JP2609439B2 - Method for producing polyaniline film and composite thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyaniline film and a composite having improved processability by using an organic base. More specifically, the present invention provides
The aniline is oxidatively polymerized in the presence of a protonic acid to produce a polyaniline doped with a protonic acid, and the resulting doped polyaniline is added to a solvent containing an organic base to improve its solubility, thereby improving processability. The present invention relates to a method for producing a polyaniline film and a composite thereof, comprising producing a polyaniline solution having the same.

[0002]

2. Description of the Related Art There are various kinds of conductive polymer compounds. Among them, polyaniline is simple in its production method and is superior in thermal properties to other conductive polymer compounds. Therefore, it is one of the conductive polymer substances that have been studied. However, in general, after doping the high molecular weight polyaniline to the extent that it becomes a semiconductor or a conductor, it is not possible to dissolve or plasticize the conductive polyaniline in a normal non-polar solvent or a weak polar solvent. It was considered impossible.

[0003] Since polyaniline doped with protonic acid has better electrical properties than other polymer compounds, it can be used for batteries, electron wave shielding materials, flexible electrodes, antistatic materials and the like. It is well known that the applicability is very large. However, polyaniline is structurally very rigid in polymer chains, and furthermore, polyaniline doped with protonic acid is charged, so that interactions between polymer chains are very large. Therefore, its workability is reduced and many difficult problems are encountered in its practical use.

Various methods have been proposed to solve such problems. As one example, there has been proposed a method of using a protonic acid having a large relative anion when polyaniline is doped with an acid. In fact, when camphorsulfonic acid, dodecylbenzenesulfonic acid, or the like is used as a doping reagent for polyaniline, it has been known that the solubility of polyaniline doped in an organic solvent such as chloroform or meta-cresol is improved to some extent. (Synthetic Metal, Vol.48 p.91-97, 199
2). However, in such a method, polyaniline which has been doped with hydrochloric acid during the synthesis of polyaniline must be neutralized with aqueous ammonia and then re-doped with an acid having a large relative anion as described above. There are difficulties. In addition, the use of special techniques increases the solubility of the doped polyaniline,
This method is not industrially practical.

[0005] Alternatively, after polyaniline is oxidative polymerization in the presence of a proton acid, is treated with a base, then the resulting de-doped polyaniline (Emerald base) was dissolved in N- methylpyrrolidone There is known a method of forming a polyaniline solution by using the method (Japanese Patent Application Laid-Open No. 61-195,137). However, this method also has a difficulty in that it must be processed in the form of a film or a composite in a solution state and then doped again with a protonic acid.

[0006] EP 497,514 Al describes conductive mixtures, intrinsically conductive polymers, thermoplastic polymers and processes for their preparation, wherein the polyaniline particles are contained in a thermoplastic polymer. Is evenly distributed. However, the aforementioned polyaniline particles have a PV
It is dispersed to some extent in polymers such as C, but hardly dispersed in polymers such as polyolefin polymers. International Publication No. WO / 89/01694 describes conductive polyaniline in a thermally stable form, which polyaniline is produced by using an aromatic sulfonic acid as a dopant. In this patent, the thermal stability of polyaniline was investigated by TGA analysis. According to recent research reports, polyaniline has a temperature
It is reported to be stable within 0 minutes. Therefore, it is more necessary to improve processability than polyaniline's thermal stability. No. 4,983,322 describes a conductive polyaniline form capable solution processing, is produced by using an excess of transition metals such as FeCl ₃ as a polar solvent and an oxidant. However, the thermal stability of the polyaniline produced in this patent is poor because the polyaniline contains an excess of oxidizing agent, and the polyaniline has little practicality. International Publication No. WO / 92/22911 describes a conductive polyaniline having processability and a conductive product produced therefrom. The polyaniline which can be dissolved in a solvent and melt-mixed contains a dopant. Produced by using dodecylbenzenesulfonic acid or camphorsulfonic acid having a large molecular size. However, this method is problematic in that excess dopant (dodecylbenzene sulfonic acid) must be used and special mechanical mixing must be performed to make the polyaniline processable. .

Further, Yading Wang et al., Synth. Met. 47
(1992) 255-266 describes the study of the conductivity stability of acid-doped polyaniline, and describes the stability of the conductivity of polyaniline with acids used as dopants. Synth.Me by Eli Ruckenstein et al.
t.53 (1993) 283-292 describes an emulsion method for conducting polyaniline-polystyrene composites,
The polyaniline-polystyrene complex is made in an emulsion. K. Tzou et al., Synth. Met. 53 (1993)
365-377 describes PANI with an organic dopant in a polar solvent.
A method for producing a soluble polyaniline salt solution in which a base is doped in situ is described. By adding a dopant acid to obtain a conductive polyaniline solution, neutralized polyaniline (emerald base) is dissolved in a polar solvent. I have. Yong Cao et al., Synth.Met. 48 (1992) 91-9.
7 describes the conductive polyblend of polyaniline in the bulk polymer and the processability induced by the counterion of the conductive polyaniline.The processable polyaniline is a dodecylbenzenesulfonic acid having a large molecular size as a dopant. Alternatively, it is produced by using camphor sulfonic acid.

Adam Pon et al., Polymer 34 (1993) 4235, describes a conductive polymer having processability obtained by protonation of polyaniline with a phosphate ester, and the polyaniline having processability is used as a dopant. It is manufactured by using an organic phosphoric acid.
The above-mentioned articles and the like mainly relate to the production of polyaniline complex, and the article of Yong Cao is disclosed in U.S. Pat.
No. 3,322. Adam Pon's paper is Yong Cao
Is a subordinate concept of the paper. The conductivity and processability of polyaniline prepared by using organophosphoric acid instead of dodecylbenzene sulfonic acid described in Adam Pon's paper are inferior to those of the polyaniline described in Yong Cao's paper .

[0009]

The polyaniline doped with an acid generally has better thermal properties and conductivity than other polymer compounds. However, in its structure, polyaniline has a very high rigidity of a polymer chain,
Acid-doped polyaniline is charged and has very high interactions between the polymer chains, thus greatly reducing its processability. As a result, there are many difficulties in the practical use of the above polyanilines. Therefore, by dissolving polyaniline in a solvent,
There has been a strong demand for a polyaniline film and a composite thereof capable of increasing its solubility and improving its practicality.

[0010]

Means for Solving the Problems Here, the present inventors,
In order to solve the conventional disadvantages as described above, as a result of intensive research, aniline was oxidized and polymerized in the presence of a protonic acid, and the resulting doped polyaniline was dissolved in an organic solvent containing an amine as an organic base. It has been found that a polyaniline solution having processability can be obtained.
Thereafter, a conductive polyaniline film and a composite thereof can be manufactured without re-doping with a protonic acid.

The present invention relates to a method for producing a polyaniline composite mixed with a general-purpose polymer resin having a high molecular weight, which can be used for melt processing, and relates to a method for producing a conductive plastic product by a conventional plastic technique such as injection molding and compression molding. Can be manufactured. Further, a polyaniline derivative having the following structural formula can also be used in the present invention.

[0012]

Embedded image

(In the above formula, R¹Is H, or methyl,
Alkyl groups such as chill and propyl, alkyl ether groups and
Is an alkyl ester group, R is H, -OH, -CH
_Three, Hydrocarbon group, -OCH_ThreeOr with an alkyl ether group
Yes, X is Cl^-, OTs ^-, Dodecylbenzenesul
Phonate or polymer sulphonic group) The object of the present invention is to treat aniline in the presence of a protic acid.
And oxidatively polymerize the resulting doped polyaniline.
In an organic solvent containing amines as an organic base
Polyaniline soluble with its processability that increases its solubility
It is to provide a method for producing a liquid.

Another object of the present invention is to produce a polyaniline-coated film by coating the above-mentioned polyaniline solution and then drying it, or by casting the above-mentioned polyaniline solution and then drying it. And a method for producing a polyaniline film. Another object of the present invention is to mix the above polyaniline solution with a general-purpose polymer compound,
An object of the present invention is to provide a method for producing a conductive polyaniline composite film after coating or casting.

[0015] Another object of the present invention is to mix the above-mentioned polyaniline solution with a general-purpose polymer, precipitate in methanol, and then dry to obtain a workable polyaniline general-purpose polymer. An object of the present invention is to provide a method for producing a polyaniline composite having processability by forming and then melt-mixing the composite. In the production of the conductive polyaniline of the present invention, after preparing 1 liter of an aniline aqueous solution containing 0.02M to 0.5M aniline, 0.3 to 1M of protonic acid and 0.5M of ammonium persulfate as oxidizing agent Add ~ 1.5M to the above aqueous aniline solution. Then at -10 ° to 80 ° C for 10 minutes
After reacting for 24 hours, the produced polyaniline is filtered to synthesize polyaniline doped with protonic acid. The polyaniline thus synthesized is washed with distilled water and methanol and then dried in vacuum. Next, the dried polyaniline is mixed with an amine which is an organic base having a mole number of 1 to 100 times the number of moles of nitrogen contained in the polyaniline, and then N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfo Polyaniline may be processed in various forms by dissolving it in a polar solvent such as quisad (DMSO), and then dried to produce a final molded conductive polyaniline film and composite.

The amine which is an organic base used in the present invention can be represented by the following general formulas I and II.

[0017]

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In the above formula, R ₁ , R ₂ , R ₃ and R
₄ is hydrogen or an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 2 to 20 carbon atoms including an alcohol group, a carbonyl group or an ester group, and R ₅ is an aryl group. A group, a naphthalene group, an alkyl chain compound having 5 to 10 carbon atoms, or an alkyl group having 2 to 20 carbon atoms.

Hereinafter, the present invention will be described in more detail as follows. The polyaniline doped with a protonic acid is replaced with a polyaniline having a molar number of 1 to 10
After mixing with 0 times the organic base, it is mixed well mechanically. Although any protonic acid used in the present invention can be used, toluenesulfonic acid, dodecylbenzenesulfonic acid, campasulfonic acid, alkylnaphthalenesulfonic acid, alkylsulfonic acid, etc., which are heat-stable during subsequent processing, can be used. It is desirable to use an alkyl or aromatic sulfonic acid, or an acid such as alkylphenylphosphoric acid or alkylphosphoric acid. As the amine compound used in the present invention, for example, ammonia, methylamine, ethylamine, propylamine, dodecylamine, ethylenediamine, N-butylethanolamine, decylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, dimethyl Amine, trimethylamine, diethylamine, triethylamine, dipropylamine, tripropylamine,
Tributylamine and the like can be used. However, in order to evaporate and remove the used amine while drying the complex, it is preferable to use a low-boiling amine, that is, trimethylamine, triethylamine, tripropylamine or the like.

Here, in particular, the amine is suitably selected and used because the electrical properties of the conductive polyaniline film and the composite are changed depending on the kind of the amine used in adding the solvent or the amount of the amine used. It is important to. That is, the amount of the amine used may be 1 to 100 times the number of moles of nitrogen contained in the polyaniline.
20 times is desirable, and if necessary, it is desirable to select and use an appropriate amount depending on the desired conductive polyaniline film or composite.

The concentration of the polyaniline solution having processability according to the present invention is preferably such that the polyaniline solute to the solvent is 0.01 to 30% by weight, more preferably 0.1 to 10% by weight. It is preferable that the concentration of the polyaniline solution be appropriately selected and used depending on the physical properties of the conductive polyaniline film and the composite as required.

The method for processing polyaniline according to the present invention is shown in the process diagram of FIG. The processing temperature condition of the polyaniline according to the present invention is to prepare a film by casting a polyaniline solution, or to mix a polyaniline solution with a general-purpose polymer resin to produce a composite, and then to dry it.
Drying can be performed at normal temperature or high temperature, but generally it is desirable to dry at high temperature. The drying temperature is preferably from 25 ° to 200 ° C, most preferably from 50 ° to 150 ° C. If the drying temperature is too high, the conductive polymer material is decomposed, and the physical properties of this polymer material may be reduced.If the temperature is too low, it takes a long time to dry, so It is good to select and use.

The conductive polyaniline solution according to the present invention comprises:
The transparent general-purpose resin film can be coated by using a solution casting method and used for producing a film of a transparent conductive polymer material. Representative examples of such general-purpose resin films include polyethylene terephthalate, low-density polyethylene, high-density polyethylene,
Various general-purpose polymer films such as polypropylene, polycarbonate, and polyacrylate can be used, and it is preferable to select an appropriate polymer film depending on the use of the film coated with the conductive polymer material.

The general-purpose polymer resin that can be used in the conductive polyaniline composite according to the present invention includes various thermoplastic resins such as polystyrene, polyvinyl chloride, polyvinyl alcohol, polymethyl methacrylate, polymethyl acrylate, polyester, polyamide, and polyurethane. The resin may be appropriately selected and used depending on the use of the conductive polymer composite.

As described above, an advantage of the present invention is that aniline is oxidatively polymerized in the presence of a protonic acid to produce a protonic acid-doped polyaniline, and the resulting doped polyaniline is converted to an organic base. dissolved in a solvent, without going through a process of de-doping, the final polyaniline moldings or composite molded article can be easily manufactured, because processes can be shortened by the method of the present invention, industrially excellent effects There is.

The polyaniline general-purpose polymer composite produced by the present invention can be melt-processed, which was not possible with existing polyaniline, and can be molded into a polyaniline composite. It is very advantageous. Hereinafter, the present invention based on the following examples,
This will be described more specifically.

Example 1 Synthesis of polyaniline 38.04 g (0.2 mol) of paratoluenesulfonic acid was completely dissolved in 285 ml of distilled water in a water bath at 20 ° C., and 9.11 ml (0. .1 mol). 25.05 g of ammonium persulfate was added to this mixture.
(0.11 mol) in 96.4 ml of distilled water was slowly added dropwise over 1 hour, and the resulting deep blue-green polymer was thoroughly washed with water and methanol, and then dried in air. Let dry. In place of para-toluenesulfonic acid used as a dopant, an experiment was conducted in the same manner using hydrochloric acid, dodecylbenzenesulfonic acid, and butylnaphthalenesulfonic acid. It was measured. The results are shown in Table 1 below. Their solubility was measured using an ultraviolet absorption spectrum. First, a black line was formed with a solution in which the synthesized polyaniline was completely dissolved, and the solubility was measured based on the black line. Further, triethylamine was added in an amount of about 1 mole times the number of moles of nitrogen contained in polyaniline, and the solubility was measured.

The results are shown in Table 1 below.

[0029]

[Table 1]

Example 2 Casting of polyaniline 200 mg of polyaniline synthesized in the same manner as in Example 1.
And 1 ml of triethylamine or tripropylamine and N-
After adding and dissolving 4 ml of methylpyrrolidone, the solution was cast on a glass plate and dried in an electric furnace at 80 ° C. The dried film was impregnated in water to separate it from the glass plate, and then dried. After measuring the conductivity of the conductive polyaniline film, the result was 7 × 10 ⁻¹ S / cm.
Met.

[0031]Example 3 Polyaniline and polyvinyl chloride
Blend casting 0.5 g of the polyaniline obtained in Example 1 was added to triethylamido.
And 5 ml of tripropylamine were added and mixed well.
Then, add 20 ml of N-methylpyrrolidone and completely dissolve
I let it. 4.5 g of polyvinyl chloride in tetrahydrofuran
To prepare a 10% solution, and add this solution to the above port.
Thoroughly mixed with the lianiline N-methylpyrrolidone solution
After that, casting on a glass plate, then 80 ° C
And dried in an electric furnace to obtain a film. Of this film
As a result of measuring the conductivity, 1 × 10 ^-FiveS / cm.

Example 4 Polyaniline and polyvinyl chloride
To 0.5 g of the polyaniline obtained in Example 1, 5 ml of triethylamine or tripropylamine was added and mixed well, and 20 ml of N-methylpyrrolidone was added to dissolve completely. 4.5 g of polyvinyl chloride was dissolved in tetrahydrofuran to prepare a 10% solution, and this solution was thoroughly mixed with the above polyaniline N-methylpyrrolidone solution, and then mixed with methanol and 5% hydrochloric acid (3: 1). The mixture was poured into 1.6 liters of precipitate, then filtered, washed with water and methanol, and dried under vacuum. These are made into pellets at room temperature, and the conductivity is measured.
As a result of manufacturing a film with a compressor and measuring the conductivity,
They were 2 × 10 ⁻⁴ S / cm and 8 × 10 ⁻⁶ S / cm, respectively.

Example 5 Polyaniline and polymethyl meta
Preparation of acrylate complex To 0.5 g of the polyaniline obtained in Example 1, 5 ml of triethylamine or tripropylamine was added and mixed well, and then 30 ml of N-methylpyrrolidone was added to completely dissolve it. 4.5 g of polymethyl methacrylate is dissolved in tetrahydrofuran to make a 10% solution, and this solution is completely mixed with the above polyaniline N-methylpyrrolidone solution, and then mixed with methanol and 5% hydrochloric acid (3: 1). The solution was poured into 1.6 liters of precipitate, then filtered, washed with water and methanol, and dried under vacuum. Complexes of different concentrations were made while varying the amounts of polyaniline and polymethyl methacrylate, and pellets were formed at room temperature, and the conductivity was measured. The conductivity with respect to the concentration is shown in Table 2 below.

[0034]

[Table 2]

Example 6 Polyaniline and polystyrene
Preparation of the Composite To 0.5 g of the polyaniline obtained in Example 1, 5 ml of triethylamine or tripropylamine was added and mixed well, and then 30 ml of N-methylpyrrolidone was added to completely dissolve it. A 10% solution is prepared by dissolving 4.5 g of polystyrene in tetrahydrofuran, and this solution is completely mixed with the above polyaniline N-methylpyrrolidone solution, and then a mixed solution of methanol and 5% hydrochloric acid (3: 1). 1.
Poured into 6 liters, precipitated, then filtered, washed with water and methanol, and dried in vacuo. From these, pellets are formed at room temperature, and the conductivity is measured.
As a result of forming a film with a compressor at 0 ° C. and measuring its conductivity, 5 × 10 ⁻⁶ S / cm and 1 × 10
^-5 S / cm.

Example 7 Polyvinyl chloride composite
Conductivity The polyaniline-polyvinyl chloride composite prepared in Example 4 and polyvinyl chloride were mixed at an appropriate ratio and extruded at 150 ° C. through an extruder. The obtained polyaniline-polyvinyl chloride composite was found to be a conductive polymer composite in which polyaniline was uniformly dispersed. As a result of mixing and extruding 10 g of the polyaniline-polyvinyl chloride composite containing 30% of polyaniline with 90 g of polyvinyl chloride, the resulting polyaniline-polyvinyl chloride composite has a conductivity of 1 × 10 ⁻⁶ S / cm. Met. It was observed with a scanning microscope that polyaniline was very uniformly dispersed in the polyvinyl chloride composite.

Example 8 Polymethyl methacrylate composite
The polyaniline polymethyl methacrylate composite produced in Example 5 was mixed with polymethyl methacrylate and compressed in the same manner as in Example 7. Polyaniline polymethyl methacrylate complex 1 containing 30% polyaniline
0 g with 90 g of polymethyl methacrylate
As a result of extrusion at 0 ° C., the resulting polyaniline polymethyl methacrylate composite has a conductivity of 1 × 10 ⁻⁵ S / cm.
Met.

Example 9 Conductivity of Polystyrene Composite The polyaniline polystyrene composite produced in Example 6 was mixed with polystyrene and extruded in the same manner as in Example 8. 10 g of a polyaniline polystyrene composite containing 30% of polyaniline is mixed with 90 g of polystyrene to form a mixture.
As a result of extrusion at a temperature of ° C., the resulting polyaniline polystyrene composite had a conductivity of 1 × 10 ⁻⁵ S / cm.

Example 10 Conductivity of Polyethylene Composite 5 g of the polyaniline polymethacrylate composite prepared in Example 5 was mixed with 9 g of high-density polyethylene and extruded. As a result, the conductivity of the polyaniline polyethylene composite was 1 ×. It was 10 ^-7 S / cm.

[0040]

The polyaniline film and the composite thereof produced according to the present invention have a conductivity of 10 ^-1 S / cm.
Since it is 10 ^-7 S / cm, it can be used as an electron wave shielding material or an antistatic material. In particular, in the case of the polyaniline composite, melt processing and molding processing are possible, so that various forms of product can be developed, and therefore, the industrial application effect is large.

[Brief description of the drawings]

FIG. 1 is a process chart of a method for producing polyaniline of the present invention.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C08L 79/00 LQZ C08L 79/00 LQZ (72) Inventor Lee Myung Soo South Korea Jae-Yup-Dong, Kang Soon, 1402-1703 (72) Inventor Park Seung Hai, Republic of Korea, Tae-Jung, Yousun-K, Sing Sung-Dong, 155 (56) References Hei 7-330901 (JP, A)

Claims (5)

(57) [Claims] 1. The following steps: oxidizing and polymerizing aniline in the presence of a protonic acid and an oxidizing agent to produce a polyaniline doped with a protonic acid; washing the polyaniline with distilled water and methanol, and drying; Mixing the resulting polyaniline with an organic base, dissolving the resulting mixture in a polar solvent to form a polyaniline solution, and then coating or casting the polyaniline solution to form a film. Film production method. 2. The following steps: oxidizing and polymerizing aniline in the presence of a protonic acid and an oxidizing agent to produce a polyaniline doped with a protonic acid; washing the polyaniline with distilled water and methanol, and drying; Mixing the resulting polyaniline with an organic base, dissolving the resulting mixture in a polar solvent to form a polyaniline solution, mixing this polyaniline solution with a general-purpose polymer compound, and then mixing the resulting mixture A method for producing a polyaniline composite film, comprising forming a film by coating or casting. 3. The following steps: oxidizing and polymerizing aniline in the presence of a protonic acid and an oxidizing agent to produce a polyaniline doped with a protonic acid; washing the polyaniline with distilled water and methanol, and drying; Mixing the obtained polyaniline with an organic base, dissolving the obtained mixture in a polar solvent to form a polyaniline solution, mixing the polyaniline solution with a general-purpose polymer compound, and mixing the obtained mixture with methanol. A method for producing a processable polyaniline composite, comprising: precipitating in a solution, drying the precipitate to form a processable polyaniline general-purpose polymer compound composite, and then melt-mixing the composite. . 4. The general-purpose polymer compound is polystyrene,
4. The method according to claim 2, wherein the method is polyvinyl chloride or polymethyl methacrylate. 5. The method according to claim 1, wherein the organic base is triethylamine or tripropylamine.