CN101302294B - Preparation of polyaniline nano-wire/nano-particle compound system - Google Patents

Abstract

The invention relates to a method for preparing a polyaniline nano wire/nano particle complex system. The method is characterized in that the method takes fat-soluble sucrose octaacetate containing eight branch chains as a template and a homogeneous system formed by water and water-soluble organic solvents as the reaction medium and prepares a polyaniline nano wire/nano particle complex system by utilizing a template polymerization method and taking hydrochloric acids as doping acids, which facilitates the utilization of branch chains of sucrose octaacetate molecules to initiate the stereotactic polymerization of aniline to prepare the polyaniline nano wire/nano particle complex system; moreover, the use of water and water-soluble organic solvents as a reaction system avoids the environmental pollution of fat phase organic solvents in interfacial polymerization and emulsion polymerization; moreover, the water-soluble organic solvents are also good solvents for a plurality of polymers, thereby providing a new research method for preparing polyaniline conductive composite materials and having better use value.

Description

A kind of preparation method of polyaniline nanowire/nanoparticle composite system

technical field

The invention relates to a preparation method of a polyaniline nanowire/nanoparticle composite system, which is composed of fat-soluble sucrose octaacetate containing eight branched chain structures as a template, hydrochloric acid as a dopant, water and a water-soluble organic solvent The homogeneous system is the reaction medium, which is prepared through a series of steps by template polymerization.

Background technique

Polyaniline nanostructures such as nanowires, nanotubes, nanoparticles, etc. have different properties from ordinary polyaniline random particles. When the characteristic dimension of the material reaches the nanometer size, its performance will change significantly compared to the bulk material. In the manufacture of nano Functional devices and other aspects play an important role. In recent years, researchers have made great progress in the preparation of nano-polyaniline, but the preparation of polyaniline nanowire/nanoparticle composite systems with adjustable morphological parameters and excellent electromagnetic properties is still the key to realize their technical applications .

The methods currently used to prepare polyaniline nanowire/nanoparticle composite systems are mainly template method, self-assembly method, interfacial polymerization, seed polymerization and other methods. These methods generally have the following problems: (1) the method used after the aniline polymerization is completed The template agent is not easy to remove; (2) the environmental pollution of the oil phase organic solvent in the reaction medium; (3) the production cost is high; (4) the morphology parameters and electromagnetic properties of the polyaniline nanowire/nanoparticle composite system are difficult to control.

Contents of the invention

technical problem to be solved

In order to avoid the deficiencies of the prior art, the present invention proposes a method for preparing a polyaniline nanowire/nanoparticle composite system. On the basis of preparing nano-polyaniline, the fat-soluble sucrose octaacetic acid containing eight branched Ester is used as a template, and a homogeneous system composed of water and a water-soluble organic solvent is used as a reaction medium. A polyaniline nanowire/nanoparticle composite system with controllable morphology parameters and excellent electromagnetic properties and a preparation method thereof are obtained. The preparation method described in the invention has the advantages of no pollution to the environment, simple process, high yield and easy industrial production, and the obtained polyaniline nanofiber/nanoparticle composite system has good electromagnetic properties. The polyaniline nanowire/nanoparticle composite system synthesized by the invention can be applied to the fields of stealth materials, electromagnetic shielding materials, antistatic materials and the like.

Technical solutions

A preparation method of a polyaniline nanowire/nanoparticle composite system, characterized in that the steps are as follows:

Step 1, dissolving 0.1-10 parts of sucrose octaacetate in a homogeneous system composed of 30-200 parts of water and a water-soluble organic solvent;

Step 2, dissolving 5 to 20 parts of hydrochloric acid in the above-mentioned homogeneous system under stirring conditions to form a hydrochloric acid solution;

Step 3, adding 2 to 10 parts of aniline under stirring conditions to form component A;

Step 4. Add component B to component A drop by drop continuously under stirring condition, the dropping speed is 1.0ml/min～5.0ml/min, after the dropwise addition, continue to react for 3～12 hours, the reaction temperature is controlled Between 0°C and 5°C; the component B is: dissolving 4-50 parts of oxidant ammonium persulfate in a homogeneous system formed by 20-50 parts of water and a water-soluble organic solvent to form component B;

Step 5, after filtering the reaction product, wash with methanol, acetone and deionized water respectively until the filtrate is colorless;

Step 6, performing secondary doping with hydrochloric acid aqueous solution, the concentration of hydrochloric acid used for secondary doping is 0.5M-4.0M, and the doping time is 3-12 hours;

Step 7, vacuum drying after washing to obtain the polyaniline nanowire/nanoparticle composite system, the vacuum degree during vacuum drying is 0.6MPa-0.9MPa, and the drying temperature is 60°C-100°C;

The units of each component in the above steps are parts by mass.

The sucrose octaacetate is a fat-soluble small organic molecular compound containing eight branched chain structures.

The water-soluble organic solvent is an organic solvent that alcohols or ketones can form a homogeneous system with water, wherein the volume content of the water-soluble organic solvent is 0-100%.

Beneficial effect

The preparation method of the polyaniline nanowire/nanoparticle composite system involved in the present invention is characterized in that: (1) the present invention adopts fat-soluble sucrose octaacetate containing eight branched chain structures as a template, and adds persulfuric acid drop by drop The ammonium solution makes aniline use sucrose octaacetate molecules as a template during the polymerization process to aggregate in the form of a nanowire/nanoparticle composite system. Using sucrose octaacetate as a template is conducive to the synthesis of polyaniline nanowire/nanoparticle composite system with adjustable microscopic morphology parameters and excellent electromagnetic properties; (2) using a homogeneous system formed by water and a water-soluble organic solvent as a reaction medium, It avoids the environmental pollution of the oil phase organic solvent in the interface polymerization and emulsion polymerization; (3) the water-soluble organic solvent is also a good solvent for many polymers, which provides a new research idea for the preparation of polyaniline nano-conductive composite materials, and has relatively great practical value. Scanning electron micrograph (SEM) and X-ray diffraction pattern (XRD) of polyaniline nanowire/nanoparticle composite system prepared with sucrose octaacetate as template and homogeneous system formed by water and water-soluble organic solvent as reaction medium As shown in Figure 1 and Figure 2; the polyaniline nanowire/nanoparticle composite system prepared with sucrose octaacetate as the template and the homogeneous system formed by water and water-soluble organic solvent as the reaction medium is in the range of 8.2GHz to 12.4GHz The electrical loss performance and magnetic loss performance are shown in Figure 3 and Figure 4.

Description of drawings

Figure 1: Scanning electron microscope (SEM) photographs of the polyaniline nanowire/nanoparticle composite system prepared with sucrose octaacetate as a template, a homogeneous system formed by water and a water-soluble organic solvent: (a) in water, (b) in water In a homogeneous system formed with a water-soluble organic solvent, (c) in a water-soluble organic solvent.

Figure 2: The X-ray diffraction (XRD) pattern of the polyaniline nanowire/nanoparticle composite system prepared by using sucrose octaacetate as a template, a homogeneous system formed by water and a water-soluble organic solvent: (a) in water, (b ) in a homogeneous system formed by water and a water-soluble organic solvent, and (c) in a water-soluble organic solvent.

Figure 3: Diagram of the dielectric properties of the polyaniline nanowire/nanoparticle composite system prepared by using sucrose octaacetate as a template, a homogeneous system formed by water and a water-soluble organic solvent, wherein (a) the real part of the dielectric constant; ( b) Imaginary part of permittivity; (c) Dielectric loss.

Figure 4: The magnetic performance diagram of the polyaniline nanowire/nanoparticle composite system prepared by using sucrose octaacetate as a template, a homogeneous system formed by water and a water-soluble organic solvent, where (a) the real part of the magnetic permeability; (b) ) Imaginary part of permeability; (c) Magnetic loss.

Detailed ways

Now in conjunction with embodiment, accompanying drawing, the present invention will be further described:

Example 1:

(1) 0.1 part of sucrose octaacetate is dissolved and dispersed in 30 parts of water reaction medium;

(2) Dissolve 5 parts of hydrochloric acid in the above-mentioned solution under stirring condition;

(3) Add 2 parts of aniline under stirring condition to form component A;

(4) 5 parts of ammonium persulfate are dissolved in 20 parts of water to form component B;

(5) Add component B to component A drop by drop continuously under stirring condition, the dropping rate is 1.0ml/min～5.0ml/min, after the dropwise addition, continue to react for 3～12 hours, the reaction temperature is controlled Between 0°C and 5°C;

(6) After filtering the reaction product, wash with methanol, acetone and deionized water respectively until the filtrate is colorless;

(7) carry out secondary doping with hydrochloric acid aqueous solution, the hydrochloric acid concentration that secondary doping is used is 0.5M～4.0M, and the time of doping is 3～12 hours;

(8) Vacuum drying after washing to obtain the polyaniline nanowire/nanoparticle composite system, the vacuum degree during vacuum drying is 0.6MPa-0.9MPa, and the drying temperature is 60°C-100°C.

Example 2:

(1) water and water-soluble organic solvent are mixed in a volume ratio of 1:1 to form a homogeneous system of 70 parts;

(2) Dissolving 2 parts of sucrose octaacetate in the above system;

(3) 5 parts of hydrochloric acid are dissolved in the above-mentioned solution under the condition of stirring;

(4) Add 4 parts of aniline under stirring condition to form component A;

(5) Dissolving 10 parts of ammonium persulfate in 20 parts of a homogeneous system formed by mixing water and a water-soluble organic solvent in a ratio of 1:1 by volume to form component B;

(6) Continuously add component B dropwise to component A under stirring condition, the dropping speed is 1.0ml/min～5.0ml/min; continue to react for 3～12 hours after the dropwise addition, the reaction temperature is controlled at Between 0°C and 5°C;

(7) After filtering the reaction product, wash with methanol, acetone and deionized water respectively until the filtrate is colorless;

(8) carry out secondary doping with hydrochloric acid aqueous solution, the hydrochloric acid concentration that secondary doping is used is 0.5M～4.0M, and the time of doping is 3～12 hours;

(9) Vacuum drying after washing to obtain the polyaniline nanofiber/nanoparticle composite system, the vacuum degree during vacuum drying is 0.6MPa-0.9MPa, and the drying temperature is 60°C-100°C.

Example 3:

(1) 3 parts of sucrose octaacetate are dissolved and dispersed in 100 parts of water reaction medium;

(2) Dissolve 5 parts of hydrochloric acid in the above-mentioned solution under stirring condition;

(3) Add 2 parts of aniline under stirring condition to form component A;

(4) 5 parts of ammonium persulfate are dissolved in 20 parts of water to form component B;

(5) Add component B to component A drop by drop continuously under stirring condition, the dropping rate is 1.0ml/min～5.0ml/min, after the dropwise addition, continue to react for 3～12 hours, the reaction temperature is controlled Between 0°C and 5°C;

(6) After filtering the reaction product, wash with methanol, acetone and deionized water respectively until the filtrate is colorless;

(7) carry out secondary doping with hydrochloric acid aqueous solution, the hydrochloric acid concentration that secondary doping is used is 0.5M～4.0M, and the time of doping is 3～12 hours;

(8) Vacuum drying after washing to obtain the polyaniline nanowire/nanoparticle composite system, the vacuum degree during vacuum drying is 0.6MPa-0.9MPa, and the drying temperature is 60°C-100°C.

Example 4:

(1) water and water-soluble organic solvent are mixed in the ratio of volume ratio 3: 2 to form 150 parts of homogeneous system;

(2) Dissolving 5 parts of sucrose octaacetate in the above system;

(3) 10 parts of hydrochloric acid are dissolved in the above-mentioned solution under the condition of stirring;

(4) Add 10 parts of aniline under stirring condition to form component A;

(5) Dissolving 50 parts of ammonium persulfate in 50 parts of a homogeneous system formed by mixing water and a water-soluble organic solvent in a ratio of 3:2 by volume to form component B;

(6) Continuously add component B dropwise to component A under stirring condition, the dropping speed is 1.0ml/min～5.0ml/min; continue to react for 3～12 hours after the dropwise addition, the reaction temperature is controlled at Between 0°C and 5°C;

(7) After filtering the reaction product, wash with methanol, acetone and deionized water respectively until the filtrate is colorless;

(8) carry out secondary doping with hydrochloric acid aqueous solution, the hydrochloric acid concentration that secondary doping is used is 0.5M～4.0M, and the time of doping is 3～12 hours;

(9) Vacuum drying after washing to obtain the polyaniline nanofiber/nanoparticle composite system, the vacuum degree during vacuum drying is 0.6MPa-0.9MPa, and the drying temperature is 60°C-100°C.

Example 5:

(1) 10 parts of sucrose octaacetate are dissolved in 200 parts of water-soluble organic solvent medium;

(2) 20 parts of hydrochloric acid are dissolved in the above-mentioned solution under the condition of stirring;

(3) Add 10 parts of aniline under stirring condition to form component A;

(4) 50. parts of ammonium persulfate are dissolved in 50 parts of water-soluble organic solvents to form component B;

(5) Add component B dropwise to component A continuously under stirring condition, the dropping speed is 1.0ml/min～5.0ml/min; continue to react for 3～12 hours after dropping, the reaction temperature is controlled at Between 0°C and 5°C;

(6) After filtering the reaction product, wash with methanol, acetone and deionized water respectively until the filtrate is colorless;

(7) carry out secondary doping with hydrochloric acid aqueous solution, the hydrochloric acid concentration that secondary doping is used is 0.5M～4.0M, and the time of doping is 3～12 hours;

(8) Vacuum drying after washing to obtain the polyaniline nanofiber/nanoparticle composite system, the vacuum degree during vacuum drying is 0.6MPa-0.9MPa, and the drying temperature is 60°C-100°C.

The present invention uses fat-soluble sucrose octaacetate containing eight branched chains as a template agent, a homogeneous system composed of water and a water-soluble organic solvent as a reaction medium, and prepares polyaniline nanowires through a template polymerization method using hydrochloric acid as a doping acid. /nanoparticle composite system, which is beneficial to use the branched chain in the sucrose octaacetate molecule to initiate the directional polymerization of aniline to prepare the polyaniline nanowire/nanoparticle composite system, and use water and water-soluble organic solvent as the reaction system to avoid interfacial polymerization And the environmental pollution of oil-phase organic solvents in emulsion polymerization, in addition, water-soluble organic solvents are also good solvents for many polymers, which provides a new research idea for the preparation of polyaniline conductive composite materials, and has great practical value. According to the polyaniline nanowire/nanoparticle composite system synthesized by using fat-soluble sucrose octaacetate as a template and a homogeneous system formed by water and a water-soluble organic solvent as a reaction medium, its morphology parameters can be changed by changing the sucrose The reaction parameters such as the consumption of octaacetate, the volume content of water-soluble organic solvent, the concentration of doping acid, reaction time and reaction temperature are controlled.

Claims (2)

1. the preparation method of polyaniline nano-line/nano particle compound system is characterized in that step is as follows:

Step 1,0.1～10 part of Sucrose octaacetate is dissolved in the homogeneous system that 30～200 parts of water and water-miscible organic solvent form;

Step 2, under agitation condition, hydrochloric acid is dissolved in the above-mentioned homogeneous system for 5～20 parts and forms hydrochloric acid soln;

Step 3, under agitation condition, add 2～10 parts of aniline and form component A;

Step 4, under agitation condition component B dropwise is added drop-wise among the component A continuously, rate of addition is 1.0ml/min～5.0ml/min, after dropwising, continues reaction 3～12 hours, and temperature of reaction is controlled between 0 ℃～5 ℃; Described component B is: 4～50 parts of oxygenant ammonium persulphates are dissolved in the homogeneous system that 20～50 parts of water and water-miscible organic solvent form form component B;

Step 5, use methyl alcohol, acetone and deionized water wash colourless respectively after will reaction product filtering to filtrate;

Step 6, carry out secondary doping with aqueous hydrochloric acid, the concentration of hydrochloric acid that secondary doping is used is 0.5M～4.0M, and the adulterated time is 3～12 hours;

Step 7, washing final vacuum are drying to obtain polyaniline nano-line/nano particle compound system, and the vacuum tightness during vacuum-drying is 0.6MPa～0.9MPa, and the exsiccant temperature is 60 ℃～100 ℃;

Each component unit is a mass parts in the above-mentioned steps.

2. the preparation method of polyaniline nano-line according to claim 1/nano particle compound system is characterized in that: described Sucrose octaacetate is a kind of fat-soluble organic micromolecule compound that contains eight branched structures.

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