar aniline monomer and is added dropwise to initiate polymerization of aniline monomer, adding 0.1mol/L NaOH solution after reaction for 25 hours, adjusting the pH to 8-9 to completely precipitate rare earth particles, filtering and washing to obtain uniformly dispersed nano-scale montmorillonite/Ce (OH)3，Pr2O3Polyaniline nano-rod three-phase composite material. Montmorillonite and rare earth nanoparticles in the composite materialsub-Ce (OH)3Rare earth nano particle Pr2O3And the polyaniline nano-rod comprises the following components in parts by mass: rare earth nanoparticles Ce (OH)312 parts of rare earth nano particle Pr2O38 parts of aniline 100 parts and montmorillonite 15 parts.
Example 4, 100 parts of aniline monomer, 40 parts of p-toluenesulfonic acid and 22 parts of cetyltrimethylammonium chloride were dissolved in 800 to 1200 parts of dispersion medium, and stirred uniformly, and then 20 parts of PrCl was added thereto3With CeCl3Mixed rare earth salts (PrCl)3With CeCl350 percent and 50 percent) of the aqueous solution, and ultrasonically dispersing for 50 minutes at room temperature to form reverse micelle emulsion; then in N2Adding the reverse micelle emulsion into aqueous dispersion containing 15 parts of organic montmorillonite dropwise under protection, heating to 65 ℃, carrying out magnetic stirring to disperse intercalation for 3 hours, then cooling, transferring the reactant into ice water bath at about 4 ℃, adding ammonium persulfate initiator aqueous solution which is equal to molar amount of aniline monomer dropwise to initiate polymerization of aniline monomer, adding 0.1mol/L NaOH solution after 24 hours of reaction, adjusting the pH to 8-9 to completely precipitate rare earth particles, filtering and washing to obtain uniformly dispersed nano-scale montmorillonite/Ce (OH)3，Pr2O3Polyaniline nano-rod three-phase composite material. Montmorillonite and rare earth nano-particle Ce (OH) in the composite material3Rare earth nano particle Pr2O3And the polyaniline nano-rod comprises the following components in parts by mass: rare earth nanoparticles Ce (OH)310 portions of rare earth nano particle Pr2O310 parts of aniline, 100 parts of montmorillonite and 15 parts of montmorillonite.
Example 5 dissolving 100 parts of aniline monomer, 50 parts of hydrochloric acid and 25 parts of alkylphenol ethoxylate in 1200 parts of water, stirring, adding 25 parts of PrCl3With CeCl3Mixed rare earth salts (PrCl)3With CeCl3The mass ratio of (A) to (B) is 40% and 60%, respectively. ) Stirring the aqueous solution, and performing ultrasonic dispersion for 60 minutes at room temperature to form reverse micelle emulsion; then in N2Adding the reverse micelle emulsion into aqueous dispersion containing 20 parts of organic montmorillonite dropwise under protection, heating to 60 ℃, magnetically stirring to disperse intercalation for 3 hours, and then coolingWarm, the reactant is transferred to an ice water bath at about 5 ℃, and persulfuric acid which is equimolar with the aniline monomer is added dropwiseAmmonium initiator aqueous solution causes polymer monomer to initiate polymerization, 0.1mol/L NaOH solution is added after 24 hours of reaction, the PH is adjusted to 8-9 to cause rare earth particles to be completely precipitated, and then filtration and washing are carried out to obtain nano-montmorillonite/Ce (OH) with uniform dispersion3，Pr2O3Polyaniline nano-rod three-phase composite material. Montmorillonite and rare earth nano-particle Ce (OH) in the composite material3Rare earth nano particle Pr2O3And the polyaniline nano-rod comprises the following components in parts by mass: rare earth nanoparticles Ce (OH)315 parts of rare earth nano particle Pr2O310 parts of aniline, 100 parts of montmorillonite and 20 parts of montmorillonite.
The observation of a scanning electron microscope and a transmission electron microscope shows that the montmorillonite layer is stripped, the polyaniline nanorod is coated on the montmorillonite layer, the diameter of the polyaniline nanorod is about 15-25 nm, the thickness of the stripped soil layer is about 10-20 nm, the stripping of the expanded montmorillonite can be obviously seen, a uniform nanorod composite material is formed, the average particle size of rare earth nanoparticles is about 10-15 nm, and the growth space of the composite nanoparticles is effectively limited due to the small size and uniform distribution of an emulsion microreactor. And the montmorillonite layer and the rare earth nano particles are simultaneously introduced into the composite material, so that the thermal stability of the polymer is greatly improved, and the electrochemical performance of the composite material is greatly improved. Analyzing the complete polymerization of the monomer from the infrared spectrogram, wherein the characteristic absorption peak of the montmorillonite is mainly 1037cm-1To 1098cm-1The strong absorption band of (A) is the skeletal vibration of Si-O-Si at 600cm-1～640cm-1The bending vibration peaks of Si-O and Al-O are at 3445cm-1The peak of (2) is a stretching vibration peak of-OH. In addition, the characteristic absorption peak of polyaniline is mainly at 832cm-1The peak is the absorption peak of the out-of-plane bending vibration of C-H on the substituted benzene and is 1308cm-1The peak is the stretching vibration of C-N bond at 1498cm-1And 1590cm-1The absorption peaks correspond to characteristic absorption peaks of benzene-type and quinoid structures on a polyaniline chain respectively, and the characteristic polyThe characteristic peak of the electron delocalization degree on the aniline chain appears at 1166cm-1To (3). Obviously, the characteristic peak of montmorillonite and pure polyaniline is montmorillonite/Ce (OH)3，Pr2O3The infrared spectrogram of the polyaniline nano-rod three-phase composite material shows that the montmorillonite/Ce (OH) is obtained as the environment of functional groups in the composite material is more complex and the peak position is slightly shifted3，Pr2O3Polyaniline nano-rod three-phase composite material.
The analysis of thermal TG shows that the heat resistance of the material is improved, and 1, 2 and 3 in the figure are respectively O-MMT, montmorillonite/Ce (OH)3，Pr2O3TG curves of polyaniline nanorod three-phase composite material and pure polyaniline. As can be seen from the TG curve, the thermal decomposition temperature of O-MMT is 260 ℃, and the montmorillonite/Ce (OH)3，Pr2O3The thermal decomposition temperature of the polyaniline nanorod three-phase composite material is 245 ℃, the thermal decomposition temperature of pure PMMA is 215 ℃, and the thermal stability of the composite material is obviously improved compared with that of pure polyaniline. Research shows that polyaniline and nano Ce (OH)3，Pr2O3An interaction exists between the interface of the particles and MMT due to the lamellar structure of the heat-resistant montmorillonite to polyaniline and Ce (OH) in the nanometer space3，Pr2O3The barrier and protection effects of the polyaniline film limit the activity of interlayer polyaniline molecules and delay the thermal decomposition reaction; on the other hand, gas circulation between the layers is not smooth, so that thermal decomposition of polyaniline is further inhibited. In addition, the first and second substrates are,the maximum thermal weight loss temperature (T) of pure polyaniline can be seen from the TG curvedm) At 510 ℃ and montmorillonite/Ce (OH)3，Pr2O3T of polyaniline nanorod three-phase-element composite materialdmAt 550 ℃ the decomposition temperature of the matrix was increased, for reasons other than the restriction of the MMT lamellar space and the Ce (OH)3，Pr2O3A large number of surface atoms of the nano particles have strong intermolecular interaction with polyaniline, and meanwhile, the rare earth nano particles increase the crosslinking degree of polyaniline molecular chains, so that the energy required by thermal decomposition is improved, namely the heat resistance of the material is improved. With TH281The conductivity of the composite material is measured by an 8-type automatic element analyzer, and the result shows that the conductivity of the material is obviously improved.
Claims (10)
1. montmorillonite/Ce (OH)3，Pr2O3The preparation method of the polyaniline nanorod three-phase composite material comprises the steps of dissolving 100 parts of aniline monomer, 10-50 parts of dopant and 15-25 parts of surfactant in 800-1200 parts of dispersion medium, uniformly stirring, and adding 10-25 parts of PrCl3With CeCl3Mixing the aqueous solution of the rare earth salt, stirring, and ultrasonically dispersing for 30-60 minutes at room temperature to form reverse micelle emulsion; then in N2Adding the reverse micelle emulsion into aqueous dispersion containing 5-20 parts of organic montmorillonite dropwise under protection, adjusting the temperature to 60-80 ℃, dispersing intercalation for 2-3 hours by magnetic stirring, then cooling to 0-5 ℃, adding initiator aqueous solution with the same mole as aniline monomer to initiate polymerization of polymer monomer, adding precipitator of rare earth nanoparticles after reaction for 24-30 hours to completely precipitate rare earth particles, filtering and washing to obtain montmorillonite/Ce (OH)3，Pr2O3Polyaniline nano-rod three-phase composite material.
2. montmorillonite/Ce (OH) as in claim 13，Pr2O3The preparation method of the polyaniline nanorod three-phase composite material is characterized by comprising the following steps of: the dopant is any one of sulfosalicylic acid, polystyrene sulfonic acid, dodecyl sulfuric acid, p-toluenesulfonic acid and hydrochloric acid.
3. montmorillonite/Ce (OH) as in claim 13，Pr2O3The preparation method of the polyaniline nanorod three-phase composite material is characterized by comprising the following steps of: the surfactant is an anionic surfactant, a cationic surfactant or a nonionic surfactant, wherein the anionic surfactant is sodium dodecyl sulfate or sodium stearate or stearic acid; the cationic surfactant is hexadecyl trimethyl ammonium chloride; the nonionic surfactant is an alkaneAlkylphenol ethoxylates.
4. montmorillonite/Ce (OH) as in claim 13，Pr2O3The preparation method of the polyaniline nanorod three-phase composite material is characterized by comprising the following steps of: the dispersion medium is water.
5. montmorillonite/Ce (OH) as in claim 13，Pr2O3The preparation method of the polyaniline nanorod three-phase composite material is characterized by comprising the following steps of: the initiator is ammonium persulfate or ferric p-toluenesulfonate.
6. montmorillonite/Ce (OH) as in claim 13，Pr2O3The preparation method of the polyaniline nanorod three-phase composite material is characterized by comprising the following steps of: the precipitant of the rare earth nano particles is NaOH solution.
7. montmorillonite/Ce (OH) as in claim 13，Pr2O3The preparation method of the polyaniline nanorod three-phase composite material is characterized by comprising the following steps of: PrCl in the mixed rare earth salt3With CeCl3The weight ratio of the components is as follows: PrCl320％-50％，CeCl380％～50％。
8. montmorillonite/Ce (OH) prepared by the process of claim 13，Pr2O3The polyaniline nanorod three-phase composite material is characterized in that: montmorillonite, rare earth nano particle Ce (OH)3，Pr2O3Closely combined with polyaniline nano-rods and uniformly dispersed in aniline monomer in nano-scale.
9. montmorillonite/Ce (OH) of claim 83，Pr2O3Polyaniline nano-rod three-phase element composite materialThe material is characterized in that: the montmorillonite and rare earth nano-particle Ce (OH)3，Pr2O3And the polyaniline nano-rod comprises the following components in parts by mass: rare earth element sodiumRice grains Ce (OH)3，Pr2O310-25 parts of aniline, 100 parts of montmorillonite and 5-20 parts of montmorillonite.
10. montmorillonite/Ce (OH) of claim 83，Pr2O3The polyaniline nanorod three-phase composite material is characterized in that: the montmorillonite and rare earth nano-particle Ce (OH)3Rare earth nano particle Pr2O3And the polyaniline nano-rod comprises the following components in parts by mass: rare earth nanoparticles Ce (OH)35-20 parts of rare earth nano particle Pr2O32-12.5 parts of aniline, 100 parts of montmorillonite and 5-20 parts of montmorillonite.
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| CN1267682A (en) * | 2000-03-17 | 2000-09-27 | 中国石油天然气股份有限公司兰州石化分公司 | Composite nanometer-level polypropylene/montmorillonoid material and its preparation |
| CN1289783A (en) * | 1999-09-24 | 2001-04-04 | 中国科学院化学研究所 | Process for inserting oligomerizing catalyst between montmorillonite layers |
| CN1352213A (en) * | 2000-11-15 | 2002-06-05 | 北京中商世纪纳米塑胶材料有限公司 | Spreading material for sports ground prepared from polyurethane/nanometer montorillonoid and its preparing method |
| CN1376739A (en) * | 2001-03-22 | 2002-10-30 | 中国科学院化学研究所 | Process for preparing nano montmorillonite/polyurethane composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1289783A (en) * | 1999-09-24 | 2001-04-04 | 中国科学院化学研究所 | Process for inserting oligomerizing catalyst between montmorillonite layers |
| CN1267682A (en) * | 2000-03-17 | 2000-09-27 | 中国石油天然气股份有限公司兰州石化分公司 | Composite nanometer-level polypropylene/montmorillonoid material and its preparation |
| CN1352213A (en) * | 2000-11-15 | 2002-06-05 | 北京中商世纪纳米塑胶材料有限公司 | Spreading material for sports ground prepared from polyurethane/nanometer montorillonoid and its preparing method |
| CN1376739A (en) * | 2001-03-22 | 2002-10-30 | 中国科学院化学研究所 | Process for preparing nano montmorillonite/polyurethane composition |
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