JP2009120762A - Polyaniline complex, composition of the same, and formed article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyaniline complex which gives a formed article exhibiting excellent heat resistance while having high electrical conductivity, and to provide a composition of the same. <P>SOLUTION: The polyaniline complex is a substituted or unsubstituted polyaniline complex, which is protonated with a compound represented by formula (I) (wherein, X is an acidic group; n is an integer of 1 or more; and m is an integer of 0 or more). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel polyaniline composite, a conductive composition thereof and a molded article obtained therefrom, and particularly relates to a conductive polyaniline composition and a molded article excellent in heat resistance.

  Polyaniline is a well-known material as one of conductive polymers. In addition to its electrical properties, polyaniline has the advantage and property of being able to be synthesized relatively easily from inexpensive aniline and exhibiting excellent stability against air or the like in a state of conductivity.

  As a method for producing polyaniline, a method of electrolytic oxidation polymerization or chemical oxidation polymerization of aniline or aniline derivatives is known.

  In electrolytic oxidation polymerization, a film having excellent electrical properties can be obtained. However, in general, the production cost is higher than chemical oxidation polymerization, and it is not suitable for mass production. Have difficulty.

  On the other hand, in order to obtain a conductive aniline or aniline derivative polymer by chemical oxidative polymerization, in general, a dopant (doping agent) is added to polyaniline obtained in a non-conductive base state (so-called emeraldine base state). The process of nation is required. However, polyaniline in the non-conductive base state is not suitable for industrial production because it hardly dissolves in most organic solvents. Furthermore, the conductive polyaniline (so-called emeraldine salt state) generated after the protonation is substantially insoluble and infusible, and it is difficult to easily manufacture a conductive composite material and a molded body thereof.

In response to the above problems, the present inventors have developed a soluble conductive polyaniline complex and a composition thereof that are easy to manufacture and handle (Patent Document 1). Moreover, this polyaniline composition has a high electrical conductivity.
International Publication No. 2005/052058 Pamphlet

Although the polyaniline complex and the composition thereof described in Patent Document 1 have excellent properties, the heat resistance of the obtained molded body is not necessarily high. There was a tendency for the conductivity to decrease when exposed to some degree.
Accordingly, an object of the present invention is to provide a polyaniline composite and a composition thereof that give a molded article exhibiting excellent heat resistance while being highly conductive.

｛式中、Ｘは、酸性基であり、Ｒは、それぞれ独立して、−Ｒ^１、−ＯＲ^１、−ＣＯＲ^１、−ＣＯＯＲ^１、−ＣＯ（ＣＯＲ^１）、又は−ＣＯ（ＣＯＯＲ^１）［ここで、Ｒ^１は、炭素数が４以上の置換基を含んでもよい炭化水素基、シリル基、−（Ｒ^２Ｏ）ｘ−Ｒ^３基、又は−（ＯＳｉＲ^３ _２）ｘ−ＯＲ^３基（Ｒ^２はアルキレン基であり、Ｒ^３はそれぞれ同一でも異なってもいてもよい炭化水素基であり、ｘは１以上の整数である）である］であり、任意のＲ同士が結合し環を形成していてもよい。ｎは１以上の整数であり、ｍは０以上の整数である。｝
２．実質的に水と混和しない有機溶剤に溶解している、１記載の置換又は未置換ポリアニリン複合体、及び
フェノール性水酸基を有する化合物
を含む導電性ポリアニリン組成物。
３．前記フェノール性水酸基を有する化合物が、芳香環を２個以上含む化合物である２記載の導電性ポリアニリン組成物。
４．実質的に水と混和しない有機溶剤中、前記式（Ｉ）で示される化合物の存在下で、置換又は未置換アニリンを化学酸化重合させる１記載の置換又は未置換ポリアニリン複合体の製造方法。
５．１記載の置換又は未置換ポリアニリン複合体に、フェノール性水酸基を有する化合物を添加する導電性ポリアニリン組成物の製造方法。
６．２又は３に記載の導電性ポリアニリン組成物から得られる導電性成形体。 According to the present invention, the following polyaniline complex and its composition are provided.
1. A substituted or unsubstituted polyaniline complex that is protonated with a compound represented by the following formula (I).

{In the formula, X is an acidic group, and each R is independently -R ¹ , -OR ¹ , -COR ¹ , -COOR ¹ , -CO (COR ¹ ), or -CO (COOR ¹ ). [Wherein R ¹ is a hydrocarbon group, silyl group, — (R ² O) x —R ³ group, or — (OSiR ³ ₂ ) x —OR ³ , which may contain a substituent having 4 or more carbon atoms. A group (R ² is an alkylene group, R ³ is a hydrocarbon group which may be the same or different, and x is an integer of 1 or more), and any R is bonded to each other. A ring may be formed. n is an integer of 1 or more, and m is an integer of 0 or more. }
2. 2. A conductive polyaniline composition comprising a substituted or unsubstituted polyaniline complex according to 1, which is dissolved in an organic solvent substantially immiscible with water, and a compound having a phenolic hydroxyl group.
3. 3. The conductive polyaniline composition according to 2, wherein the compound having a phenolic hydroxyl group is a compound containing two or more aromatic rings.
4). The method for producing a substituted or unsubstituted polyaniline complex according to 1, wherein the substituted or unsubstituted aniline is chemically oxidatively polymerized in an organic solvent substantially immiscible with water in the presence of the compound represented by the formula (I).
The manufacturing method of the electroconductive polyaniline composition which adds the compound which has a phenolic hydroxyl group to the substituted or unsubstituted polyaniline complex of 5.1.
A conductive molded body obtained from the conductive polyaniline composition according to 6.2 or 3.

  ADVANTAGE OF THE INVENTION According to this invention, the polyaniline composite_body | complex which gives the molded object which is highly conductive and has the outstanding heat resistance, and its composition can be provided.

  The polyaniline complex of the present invention exhibits high heat resistance by protonating the protonic acid represented by the above formula (I). In addition, a molded body obtained from a composition obtained by adding a small amount of a compound having a phenolic hydroxyl group to the composite has improved electrical characteristics such as conductivity. Furthermore, when the compound having a phenolic hydroxyl group is a compound containing two or more aromatic rings, the resulting molded body has high conductivity and little decrease in conductivity due to heat, and because of its uniformity, transparency Highly conductive articles.

｛式中、Ｘは、酸性基であり、Ｒは、それぞれ独立して、−Ｒ^１、−ＯＲ^１、−ＣＯＲ^１、−ＣＯＯＲ^１、−ＣＯ（ＣＯＲ^１）、又は−ＣＯ（ＣＯＯＲ^１）［ここで、Ｒ^１は、炭素数が４以上の置換基を含んでもよい炭化水素基、シリル基、−（Ｒ^２Ｏ）ｘ−Ｒ^３基、又は−（ＯＳｉＲ^３ _２）ｘ−ＯＲ^３基（Ｒ^２はアルキレン基であり、Ｒ^３はそれぞれ同一でも異なってもいてもよい炭化水素基であり、ｘは１以上の整数である）である］であり、任意のＲ同士が結合し環を形成していてもよい。ｎは１以上の整数であり、ｍは０以上の整数である。｝ The substituted or unsubstituted polyaniline complex (also simply referred to as polyaniline complex) of the present invention is a complex in which a substituted or unsubstituted polyaniline (also simply referred to as polyaniline) is protonated with a compound represented by the following formula (I). .

{In the formula, X is an acidic group, and each R is independently -R ¹ , -OR ¹ , -COR ¹ , -COOR ¹ , -CO (COR ¹ ), or -CO (COOR ¹ ). [Wherein R ¹ is a hydrocarbon group, silyl group, — (R ² O) x —R ³ group, or — (OSiR ³ ₂ ) x —OR ³ , which may contain a substituent having 4 or more carbon atoms. A group (R ² is an alkylene group, R ³ is a hydrocarbon group which may be the same or different, and x is an integer of 1 or more), and any R is bonded to each other. A ring may be formed. n is an integer of 1 or more, and m is an integer of 0 or more. }

  The conductive polyaniline composition of the present invention includes the above polyaniline complex and a compound having a phenolic hydroxyl group (hereinafter referred to as a phenolic compound) dissolved in an organic solvent that is substantially immiscible with water.

  The polyaniline composite of the present invention, the composition thereof, and the molded product obtained from them exhibit high heat resistance by allowing the protonic acid represented by the above formula (I) to be protonated in the polyaniline composite.

  Furthermore, when a phenolic compound containing two or more aromatic rings is used as the phenolic compound, a decrease in electrical conductivity due to heat is suppressed. A highly heat-resistant conductive material having a high thermal decomposition temperature and a small decrease in electrical conductivity (conductivity) due to heat can be obtained.

The substituted or unsubstituted polyaniline in the polyaniline complex of the present invention is preferably a high molecular weight body having a weight average molecular weight of 10,000 g / mol or more. Thereby, the intensity | strength and ductility of the electroconductive article obtained from a composition can be improved. There is no particular upper limit for the weight average molecular weight, polyaniline having a weight average molecular weight of about several million g / mol can be produced, and the conductive polyaniline composition of the present invention can also be produced. However, from the viewpoint of dissolution, the weight average molecular weight is preferably about 10,000,000 or less.
The molecular weight of polyaniline is measured by gel permeation chromatography (GPC).
Examples of the substituent of the substituted polyaniline include a linear or branched hydrocarbon group such as a methyl group, an ethyl group, a hexyl group, and an octyl group, an alkoxyl group such as a methoxy group and a phenoxy group, an aryloxy group, and a CF ₃ group. And halogen-containing hydrocarbon groups.

上記式において、Ｘは、酸性基であり、例えば、−ＳＯ_３ ⁻基、−ＰＯ_３ ^２−基、−ＰＯ_４（ＯＨ）⁻基、−ＯＰＯ_３ ^２−基、−ＯＰＯ_２（ＯＨ）⁻基、−ＣＯＯ⁻基等が挙げられる。これらの中では、酸性度が高く、ドープし易い点で−ＳＯ_３ ⁻基が好ましい。 In the polyaniline complex of the present invention, a compound represented by the following formula (I) is protonated to polyaniline.

In the above formula, X is an acidic group, for example, —SO ₃ ^— group, —PO ₃ ^2- group, —PO ₄ (OH) ^— group, —OPO ₃ ^2- group, —OPO ₂ (OH) ^—. group, -COO ^- group and the like. Among these, high acidity, -SO ₃ in terms easily doped ^- group.

Each R is independently —R ¹ , —OR ¹ , —COR ¹ , —COOR ¹ , —CO (COR ¹ ), or —CO (COOR ¹ ). Here, R ¹ is a hydrocarbon group, silyl group, — (R ² O) x —R ³ group, or — (OSiR ³ ₂ ) x—OR ³ group (which may contain a substituent having 4 or more carbon atoms) ( R ² is an alkylene group, R ³ is a hydrocarbon group which may be the same or different, and x is an integer of 1 or more. Examples of when R ¹ is a hydrocarbon group include linear or branched butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, pentadecyl, eicosanyl, etc. Can be mentioned.

  n is an integer greater than or equal to 1, Preferably it is an integer of 1-2. m is an integer greater than or equal to 0, Preferably it is an integer of 0-1.

（式中、Ｘは、酸性基であり、Ｒ^１０，Ｒ^１１はそれぞれ炭素数４〜２４の直鎖又は分岐状のアルキル基、−（Ｒ²Ｏ）ｘ−Ｒ^３基、又は−（ＯＳｉＲ^３ _２）ｘ−ＯＲ^３基（Ｒ^２は炭素数２〜４のアルキレン基であり、Ｒ^３はそれぞれ炭素数２〜１０の炭化水素基であり、ｘは１〜４の整数である）である。ｐは０又は１である。）
Ｒ^１０及びＲ^１１は好ましくは炭素数４〜２４の直鎖又は分岐状のアルキル基又は−（Ｒ²Ｏ）ｘ−Ｒ^３基であり、より好ましくは炭素数４〜２４の直鎖又は分岐状のアルキル基である。具体例としては、直鎖又は分岐状のブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基等が挙げられる。 The compound represented by the formula (I) is preferably a compound represented by the following formula (II).

(In the formula, X is an acidic group, and R ¹⁰ and R ¹¹ are each a linear or branched alkyl group having 4 to 24 carbon atoms, — (R ² O) x—R ³ group, or — (OSiR). ³ ₂ ) x-OR ³ group (R ² is an alkylene group having 2 to 4 carbon atoms, R ³ is a hydrocarbon group having 2 to 10 carbon atoms, and x is an integer of 1 to 4). (P is 0 or 1)
R ¹⁰ and R ¹¹ are preferably a linear or branched alkyl group having 4 to 24 carbon atoms or a — (R ² O) x -R ³ group, and more preferably a linear or branched group having 4 to 24 carbon atoms. In the form of an alkyl group. Specific examples include linear or branched butyl groups, pentyl groups, hexyl groups, octyl groups, decyl groups, and the like.

  The organic protonic acid represented by the formula (I) has a function of protonating polyaniline and exists as a dopant (counter anion) in the polyaniline complex. That is, in the composition of this invention, two types of compounds, an organic protonic acid and a phenolic compound, function as a dopant.

  In the polyaniline complex, the composition ratio between the polyaniline and the compound represented by the formula (I) is not particularly limited. However, the molar ratio of the polyaniline monomer unit / the compound represented by the formula (I) obtains high conductivity. From the viewpoint, it is usually 2 to 4, preferably 2 to 2.5.

The polyaniline complex can be produced by a chemical oxidative polymerization method or an electrolytic polymerization method.
Preferably, the substituted or unsubstituted aniline is chemically oxidatively polymerized in an organic solvent substantially immiscible with water in the presence of the organic protonic acid represented by the above formula (I) or a salt thereof.
Reference can be made to the above-mentioned International Publication No. 2005/052058 for specific production conditions of the chemical oxidative polymerization method and electrolytic polymerization method.

  The organic protonic acid represented by the above formula (I) or a salt thereof used in the present invention can be produced using a known method. For example, a corresponding norbornene ester derivative can be obtained by reacting a norbornene dicarboxylic acid anhydride derivative with a desired alcohol. By hydrosulfonylating this with sodium bisulfite or the like, a corresponding sulfonic acid derivative of norbornene ester can be obtained.

  The phenolic compound used in the composition of the present invention is not particularly limited, and is a compound represented by ArOH (where Ar is an aryl group or a substituted aryl group). Specifically, phenol, o-, m- or p-cresol, o-, m- or p-ethylphenol, o-, m- or p-propylphenol, o-, m- or p-butylphenol, o Substituted phenols such as-, m- or p-chlorophenol, salicylic acid, hydroxybenzoic acid and hydroxynaphthalene; polyhydric phenolic compounds such as catechol and resorcinol; and polymers such as phenolic resins, polyphenols and poly (hydroxystyrene) A compound etc. can be illustrated.

  In the composition of the present invention, the phenolic compound is present as a dopant, not as a solvent. The fact that the phenolic compound is a dopant means that the molded product produced from the composition of the present invention to which the phenolic compound is added has a very high electrical conductivity compared to the molded product to which this compound is not added (Examples and Comparative Examples). And the molded body obtained from the conductive polyaniline composition of the present invention containing the phenolic compound and the molded body obtained from the polyaniline composite not containing the phenolic compound after the organic solvent is removed are different from each other in UV. It is evident that the phenolic compound remains in the molded article after the removal of the organic solvent, which is supported by showing a -vis (ultraviolet visible) spectrum. That is, if the phenolic compound is a simple solvent, it is easily volatilized and removed by applying heat when forming a molded body. However, it is charged when it is present as a dopant, so that it requires a large amount of energy to be removed from the polyaniline and cannot be removed by heating to a degree of volatilization.

The addition amount of the phenolic compound in the composition of the present invention is usually 0.01 to 1000% by mass, preferably 0.5 to 500% by mass, based on the substituted or unsubstituted polyaniline complex that has been protonated. is there.
Moreover, it is preferable that the mole number concentration of a phenolic compound is the range of 0.01 mol / L-5 mol / L in the whole composition. If the amount of this compound added is too small, the effect of improving conductivity may not be obtained. In addition, when the amount is too large, the uniformity of the composition is impaired, and when removing the solvent by volatilization, a great amount of heat and time are required, resulting in a material with impaired transparency and electrical characteristics. There is a fear.

From the viewpoint of heat resistance, the phenolic compound preferably has two or more aromatic rings, and more preferably has two aromatic rings. The phenolic compound having two or more aromatic rings is not particularly limited as long as it has aromaticity, for example, two or more aromatic rings such as a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, and a pyrrole ring. And having at least one phenolic hydroxyl group can be used.
As such a compound, a compound represented by the following formula (III) can be preferably used.

Ar-X-Ar '(III)
[Wherein, X is a single bond, a group containing an oxygen atom, a nitrogen atom, or a group containing a carbon atom, and Ar and Ar ′ are aromatic ring groups, which may be the same or different. Ar and / or Ar ′ has at least one hydroxyl group. Ar and Ar ′ may have one or more substituents selected from the group consisting of a halogen atom, a nitro group, a nitrile group, an amino group, a cyano group, and a carbonyl group. ]

X is a single bond, an oxygen atom, —NH—, —NHCO—, —COO—, —CO—, —COCH ₂ —, —OCO—, —CH ₂ —, —C ₂ H ₄ —, —C ₃ H _6- and the like can be mentioned. From the standpoint of obtaining heat resistance and high electrical conductivity, preferred examples of X include an oxygen atom.
One or two X can be present in the phenolic compound. When two are present, the two Xs may be the same or different. As such, for example, a single bond and -CH 2 as X _- fluorene structure having a like.

Of the substituents on Ar and Ar ′, examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, and an isobutyl group.
Examples of other substituents for Ar and Ar ′ include halogen, amino group, cyano group, nitro group, nitrile group, and carbonyl group.
A plurality of substituents on Ar or Ar ′ may be bonded to each other to form a ring. Examples of the ring structure include a cyclohexyl ring, a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, and a pyrrole ring.

  Moreover, as a preferable phenolic compound other than the compound of the formula (III) in which two aromatic rings are bonded via X, a phenolic compound in which a hydroxyl group is added to a polycyclic aromatic ring such as a naphthalene ring or an anthracene ring is used. Can be mentioned. Such a compound is preferable in that it exhibits heat resistance and high conductivity. Examples of such a compound include α-naphthol and β-naphthol.

  The phenolic compound containing two or more aromatic rings is preferably a phenolic compound having a melting point of room temperature or higher or a boiling point of 200 ° C. or higher at room temperature. Particularly preferable examples include 2-, 3-, or 4-hydroxybiphenyl, 2-, 3-, or 4-phenoxyphenol, 1- or 2-naphthol, and the like.

  Examples of organic solvents that are substantially immiscible with water (water-immiscible organic solvents) used in the composition of the present invention include hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin; methylene chloride, chloroform, Halogen-containing agents such as carbon tetrachloride, dichloroethane, tetrachloroethane; ester solvents such as ethyl acetate, and the like. Among these, toluene, xylene, chloroform, trichloroethane, and ethyl acetate are preferable in that the solubility of the polyaniline complex is excellent.

The polyaniline composition of the present invention can be produced by adding a phenolic compound to a polyaniline complex dissolved in a water-immiscible organic solvent.
The ratio of the polyaniline complex in the water-immiscible organic solvent is usually 900 g / L or less, preferably 0.01 to 300 g / L or less, depending on the type of the water-immiscible organic solvent. If the content of the polyaniline complex is too high, the solution state cannot be maintained, and it becomes difficult to handle the molded body, the uniformity of the molded body is impaired, and consequently the electrical properties and mechanical strength of the molded body. There is a risk of lowering transparency. On the other hand, if the content of the polyaniline complex is too small, only a very thin film can be produced when the film is formed by the method described later, which may make it difficult to produce a uniform conductive film.

A phenolic compound is added to a solution in which the polyaniline complex is dissolved in a water-immiscible organic solvent. Specifically, the phenolic compound may be added in a solid state or in a liquid state, or may be added in a state dissolved or suspended in a water-immiscible solvent. Preferably, an appropriate solvent addition method is selected so as to be in a dissolved state even after the addition.
The molar concentration of the phenolic compound in the entire polyaniline composition is preferably in the range of 0.01 mol / L to 5 mol / L. In this range, particularly excellent conductivity can be obtained. In particular, the range is preferably from 0.2 mol / L to 2 mol / L.

Other resin materials, inorganic materials, curing agents, or plasticizers may be added to the polyaniline composition of the present invention depending on the purpose.
Other resin materials are added for the purpose of, for example, a binder substrate, a plasticizer, a matrix substrate, and specific examples thereof include, for example, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polycarbonate, polyethylene glycol, polyethylene oxide, Examples thereof include polyacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, and polyvinyl alcohol. When the composition of the present invention contains other resin materials, the composition of the present invention becomes a conductive composite material.

  Inorganic materials are added for the purpose of, for example, improving strength, surface hardness, dimensional stability and other mechanical properties. Specific examples thereof include silica (silicon dioxide), titania (titanium oxide), alumina ( Aluminum oxide) and the like.

  The curing agent is added, for example, for the purpose of improving strength, surface hardness, dimensional stability and other mechanical properties, and specific examples thereof include, for example, thermosetting agents such as phenol resins, acrylate monomers and photopolymerization. Examples thereof include a photo-curing agent using a property initiator.

  The plasticizer is added for the purpose of improving mechanical properties such as tensile strength and bending strength, and specific examples thereof include phthalic acid esters and phosphoric acid esters.

A conductive molded body is obtained from the polyaniline composition of the present invention. Specifically, the conductive molded body is obtained by drying the polyaniline composition of the present invention and removing the organic solvent.
For example, a conductive film can be manufactured by applying to a substrate such as glass, a resin film, or a sheet having a desired shape and removing the organic solvent.

  As a method for applying the composition of the present invention to a substrate, known general methods such as a casting method, a spray method, a dip coating method, a doctor blade method, a barcode method, a spin coating method, a screen printing, a gravure printing method, etc. The method can be used.

  In order to remove the water-immiscible organic solvent, the organic solvent may be volatilized by heating. As a method for volatilizing the water-immiscible organic solvent, for example, heating is performed at a temperature of 250 ° C. or less, preferably 50 to 200 ° C. under an air stream, and further, heating is performed under reduced pressure as necessary. Note that the heating temperature and the heating time are not particularly limited, and may be appropriately selected depending on the material to be used.

  Moreover, it can also be set as the self-supporting molded object which does not have a base material. In the case of forming a self-supporting molded body, preferably, when the above-described other resin material is added to the composition of the present invention, a molded body having a desired mechanical strength can be obtained.

  When the molded product of the present invention is a film or a film, the thickness is usually 1 mm or less, preferably 10 nm to 50 μm. A film having a thickness in this range is advantageous in that it does not easily crack during film formation and has uniform electrical characteristics.

  These molded articles may be composed of only a single conductive composition, that is, only a polyaniline base composition, or may be composed of several polymers constituting the conductive composite.

<Example 1>
(1) Synthesis of sodium 3,4-bis [(2-ethylhexyl) oxycarbonyl] cyclohexanesulfonate 4-cyclohexene-1,2-dicarboxylic acid di (2-ethylhexyl) ester (manufactured by Tokyo Chemical Industry Co., Ltd.) under an argon gas stream ) 80 g and isopropyl alcohol 900 mL were charged, and a solution of sodium hydrogen sulfite (manufactured by Wako Pure Chemical Industries, Ltd.) 42.3 g of water 660 mL was added. The solution was heated to reflux temperature and stirred at 80-83 ° C. for 16 hours. During this time, 1.66 g of 2,2′-azobis (isobutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) was added every hour from the start of reflux to 1 to 5 hours later, then 9 hours and 10 hours later. did. The reaction solution was cooled to room temperature and then concentrated under reduced pressure. The concentrated residue was dissolved in 1 L of an ethyl acetate / hexane mixed solution, 250 g of silica gel was added and stirred, and the solution was separated by filtration. Further, extraction was performed twice from silica gel with 1 L of ethyl acetate / hexane solution, and the filtrates were combined and concentrated under reduced pressure. The concentrated solution was purified by column chromatography (silica gel 1500 g, developing solvent: ethyl acetate / hexane), the purified product was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 3,4-bis [(2- Ethylhexyl) oxycarbonyl] sodium cyclohexanesulfonate (Na salt of Compound A represented by the following formula) was obtained 52.4 g.

(2) Production of polyaniline complex 8.0 g of sodium 3,4-bis [(2-ethylhexyl) oxycarbonyl] cyclohexanesulfonate synthesized in (1) above was stirred and dissolved in 200 mL of toluene, and this solution was dissolved in a nitrogen stream. The solution was placed in a 2 L glass reactor placed below, and 7.2 mL of aniline (manufactured by Wako Pure Chemical Industries, Ltd.) was added to this solution and dissolved by stirring. The flask was cooled with a constant temperature bath, and 600 mL of 1N hydrochloric acid was added to the solution.
Next, in a state where the solution was cooled to 5 ° C., a solution obtained by dissolving 14.6 g of ammonium persulfate in 200 mL of 1N hydrochloric acid was dropped from a dropping funnel, and the reaction was completed in 2 hours. Stirring was carried out while maintaining the internal temperature of the solution at 5 ° C. for 20 hours from the start of dropping.

The reaction solution was transferred to a separatory funnel, 200 mL of toluene was added, and the mixture was allowed to stand at room temperature. The aqueous phase (lower phase) separated into two phases by standing was extracted to obtain a crude polyaniline complex toluene solution.
Furthermore, 200 mL of ion exchange water was added to this complex solution and stirred, and then allowed to stand to separate the aqueous phase. After performing this operation twice, the complex solution was similarly washed with 200 mL of 1N hydrochloric acid aqueous solution, allowed to stand, and then the acidic aqueous solution was separated to recover the toluene solution of the polyaniline complex.

  The insoluble matter contained in this complex solution was removed with filter paper, and a toluene solution of a polyaniline complex soluble in toluene was recovered. This solution was transferred to an evaporator, heated in a hot water bath at 40 ° C. to 70 ° C. and depressurized to evaporate volatile components to obtain 10.5 g of a polyaniline complex.

(3) Characteristics of polyaniline complex After the volatile matter was substantially removed from the polyaniline complex obtained in (2) above, elemental analysis was performed. The results are shown below.
Carbon: 63.8 wt%, Hydrogen: 7.9 wt%, Nitrogen: 4.6 wt%, Sulfur: 4.1 wt%

  From the ratio of nitrogen weight percent based on the aniline raw material and sulfur weight percent based on 3,4-bis [(2-ethylhexyl) oxycarbonyl] cyclohexanesulfonic acid, 3,4-bis [(2-ethylhexyl) in this composite The molar fraction of oxycarbonyl] cyclohexanesulfonic acid / aniline monomer unit was 0.39. Moreover, the weight average molecular weight of the polyaniline skeleton in this polyaniline complex was 112,000 g / mol.

  The molecular weight was determined by gel permeation chromatography (GPC). Specifically, TOSOH TSK-GEL GMHHR-H was used as a column, a 0.01 M LiBr / N-methylpyrrolidone solution was used, and measurement was performed at 60 ° C. and a flow rate of 0.35 ml / min. As a sample, 100 μL of a 0.2 g / L solution was injected and detected by UV at 260 nm. As a standard, the average molecular weight was calculated by the PS (polystyrene) conversion method.

  The thermogravimetric decrease curve of this polyaniline composite in an air atmosphere was determined. As a result, the 4.8% weight loss temperature (thermal decomposition temperature) when the temperature was raised from 35 ° C. to 600 ° C. at 20 ° C./min was 271 ° C.

(4) Production of Polyaniline Molded Body 1 g of the polyaniline complex obtained in (2) above was dissolved again in 20 ml of toluene to prepare a uniform polyaniline complex solution. About 1 ml of this solution is spread on a glass substrate in a range of 17 mm × 50 mm, dried at 80 ° C. for 60 minutes in an air stream to prepare a coating film having a thickness of 32 μm, and Lorester GP (manufactured by Mitsubishi Chemical Corporation; Conductivity was measured using a resistivity meter by a needle method. The electric conductivity of the obtained coating film was 0.87 S / cm.

<Example 2>
(1) Preparation of conductive polyaniline composition 1 g of the polyaniline complex obtained in Example 1 (2) was dissolved again in 20 ml of toluene to prepare a uniform polyaniline complex solution. Further, 19 mmol of m-cresol was added. By addition, a conductive polyaniline composition having an m-cresol concentration of about 0.86 mol / L was obtained.

(2) Production of conductive polyaniline molded body About 1 ml of the conductive polyaniline composition obtained in the above (1) is developed on a glass substrate in a range of 17 mm × 51 mm, and dried at 80 ° C. for 60 minutes in an air stream. A conductive coating film having a thickness of 27 μm was prepared, and the electrical conductivity was measured using a Lorester GP (manufactured by Mitsubishi Chemical Corporation; resistivity meter based on a four-probe method). The conductivity of the obtained coating film was 149 S / cm.

(3) Thermal decomposition temperature of conductive polyaniline molded body The molded body of the conductive polyaniline composition obtained in the above (2) was peeled from the glass substrate to obtain a self-supporting film. When 3.07 mg of this film was heated at a rate of 20 ° C./min from 35 ° C. to 600 ° C. in an air atmosphere in the same manner as in Example 1 (3), the weight loss was found to be 5% Temperature) was 268 ° C. Even a molded article obtained from a conductive polyaniline composition containing m-cresol showed a high thermal decomposition temperature.

<Example 3>
(1) Synthesis of 5,6-bis [(2-ethylhexyl) oxycarbonyl] bicyclo [2,2,1] sodium heptane-2-sulfonate In a container equipped with a Dean-Stark apparatus under an argon gas stream, 50 g of norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry), 1.83 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries), 79.3 g of 2-ethylhexanol (manufactured by Tokyo Chemical Industry), dried Dioxane (196 mL) and dry toluene (653 mL) were added, and the mixture was heated to reflux at 106 to 109 ° C. and reacted for 22 hours.
The reaction solution was cooled to room temperature, and the solvent was distilled off under reduced pressure and concentrated. This concentrated residue is dissolved in 1250 mL of diisopropyl ether, washed once with 500 mL of saturated aqueous sodium hydrogen carbonate solution, then 3 times with 500 mL of 0.1N aqueous sodium hydroxide solution, and further 3 times with 500 mL of ion-exchanged water. After drying over anhydrous sodium sulfate, the solvent was distilled off.

The resulting concentrated residue was purified by column chromatography (silica gel 1650 g, developing solvent: ethyl acetate / hexane) to give 5,6-bis [(2-ethylhexyl) oxycarbonyl] bicyclo [2,2,1] heptene 94. 0.0 g was obtained.
Under an argon stream, 82.5 g of 5,6-bis [(2-ethylhexyl) oxycarbonyl] bicyclo [2,2,1] heptene was dissolved in 900 mL of isopropyl alcohol, and sodium bisulfite (manufactured by Wako Pure Chemical Industries) 42 .3 g of water 660 mL aqueous solution was added.

The solution was heated and stirred at 83 ° C. for 3 hours. Further, 1.66 g of 2,2′-azobis (isobutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) was added 1 hour after the start of reflux.
The reaction solution was cooled to room temperature, and volatiles were distilled off under reduced pressure and concentrated. This concentrated solution was dissolved in 1 L of a mixed solution of acetic acid / hexane, 200 g of silica gel was added and stirred, and the solution was filtered. Furthermore, 500 mL of each mixed solvent of ethyl acetate / hexane was added to this silica gel, and the soluble component was extracted six times and separated by filtration.

The filtrates were combined and concentrated under reduced pressure, and the concentrated residue was purified by column chromatography (silica gel 2 kg, developing solvent: ethyl acetate / hexane).
From the solution, the volatile component was distilled off under reduced pressure, dissolved again in 750 mL of chloroform, dried over anhydrous sodium sulfate, and then the volatile component was distilled off under reduced pressure to give 5,6-bis [(2-ethylhexyl) oxycarbonyl] bicyclo. 93 g of sodium [2,2,1] heptane-2-sulfonate (Na salt of compound B represented by the following formula) was obtained.

(2) Production of polyaniline complex 8.17 g of sodium 5,6-bis [(2-ethylhexyl) oxycarbonyl] bicyclo [2,2,1] heptane-2-sulfonate synthesized in (1) above was added to 200 mL of toluene. The solution was stirred and dissolved in a 2 L glass reactor placed in a nitrogen stream, and 7.2 mL of aniline (manufactured by Wako Pure Chemical Industries, Ltd.) was further added to the solution and dissolved by stirring. The flask was cooled with a constant temperature bath, and 600 mL of 1N hydrochloric acid was added to the solution.

Next, in a state where the solution was cooled to 5 ° C., a solution obtained by dissolving 14.6 g of ammonium persulfate in 200 mL of 1N hydrochloric acid was dropped from a dropping funnel, and the reaction was completed in 2 hours. Stirring was carried out while maintaining the internal temperature of the solution at 5 ° C. for 20 hours from the start of dropping.
The reaction solution was transferred to a separatory funnel, 200 mL of toluene was added, and the mixture was allowed to stand at room temperature. The aqueous phase (lower phase) separated into two phases by standing was extracted to obtain a crude polyaniline complex toluene solution.

Furthermore, 200 mL of ion exchange water was added to this complex solution and stirred, and then allowed to stand to separate the aqueous phase. After performing this operation twice, the complex solution was similarly washed with 200 mL of 1N hydrochloric acid aqueous solution, allowed to stand, and then the acidic aqueous solution was separated to recover the toluene solution of the polyaniline complex.
The insoluble matter contained in this complex solution was removed with filter paper, and a toluene solution of a polyaniline complex soluble in toluene was recovered. This solution was transferred to an evaporator, heated in a hot water bath at 40 ° C. to 70 ° C. and depressurized to evaporate volatile components to obtain 10.7 g of a polyaniline complex.

(3) Characteristics of polyaniline complex After the volatile matter was substantially removed from the polyaniline complex obtained in (2) above, elemental analysis was performed. The results are shown below.
Carbon: 63.6 wt%, Hydrogen: 8.0 wt%, Nitrogen: 3.7 wt%, Sulfur: 4.3 wt%

  From the ratio of the nitrogen weight percent based on the aniline raw material and the sulfur weight percent based on 5,6-bis [(2-ethylhexyl) oxycarbonyl] bicyclo [2,2,1] heptane-2-sulfonic acid, The molar fraction of 5,6-bis [(2-ethylhexyl) oxycarbonyl] bicyclo [2,2,1] heptane-2-sulfonic acid / aniline monomer unit was 0.51. Moreover, the weight average molecular weight of the polyaniline skeleton in this polyaniline complex was 55,500 g / mol.

  A thermogravimetric decrease curve was obtained when the polyaniline composite was heated from 35 ° C. to 600 ° C. at 20 ° C./min in an air atmosphere. As a result, the 4.5% weight loss temperature (thermal decomposition temperature) was 241 ° C.

(4) Production of Polyaniline Molded Body 1 g of the polyaniline complex obtained in (2) above was dissolved again in 20 ml of toluene to prepare a uniform polyaniline complex solution. About 1 ml of this solution is spread on a glass substrate in a range of 16 mm × 50 mm, dried at 80 ° C. for 60 minutes in an air stream to prepare a conductive coating film having a thickness of 32 μm, and Lorester GP (manufactured by Mitsubishi Chemical Corporation; The conductivity was measured using a four-point probe resistivity meter. The electric conductivity of the obtained coating film was 4.38 × 10 ⁻² S / cm.

<Example 4>
(1) Preparation of conductive polyaniline composition 1 g of the polyaniline complex obtained in Example 3 (2) was dissolved again in 20 ml of toluene to prepare a uniform polyaniline complex solution. Further, 19 mmol of m-cresol was added. By addition, a uniform conductive polyaniline composition having an m-cresol concentration of about 0.86 mol / L was obtained.

(2) Production of conductive polyaniline molded body About 1 ml of the conductive polyaniline composition obtained in the above (1) is developed on a glass substrate in a range of 17 mm × 51 mm, and dried at 80 ° C. for 60 minutes in an air stream. A conductive coating film having a thickness of 24 μm was prepared, and the electrical conductivity was measured using a Lorester GP (manufactured by Mitsubishi Chemical Corporation; resistivity meter based on a four-probe method). The conductivity of the obtained coating film was 285 S / cm.

(3) Thermal decomposition temperature of conductive polyaniline molded body The molded body of the conductive polyaniline composition obtained in the above (2) was peeled from the glass substrate to obtain a self-supporting film. When 3.06 mg of this film was heated at a rate of 20 ° C./min from 35 ° C. to 600 ° C. in an air atmosphere in the same manner as in Example 3 (3), the 5% weight reduction temperature was 238 ° C. Met. Even a molded article obtained from a conductive polyaniline composition containing m-cresol showed a high thermal decomposition temperature.

<Comparative Example 1>
(1) Production of polyaniline complex Sodium di (2-ethylhexyl) sulfosuccinate (manufactured by Tokyo Chemical Industry) (3.6 g of Na salt of compound X represented by the following formula) was dissolved in 100 mL of toluene with stirring and placed under a nitrogen stream. The solution was placed in a 1 L glass reactor, and 3.6 mL of aniline (manufactured by Wako Pure Chemical Industries, Ltd.) was further added to this solution and dissolved by stirring. The flask was cooled with a constant temperature bath, and 300 mL of 1N hydrochloric acid was added to the solution.

Next, in a state where the solution was cooled to 5 ° C., a solution prepared by dissolving 5.36 g of ammonium persulfate in 100 mL of 1N hydrochloric acid was dropped from a dropping funnel, and the reaction was completed in 2 hours. Stirring was carried out while maintaining the internal temperature of the solution at 5 ° C. for 20 hours from the start of dropping.
The reaction solution was transferred to a separatory funnel, 100 mL of toluene was added, and the mixture was allowed to stand at room temperature. The aqueous phase (lower phase) separated into two phases by standing was extracted to obtain a crude polyaniline complex toluene solution.
Further, 100 mL of ion exchange water was added to the complex solution and stirred, and then allowed to stand to separate the aqueous phase. After performing this operation twice, the complex solution was washed in the same manner with 100 mL of 1N hydrochloric acid aqueous solution, and allowed to stand, then the acidic aqueous solution was separated, and the toluene solution of the polyaniline complex was recovered.
The insoluble matter contained in this complex solution was removed with filter paper, and a toluene solution of a polyaniline complex soluble in toluene was recovered. This solution was transferred to an evaporator, heated in a hot water bath at 40 ° C. to 70 ° C., and reduced in pressure to evaporate volatile components to obtain 2.4 g of a polyaniline complex.

(2) Characteristics of polyaniline complex After the volatile matter was substantially removed from the polyaniline complex obtained in (1) above, elemental analysis was performed. The results are shown below.
Carbon: 61.5 wt%, Hydrogen: 8.5 wt%, Nitrogen: 3.5 wt%, Sulfur: 5.6 wt%

  From the ratio of the nitrogen weight percent based on the aniline raw material and the sulfur weight percent based on the di (2-ethylhexyl) sulfosuccinate, the molar fraction of di (2-ethylhexyl) sulfosuccinate / aniline monomer unit in the complex is: It was 0.69. Moreover, the weight average molecular weight of the polyaniline skeleton in this polyaniline complex was 306,000 g / mol.

  A thermogravimetric decrease curve was obtained when the polyaniline composite was heated from 35 ° C. to 600 ° C. at 20 ° C./min in an air atmosphere. Thereby, the 5.0% weight loss temperature (thermal decomposition temperature) was 210 ° C.

<Comparative example 2>
(1) Preparation of conductive polyaniline composition 1 g of the polyaniline complex obtained in Comparative Example 1 (1) was dissolved again in 20 ml of toluene to prepare a uniform polyaniline complex solution, and 8 mmol of m-cresol was further added. By addition, a uniform conductive polyaniline composition having an m-cresol concentration of about 0.43 mol / L was obtained.

(2) Production of Conductive Polyaniline Molded Body About 1 ml of the conductive polyaniline composition obtained in (1) above was developed on a glass substrate in a range of 16 mm × 51 mm and dried at 80 ° C. for 60 minutes in an air stream. A conductive coating film having a thickness of 30 μm was prepared, and the electrical conductivity was measured using a Lorester GP (manufactured by Mitsubishi Chemical Corporation; resistivity meter based on a four-probe method). The conductivity of the obtained coating film was 250 S / cm.

(3) Thermal decomposition temperature of conductive polyaniline molded body The molded body of the conductive polyaniline composition obtained in the above (2) was peeled from the glass substrate to obtain a self-supporting film. Similar to Comparative Example 1 (2), the weight loss when the film was heated at 20 ° C./min from 35 ° C. to 600 ° C. in an air atmosphere was found to be 205 ° C. It was. Even in a molded article obtained from a conductive polyaniline composition containing m-cresol, the thermal decomposition temperature was low.

<Example 6>
(1) Preparation of conductive polyaniline composition 1 g of the polyaniline complex obtained in Example 1 (2) was dissolved again in 20 ml of toluene to prepare a uniform polyaniline complex solution, and further 12 mmol of 3-phenoxyphenol. Was added to obtain a uniform conductive polyaniline composition having a 3-phenoxyphenol concentration of about 0.56 mol / L.

(2) Production of conductive polyaniline thin film About 1 ml of the conductive polyaniline composition obtained in (1) above was spread on a 30 mm × 30 mm square glass substrate and spin-coated at 3,000 rpm for 1 minute. This was dried at 80 ° C. for 1 minute in an air stream to form a transparent and homogeneous thin film on the glass substrate. When the surface resistance was measured using a Lorester GP (manufactured by Mitsubishi Chemical Corporation; resistivity meter based on a four-probe method), the surface resistance value was 505Ω / □.

(3) Heat resistance test of conductive polyaniline molded body The surface resistance value after leaving the thin film of the conductive polyaniline composition obtained in (2) above as a glass substrate at 160 ° C. in a nitrogen stream for 50 hours is: It was 626Ω / □, and almost no change was observed.

<Example 7>
(1) Preparation of conductive polyaniline composition 1 g of the polyaniline complex obtained in Example 3 (2) was dissolved again in 20 ml of toluene to prepare a uniform polyaniline complex solution, and further 12 mmol of 3-phenoxyphenol. Was added to obtain a uniform conductive polyaniline composition having a 3-phenoxyphenol concentration of about 0.56 mol / L.

(2) Production of conductive polyaniline thin film About 1 ml of the conductive polyaniline composition obtained in (1) above was spread on a 30 mm × 30 mm square glass substrate and spin-coated at 3,000 rpm for 1 minute. This was dried at 80 ° C. for 1 minute in an air stream to form a transparent and homogeneous thin film on the glass substrate. When the surface resistance was measured using a Lorester GP (manufactured by Mitsubishi Chemical Corporation; resistivity meter based on a four-probe method), the surface resistance value was 922 Ω / □.

(3) Heat resistance test of conductive polyaniline molded article The surface resistance value after leaving the thin film of the conductive polyaniline composition obtained in (2) above in a nitrogen stream at 160 ° C. for 50 hours is as follows: It was 1150Ω / □, and almost no change was observed.

<Comparative Example 3>
(1) Preparation of conductive polyaniline composition 1 g of the polyaniline complex obtained in Example 5 (1) was dissolved again in 20 ml of toluene to prepare a uniform polyaniline complex solution. Further, 19 mmol of m-cresol was added. By addition, a uniform conductive polyaniline composition having an m-cresol concentration of about 0.86 mol / L was obtained.

(2) Production of conductive polyaniline thin film About 1 ml of the conductive polyaniline composition obtained in (1) above was spread on a 30 mm × 30 mm square glass substrate and spin-coated at 3,000 rpm for 1 minute. This was dried at 80 ° C. for 1 minute in an air stream to form a transparent and homogeneous thin film on the glass substrate. When the surface resistance was measured using a Lorester GP (manufactured by Mitsubishi Chemical Corporation; resistivity meter based on a four-point probe method), the surface resistance value was 115 Ω / □.

(3) Heat resistance test of conductive polyaniline molded article The surface resistance value after leaving the thin film of the conductive polyaniline composition obtained in (2) above as a glass substrate in a nitrogen stream at 160 ° C for 5 hours is It was 252Ω / □, and the resistance value doubled.

  The polyaniline composite, conductive polyaniline composition, and molded product of the present invention are used in the field of power electronics and optoelectronics. Electrostatic / antistatic materials, transparent electrodes and conductive film materials, electroluminescent element materials, circuit materials, capacitors It can be used for dielectrics / electrolytes, electrode materials for solar cells and secondary batteries, fuel cell separator materials, and the like.

Claims (6)

A substituted or unsubstituted polyaniline complex that is protonated with a compound represented by the following formula (I).

{In the formula, X is an acidic group, and each R is independently -R ¹ , -OR ¹ , -COR ¹ , -COOR ¹ , -CO (COR ¹ ), or -CO (COOR ¹ ). [Wherein R ¹ is a hydrocarbon group, silyl group, — (R ² O) x —R ³ group, or — (OSiR ³ ₂ ) x —OR ³ , which may contain a substituent having 4 or more carbon atoms. A group (R ² is an alkylene group, R ³ is a hydrocarbon group which may be the same or different, and x is an integer of 1 or more), and any R is bonded to each other. A ring may be formed. n is an integer of 1 or more, and m is an integer of 0 or more. } A conductive polyaniline composition comprising the substituted or unsubstituted polyaniline complex according to claim 1 and a compound having a phenolic hydroxyl group, which is dissolved in an organic solvent substantially immiscible with water.   The conductive polyaniline composition according to claim 2, wherein the compound having a phenolic hydroxyl group is a compound containing two or more aromatic rings.   The method for producing a substituted or unsubstituted polyaniline complex according to claim 1, wherein the substituted or unsubstituted aniline is chemically oxidatively polymerized in an organic solvent substantially immiscible with water in the presence of the compound represented by the formula (I). .   The manufacturing method of the electroconductive polyaniline composition which adds the compound which has a phenolic hydroxyl group to the substituted or unsubstituted polyaniline composite_body | complex of Claim 1.   The electroconductive molded object obtained from the electroconductive polyaniline composition of Claim 2 or 3.