CN109023589B

CN109023589B - Preparation method of ternary blending material with polyaniline and carbon black as conductive filler

Info

Publication number: CN109023589B
Application number: CN201810756227.7A
Authority: CN
Inventors: 王艳宾; 沈业鹏; 龚澳; 王标兵
Original assignee: Changzhou University
Current assignee: Changzhou University
Priority date: 2018-07-11
Filing date: 2018-07-11
Publication date: 2021-06-22
Anticipated expiration: 2038-07-11
Also published as: CN109023589A

Abstract

The invention belongs to the technical field of modification of high polymer materials, and discloses a preparation method of a ternary blending material taking polyaniline and carbon black as conductive fillers. Firstly synthesizing Polyaniline (PANI), then doping with camphorsulfonic acid (CSA) to obtain PANI-CSA, then uniformly dispersing Carbon Black (CB), PANI-CSA and compatilizer hydroquinone in a polyamide-imide solution by high-speed emulsification and ultrasonic oscillation, and then preparing the polyamide-imide/polyaniline/carbon black ternary conductive nano composite material by a wet spinning method. The conductive polyamide-imide material provided by the invention has excellent conductivity, the conductivity can reach more than 1000S/m, and the conductive polyamide-imide material can be used as a flexible wire material.

Description

Preparation method of ternary blending material with polyaniline and carbon black as conductive filler

Technical Field

The invention belongs to the technical field of high polymer material blending modification, and particularly relates to a preparation method of a ternary blending material taking polyaniline and carbon black as conductive fillers.

Background

The polyamide-imide has been widely used due to its excellent properties, and has been widely used in antistatic, insulating varnish and insulated enameled wire due to its small dielectric constant compared with other materials. In order to enhance the conductivity of the composite material, the conductivity of the composite material is enhanced by doping polyaniline, but the mechanical property of the composite material is deteriorated; the polyamide-imide and the carbon black are blended, so that the mechanical property of the composite material can be enhanced, but the conductivity is low, the polyamide-imide and the carbon black can only be used as an antistatic material generally, and the compatibility of the polyamide-imide and the carbon black is poor. And the composite material obtained by solution blending or extrusion blending of polyimide, carbon nano tubes and the like has low conductivity or poor flexibility, and cannot be well applied to the aspect of conductive materials.

Disclosure of Invention

The invention aims to: the polyamide imide/polyaniline/carbon black ternary conductive composite material is obtained by a simple wet spinning technology. The polyaniline and the carbon black have good compatibility, and the polyaniline and the carbon black can form a three-dimensional conductive network, and the conductivity of the material can be greatly improved by the three-dimensional conductive network structure, so that the polyamide imide is modified by the polyaniline and the carbon black in a synergistic manner, the conductivity can be enhanced, the mechanical property can be enhanced, and the polyaniline and the carbon black can be used for flexible lead materials.

The invention relates to a preparation method of a ternary blended flexible conducting wire material taking polyaniline and carbon black as conductive fillers, which comprises the following steps:

(1) preparation of PANI (polyaniline)

Adding newly distilled aniline into 0.2mol/L hydrochloric acid solution, stirring at 0-5 ℃ for 0.5-2 hours, slowly dropwise adding (1-3s per drop) ammonium persulfate aqueous solution, and reacting at 0-5 ℃ for 6-10 hours. And carrying out suction filtration on the reaction liquid to obtain a green solid, then respectively carrying out Soxhlet extraction on the green solid by using methanol, normal hexane and chloroform, and then carrying out vacuum drying for 12h at the temperature of 60 ℃ to obtain the polyaniline doped with hydrochloric acid, wherein the polyaniline is green powder.

(2) Preparation of PANI-CSA (Camphorsulfonic acid doped polyaniline)

Adding ammonia water accounting for 10% of the mass of the polyaniline powder doped with the hydrochloric acid into the polyaniline powder doped with the hydrochloric acid, stirring at normal temperature for 12-16 hours, washing with water to be neutral, and drying in vacuum at 60 ℃ for 12 hours to obtain the eigenstate polyaniline, wherein the eigenstate polyaniline is purple powder. Grinding camphorsulfonic acid (CSA), adding intrinsic polyaniline, fully grinding for 15min, dropwise adding m-cresol, continuously grinding for 30 min, stirring at high speed for 30 min by a high-speed emulsifying machine, and drying at 90 ℃ to obtain the PANI-CSA.

(3) Preparation of polyamideimide

Adding diacid monomer (DIDA) and p-phenylenediamine into N-methyl pyrrolidone, then adding a condensing agent and a water absorbent, heating to 80-120 ℃ in an inert atmosphere, and reacting for 2-8 hours. And (3) settling the reaction product by using ethanol or methanol, then soaking and washing the reaction product for multiple times by using warm water, drying the obtained product for 8 hours in vacuum at the temperature of 80 ℃ to obtain polyamide-imide, and dissolving the polyamide-imide in an m-cresol solvent to obtain a polyamide-imide solution.

(4) Preparation of conductive polyamide-imide composite material

Carbon Black (CB), camphorsulfonic acid doped polyaniline (PANI-CSA) and a compatilizer hydroquinone are uniformly dispersed in a polyamide imide solution through high-speed emulsification and ultrasonic oscillation, and then the polyamide imide/polyaniline/carbon black ternary conductive composite material can be prepared through a wet spinning method.

Wherein, the aniline in the step (1) is o-methylaniline or o-methoxyaniline; the molar ratio of the aniline to the ammonium persulfate is 1:0.6-1: 2.

In the step (2), the mass ratio of the polyaniline to the camphorsulfonic acid is 1:1.2-1: 1.8.

The mass ratio of the p-phenylenediamine to the diacid monomer (DIDA) in the step (3) is 1:5-1: 8; the acylating agent is pyridine (Py) or triphenyl phosphite (TPP), and the mass ratio of the diacid monomer to the acylating agent is 1:3-1: 6; the water absorbent is anhydrous calcium chloride (CaCl)₂) And one of anhydrous lithium chloride (LiCl) and anhydrous zinc chloride, wherein the mass ratio of the diacid monomer to the water absorbent is 1:4-1: 9.

In the step (4), the mass ratio of the polyamide imide to the polyaniline is 1:5-5: 1; the content of carbon black accounts for 2.5-10% of the total mass of the polyamide imide/polyaniline; the content of the compatilizer hydroquinone is 1 to 5 percent of the total mass of the polyamide imide/polyaniline.

The carbon black can be one or a combination of oil furnace conductive carbon black, heavy oil byproduct conductive carbon black and calcium carbide acetylene carbon black; the mesh number of the carbon black is 100-600 meshes. The carbon black can also be carbon black subjected to acidification or amination treatment, and the treated carbon black can further improve the compatibility of the carbon black and the polyamide imide and further improve the conductivity of the carbon black.

The structural formula of the PANI-CSA is as follows:

wherein 0< y <1, 10< n;

the structural formula of the polyamide-imide resin is shown as the following formula:

wherein Ar is₁The method comprises the following steps:

Ar₂the method comprises the following steps:

wherein x is 1, 2, 3, 5, 7, 8, 9, 10, 11, 13; n is 10-200.

Has the advantages that:

the method has the following technical advantages that:

in order to enhance the conductivity of polyimide, the polyamide-imide, polyaniline and carbon black are subjected to ternary blending for the first time, because the polyaniline and the carbon black are good in compatibility, and a three-dimensional conductive network is formed between the carbon black and the polyaniline doped with camphorsulfonic acid, the conductivity of the material can be greatly improved, so that the polyamide-imide is modified by the polyaniline and the carbon black in a synergistic manner, the conductivity of the material is greatly enhanced, and meanwhile, the mechanical property can be enhanced, so that the polyamide-imide conductive composite material can be used as a flexible wire.

The hydroquinone is selected as the compatilizer, so that the compatibility of the ternary material can be improved, a conductive network can be better formed, and the conductivity of the ternary material is improved.

Drawings

FIG. 1 is an infrared spectrum of PAI/PANI/CB ternary conductive composites of different carbon black ratios.

FIG. 2 is a graph of conductivity curves for PAI/PANI/CB ternary conductive composites of varying carbon black ratios.

FIG. 3 is a graph of the mechanical properties of PAI/PANI/CB ternary conductive composites with different carbon black ratios.

FIG. 4 is a SEM photograph of a sample of example 1.

Fig. 5 is a photograph of a flexible display of the sample of example 1.

Detailed Description

The present invention will be described in further detail with reference to the following examples, which are provided for illustration only and are not intended to limit the scope of the present invention.

Example 1

(1) Preparation of PANI (polyaniline)

Freshly distilled aniline was added to a 0.2mol/L hydrochloric acid solution, stirred at 4 ℃ for 1 hour, slowly added dropwise (1-3 seconds per drop) with an aqueous solution of ammonium persulfate (molar ratio of aniline: ammonium persulfate 1:1), and then reacted at 1 ℃ for 7 hours. And carrying out suction filtration on the reaction liquid to obtain a green solid, then respectively carrying out Soxhlet extraction on the green solid by using methanol, normal hexane and chloroform, and then carrying out vacuum drying for 12 hours at the temperature of 60 ℃ to obtain the polyaniline doped with hydrochloric acid, wherein the polyaniline is green powder.

(2) Preparation of PANI-CSA (Camphorsulfonic acid doped polyaniline)

Adding ammonia water accounting for 10% of the mass of the polyaniline powder doped with the hydrochloric acid into the polyaniline powder doped with the hydrochloric acid, stirring the mixture for 13 hours at normal temperature, washing the mixture to be neutral, and drying the mixture for 12 hours in vacuum at 60 ℃ to obtain the eigenstate polyaniline, wherein the eigenstate polyaniline is purple powder. The PANI-CSA is obtained by adopting a solution-mechanical grinding method, firstly, camphorsulfonic acid (CSA) (the mass ratio of polyaniline to camphorsulfonic acid is 1:1.3) is ground, then, eigenstate polyaniline is added, the mixture is fully ground for 15 minutes, then, m-cresol is dropwise added and continuously ground for 30 minutes, then, a high-speed emulsifying machine is used for high-speed stirring for 30 minutes, and finally, the PANI-CSA is obtained after drying at 90 ℃.

(3) Preparation of polyamideimide

3.6773g of imide diacid monomer (DIDA), 0.6021g of p-phenylenediamine were added to 15mL of N-methylpyrrolidone, and then acylating agent (15g of triphenyl phosphite (TPP)) and water absorbent (18.5g of calcium chloride (CaCl)₂) In an inert atmosphere, the temperature is raised to 100 ℃ and the reaction is carried out for 4 hours. The reaction product is settled by ethanol or methanol, then is soaked and washed for many times by warm water, and the obtained product is dried for 8 hours under vacuum at the temperature of 80 ℃.

(4) Preparation of conductive polyamide-imide composite material

384mg of PAI was weighed into a 25mL beaker, and 12mL of m-cresol was added to dissolve the PAI sufficiently at room temperature. After the PAI was completely dissolved, 24mg of carbon black (5%) and 96mg of doped polyaniline were weighed into a beaker, followed by 4.8mg of hydroquinone (1%). Stirring for half an hour by a high-speed mixer, then placing the mixture into an ultrasonic cleaner, shaking for half an hour, repeating for two times, and then pouring the mixture into a film through solution. The conductivity of the polyamide-imide conductive film is up to 333S/m, and the polyamide-imide conductive film can be curled and folded and has good flexibility.

The top infrared spectrum of FIG. 1 is the infrared spectrum of a binary conductive composite material blended with polyamideimide and polyaniline, and is used for comparison of a pure sample, and the infrared spectrum of the pure sample can be seen at 3288cm^-1The deformation vibration characteristic peak of-N-H on the amide group appears, and the C-H stretching vibration peak on the aliphatic series appears at 2854cm^-1、2929cm^-1Double peak at (1), corresponding to 1767cm^-1、1699cm^-1Then, it is the C ═ O absorption peak of the amide group, 1400cm^-1The peak of (A) is a C-N absorption peak on the amide group. In the infrared spectrum of PAI/PANI/CB, the ratio of CB is from 2.5% to 12.5%, and by comparison, the PAI has both-N-H, C ═ O on the amido bond and aliphatic C-H double peak structure, and contains semi-oxidized and semi-reduced quinoid, benzene and S ═ O in CSA of polyaniline.

FIG. 2 is a schematic representation of the effect of conductivity of polyamideimide/polyaniline/carbon black ternary composites of different carbon black content,on the premise of unchanged total concentration, the carbon black accounts for 0%, 2.5%, 5%, 10% and 12.5% of the total mass respectively, firstly, the first group is the addition of PANI with the proportion of 20%, so that an interpenetrating conductive network system is formed in an original closed network in a PAI matrix, the electric conductivity at the moment is greatly increased, but the difference of the electric conductivity is large when different carbon blacks are added, but the price of the carbon black is more expensive than that of polyaniline, so that the experiment cost is too high due to too much addition, the optimal carbon black proportion needs to be found out, as can be seen from the figure, along with the increase of the carbon black content, the electric conductivity of the composite material is increased firstly and then reduced, and the electric conductivity of a pure sample is only 33S/m^-1And when the content of the carbon black reaches 10 percent, the conductivity is 1000S/m^-1Therefore, the synergistic effect of the carbon black and the polyaniline is very obvious in enhancing the conductivity of the polyamide imide. However, at 12.5%, the conductivity of the composite material is rapidly reduced to 49S/m^-1It can be seen that, due to the excessive amount of carbon black, the material is not uniformly mixed, and the carbon black is agglomerated, which leads to the rapid decrease of the conductivity of the composite material.

Fig. 3 is a graph of the tensile strength of the polyamide imide/polyaniline/carbon black ternary composite material according to the content of different carbon blacks, and it can be seen from the graph that the tensile strength of the ternary conductive composite material increases first and then decreases with the increase of the content of the carbon black, when the content of the carbon black is 10%, the tensile strength of the composite material is the largest, and when the content of the carbon black reaches 12.5%, the tensile strength of the carbon black decreases, and the addition of the carbon black increases the tensile strength of the prepared ternary conductive composite material as a whole, which may be because the addition of the carbon black better disperses the stress applied to the film, and because the addition of the carbon black has a reinforcing effect on the mechanical properties of the composite material, the overall tensile strength of the composite material increases. The good interface compatibility of the carbon black and the polyaniline is indirectly demonstrated, and the good compatibility of the polyaniline and the carbon black fully exerts the reinforcing property of the carbon black on the composite material, so that a good synergistic effect is embodied. The mechanical property comparison of the composite material film added with different contents of carbon black shows that: as the addition amount of the carbon black is increased, the tensile strength of the composite material is firstly increased and then reduced, the 10% tensile strength is the maximum, but the tensile strength of the composite material is reduced when the addition amount of the carbon black is 12.5%, which is probably because the carbon black is agglomerated due to the excessive addition amount of the carbon black, so that the mechanical property is relatively reduced.

Fig. 4 shows that the granular polyaniline and the bead-string-shaped carbon black form a good three-dimensional conductive network structure.

FIG. 5 shows that the ternary blend material prepared has good flexibility.

Example 2

This example differs from example 1 in that in the step of preparing the conductive polyamideimide material, 2% (i.e., 9.6mg) of hydroquinone as a compatibilizer was added, and the other treatment methods were the same as those of example 1. The conductivity of the polyamide-imide conductive film is 300S/m, and the polyamide-imide conductive film has good flexibility.

Example 3

The difference between the present example and example 1 is that in the preparation step of the conductive polyamideimide material, the polyamideimide/polyaniline mass ratio is 5:1, and other treatment methods are the same as those in example 1. The conductivity of the polyamide-imide conductive film is 711S/m, and the polyamide-imide conductive film has good flexibility.

Example 4

This example differs from example 1 in that in the step of preparing the conductive polyamideimide material, 10% content (i.e., 48mg) of the aminated carbon black was added, and the other treatment means were the same as in example 1. The conductivity of the polyamide-imide conductive film is as high as 633S/m, and the polyamide-imide conductive film has good flexibility.

Comparative example 1

The difference between this example and example 1 is that in the preparation step of the conductive polyamideimide material, doped polyaniline is not added, and other processing means are the same as those in example 1. The conductivity of the polyamide-imide conductive film is only 10S/m, and the polyamide-imide conductive film has good flexibility.

Comparative example 2

This example differs from example 1 in that no carbon black was added during the step of preparing the conductive polyamideimide material, and the other treatment means were the same as in example 1. The conductivity of the polyamide-imide conductive film is only 33S/m, and the polyamide-imide conductive film has good flexibility.

Comparative example 3

The difference between this example and example 1 is that in the preparation step of the conductive polyamideimide material, the doped polyaniline was replaced by undoped polyaniline, and the other treatment means were the same as in example 1. The agglomeration phenomenon of the material is obvious.

Comparative example 4

This example is different from example 1 in that carbon black is replaced with graphite nanoplatelets in the preparation step of the conductive polyamideimide material, and other processing means are the same as those of example 1. The conductivity of the polyamide-imide conductive film is 40S/m, and the polyamide-imide conductive film has good flexibility.

Comparative example 5

This example differs from example 1 in that in the step of preparing the conductive polyamideimide material, carbon black is added in an amount of 20% and the other treatment means are the same as in example 1. The material has obvious agglomeration phenomenon. The conductivity of the polyamide-imide conductive film is 1S/m, and the polyamide-imide conductive film has good flexibility.

In the above-mentioned embodiments, all the equivalent changes and modifications based on the technical solution of the present invention should not be excluded from the scope of the present invention.

Claims

1. A preparation method of a ternary blending material taking polyaniline and carbon black as conductive fillers is characterized by comprising the following steps: the preparation method comprises the following steps:

(1) preparation of polyaniline PANI

Adding newly distilled aniline into 0.2mol/L hydrochloric acid solution, stirring for 0.5-2 hours at 0-5 ℃, slowly dropwise adding aqueous solution of ammonium persulfate at the speed of 1-3 seconds per drop, reacting for 6-10 hours at 0-5 ℃, carrying out suction filtration on the reaction solution to obtain green solid, then respectively carrying out Soxhlet extraction by using methanol, normal hexane and chloroform, and carrying out vacuum drying for 12 hours at 60 ℃ to obtain polyaniline doped with hydrochloric acid;

(2) preparation of camphorsulfonic acid doped polyaniline PANI-CSA

Adding ammonia water accounting for 10% of the mass of the polyaniline powder into the polyaniline powder doped with hydrochloric acid, stirring at normal temperature for 12-16 hours, washing with water to be neutral, and drying at 60 ℃ in vacuum for 12 hours to obtain eigenstate polyaniline; grinding the camphorsulfonic acid CSA, adding the eigen-state polyaniline, fully grinding for 15 minutes, dropwise adding m-cresol, continuously grinding for 30 minutes, stirring for 30 minutes at a high speed by a high-speed emulsifying machine, and drying at 90 ℃ to obtain PANI-CSA;

(3) preparation of polyamideimide

Adding diacid monomer DIDA and p-phenylenediamine into N-methyl pyrrolidone, then adding an acylating agent and a water absorbent, heating to 80-120 ℃ in an inert atmosphere, reacting for 2-8 hours, carrying out ethanol or methanol sedimentation treatment on a reaction product, then, carrying out immersion washing for multiple times by using warm water, carrying out vacuum drying on the obtained product for 8 hours at the temperature of 80 ℃ to obtain polyamideimide, and dissolving the polyamideimide in m-cresol solvent to obtain a polyamideimide solution;

(4) preparation of conductive polyamide-imide composite material

Uniformly dispersing carbon black CB, camphorsulfonic acid-doped polyaniline PANI-CSA and a compatilizer hydroquinone in a polyamideimide solution by high-speed emulsification and ultrasonic oscillation, and then preparing a polyamideimide/polyaniline/carbon black ternary conductive composite material by a wet spinning method;

in the step (4), the mass ratio of the polyamide imide to the polyaniline is 1:5-5: 1; the content of carbon black accounts for 2.5-10% of the total mass of the polyamide imide/polyaniline; the content of the compatilizer hydroquinone is 1 to 5 percent of the total mass of the polyamide imide/polyaniline;

the ternary blend material is used as a flexible wire material.

2. The method for preparing the ternary blend material with polyaniline and carbon black as conductive fillers according to claim 1, wherein the method comprises the following steps: the structural formula of the PANI-CSA is as follows:

wherein 0< y <1, 10< n;

wherein Ar is₁The method comprises the following steps:

Ar₂the method comprises the following steps:

or

x＝1，2，3，5，7，8，9，10，11，13；n＝10-200。

3. The method for preparing the ternary blend material with polyaniline and carbon black as conductive fillers according to claim 1, wherein the method comprises the following steps: in the step (1), aniline is o-methylaniline or o-methoxyaniline; the molar ratio of the aniline to the ammonium persulfate is 1:0.6-1: 2.

4. The method for preparing the ternary blend material with polyaniline and carbon black as conductive fillers according to claim 1, wherein the method comprises the following steps: in the step (2), the mass ratio of the polyaniline to the camphorsulfonic acid is 1:1.2-1: 1.8.

5. The method for preparing the ternary blend material with polyaniline and carbon black as conductive fillers according to claim 1, wherein the method comprises the following steps: the mass ratio of the p-phenylenediamine to the diacid monomer in the step (3) is 1:5-1: 8; the acylating agent isPyridine Py or triphenyl phosphite TPP, wherein the mass ratio of the diacid monomer to the acylating agent is 1:3-1: 6; the water absorbent is anhydrous calcium chloride CaCl₂And one of anhydrous lithium chloride LiCl or anhydrous zinc chloride, wherein the mass ratio of the diacid monomer to the water absorbent is 1:4-1: 9.

6. The method for preparing the ternary blend material with polyaniline and carbon black as conductive fillers according to claim 1, wherein the method comprises the following steps: the carbon black is one or a composition of oil furnace conductive carbon black, heavy oil byproduct conductive carbon black and calcium carbide acetylene carbon black; the mesh number of the carbon black is 100-600 meshes.