WO2005035626A1

WO2005035626A1 - Process for producing conductive polyaniline and organic polymer composition

Info

Publication number: WO2005035626A1
Application number: PCT/JP2004/015203
Authority: WO
Inventors: Tsukasa Maruyama; Yuko Sekine
Original assignee: The Yokohama Rubber Co., Ltd.
Priority date: 2003-10-08
Filing date: 2004-10-07
Publication date: 2005-04-21
Also published as: JP4372102B2; DE112004001461B4; DE112004001461T5; JPWO2005035626A1

Abstract

A process for producing a conductive polyaniline capable of being stably dispersed in organic solvents, which comprises oxidatively polymerizing aniline or a derivative thereof in a layer mixture comprising an aqueous layer and an organic layer in the presence of a sulfonic acid and/or a water-insoluble organic polymer having a protonic acid group, wherein a molecular weight modifier and, according to need, a phase-transfer catalyst are caused to coexist in the polymerization; and an organic polymer composition containing the conductive polyaniline.

Description

Method for producing conductive polyaniline and organic polymer composition

Technical field

The present invention relates to a method for producing a conductive polyaniline and an organic polymer composition containing the same, and more particularly, to a method for producing a conductive polyaniline brightly dispersed in an organic solvent and having high electric conductivity, and to a method for producing the same. The present invention relates to an organic polymer composition.

book

Background art

It is known that a conductive polymer containing electrolyte ions as dopants can be obtained by subjecting aniline or an arginine derivative to chemical oxidative polymerization. However, conductive polyamides are generally insoluble and infusible in organic solvents, and therefore have poor molding workability, and their application and development have been difficult. However, it has been reported that aniline having a surfactant structure or a derivative thereof or a salt of a surfactant and aniline is polymerized to obtain polyaniline or a polyaniline derivative soluble in an organic solvent (Japanese). Japanese Patent Application Publication No. 6-2799584). However, the solubility of this polyaniline or polyaniline derivative in an organic solvent is not always high, and there is a need for a method of producing a more soluble polyvinylamine. In addition, a conductive polymer composition comprising a substituted or unsubstituted polyvinylamine, protonic acid and an organic solvent has been reported (Japanese Patent Application Laid-Open No. 2003-1766409). Publication), there is a problem that the yield of polyazirine is 30 to 40% because the oxidizing agent Zanilin (molar ratio) at the time of polymerization of adiline is 0.5. Introducing a substituent into the side chain of aniline improves solubility. Although it is planned, it is not a general purpose product, and it is not preferable because of low yield and low conductivity. The solubility and dissolution of the polyaniline or the polyaniline derivative in the organic solvent here depends on the state in which the polyaniline or the polyaniline derivative fine particles are dispersed in the organic solvent. This indicates that the state where aniline or the polyaniline derivative is dissolved in the organic solvent is mixed. Disclosure of the invention

An object of the present invention is to provide a method for producing a conductive polyaniline stably dispersed in an organic solvent at a high yield, and a polymer composition containing the conductive polyaline obtained by the method. Aim.

According to the present invention, aniline or a derivative thereof is oxidatively polymerized in the presence of at least one water-insoluble organic polymer compound having a sulfonate and a protonic acid group in a mixed layer composed of an aqueous layer and an organic layer. In this case, a method is provided for producing a conductive polyamide stably dispersed in an organic solvent by coexisting a molecular weight modifier and, if necessary, a phase transfer catalyst.

According to the present invention, there is also provided a conductive polyaniline-containing organic polymer composition containing the conductive polyaniline and the organic polymer obtained by the above method. BEST MODE FOR CARRYING OUT THE INVENTION

It is to be understood that singular forms (a, an, the) used herein and in the appended claims, include the plural, unless the context clearly dictates otherwise. .

In the present invention, when producing polyvinylamine, a molecular weight modifier and a molecular weight modifier are added in the presence of a polymer compound having a sulfonic acid and a Z or protonic acid group. If necessary, by coexisting with a phase transfer catalyst, it is possible to synthesize a conductive polyol that can be stably dispersed in an organic solvent in high yield.

Further, when the obtained poly A two Li down and mixed with SBR in a toluene solution, the electrical conductivity of the composition containing 5 wt% of poly Aniri down against SBR is 1 0- ⁵ S cnf ¹ , and a rubber composition exhibiting a sufficient static elimination effect can be obtained.

The conductive polyaurine soluble in an organic solvent according to the present invention is usually obtained by oxidative polymerization of aniline or a derivative thereof or any mixture thereof.

Examples of the aniline derivative include an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an alkylaryl group, an arylalkyl group, and an alkoxyalkyl group at positions other than the 4-position. An aniline derivative having at least one substituent is exemplified. Preferable examples include an alkylene group having 1 to 5 carbon atoms, an alkoxy group, an alkoxyalkyl group, and an aniline derivative having preferably at least one aryl group having 6 to 10 carbon atoms as a substituent.

The oxidizing agent for the oxidative polymerization is not particularly limited as long as it can polymerize the above-mentioned aniline or its derivative, and examples thereof include ammonium persulfate, persulfuric acid, sodium persulfate, and the like. Persulfuric acids such as potassium persulfate, hydrogen peroxide, ferric chloride, ferric sulfate, potassium bichromate, potassium permanganate, ferrous hydrogen peroxide, etc. Dox initiators and the like are preferably used. These oxidizing agents may be used alone or in combination of two or more. The amount of the oxidizing agent to be used is not particularly limited as long as it is an amount capable of oxidatively polymerizing the above-mentioned aniline or a derivative thereof, but is preferably 0 with respect to 1 mol of aniline or a derivative thereof. 0.1 to 10 moles, more preferably 0.1 to 5 moles. In the present invention, at the time of oxidative polymerization of aniline or a derivative thereof, a molecular weight modifier and, if necessary, a phase transfer catalyst are co-existed in the presence of an organic polymer compound having a sulfonic acid and / or a protonic acid group. The polymerization is carried out in a mixed layer of an aqueous layer and an organic layer.

As the sulfonic acid used in the present invention, any sulfonic acid conventionally used for oxidative polymerization of aniline can be used. Specifically, an aliphatic or sulfonic acid having one or more sulfonic acid groups can be used. Aromatic sulfonic acids and salts thereof, such as alkyl sulfonic acid, aryl sulfonic acid, anolex / rare linolenosolephonic acid, CK-olefin phenol, sulfonic acid of higher fatty acid ester, and (di) alkyl sulfosuccinic acid And sulfonic acids of higher fatty acid amides, camphorsulfonic acids and salts thereof. The amount of these sulfonic acids is not particularly limited, but is preferably 0.01 to 5 mol, more preferably 0.1 to 3 mol, per 1 mol of aniline or a derivative thereof. In the polymerization, in addition to sulfonic acid, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid, and protic acids such as organic acids such as m-nitrobenzoic acid and trichloroacetic acid are required. It may be added as needed.

In the water-insoluble organic polymer compound having a protonic acid group used in the present invention, a plurality of side chains having a protonic acid group and a plurality of side chains having an affinity for an organic solvent are included in a main chain. It has a combined structure. The protonic acid group is not limited to the terminal of the side chain, and a plurality of protonic acid groups may be present in the middle of the side chain. Examples of the protonic acid group include a sulfonic acid group, a carboxyl group, a phosphoric acid group, and a sulfuric acid group, and a sulfonic acid group, a carboxyl group, and a phosphoric acid group are preferable. The water-insoluble polymer compound having a protonic acid group is not particularly limited as long as it satisfies the above structure, but has an affinity for an ethylenic unsaturated monomer having a protonic acid group and an organic solvent. And a copolymer with an ethylenically unsaturated monomer having a side chain exhibiting a property. Examples of the ethylenically unsaturated monomers having a protonic acid group include styrene snolefonic acid, vinylolenolefonic acid, arinoresulfonate, methallylsulfonic acid, and 2-methacryloyloxetyl. 1-sulfonic acid, 3-methacryloyloxypropane-1-methylsulfonic acid, 3_methacryloyloxypropane-1-sulfonic acid, 4-methacryloylonoxybutane-1-sulfonic acid , 2-acrylyl amide 2-methylpropane sulfonic acid, methallyloxy benzene sulfonic acid, methallyl sulfonic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, croton Acid, monobutyl fumarate, monobutyl maleate / re, monoethyl maleate hexanoate, hydroxypropyl maleate , Maleic anhydride, citraconic anhydride, ethyl phosphate (meth) acrylate, polyoxyethylene glycol monophosphate (meta) acrylate, propylene glycol phosphate (Meta) Atari rate and the like. Also

However, the protonic acid group of the ethylenic unsaturated monomer having a protonic acid group may be an ammonium group, an anorecary metal salt, or a salt of an organic amine group. Examples of the ethylenic unsaturated monomer having a side chain that is iscompatible with an organic solvent include styrene, -methynolethylene, macroblock styrene, 1,3-butadiene, isoprene, and 2,3-dimethyl dimethylene. 1,3-butadiene, 1,3-pentadiene, vinyl chloride, vinylidene chloride, (meth) acrylonitrile and styrene derivatives having 1 to 30 carbon atoms and having a hydrocarbon group which may contain a hetero atom. Examples thereof include a conductor, a (meth) acrylic ester derivative, a (meth) acrylamide derivative, a butyl ether derivative, and a vinyl carboxylate derivative. The copolymer may be any of a random copolymer, a block copolymer, and a graft copolymer. the above The polymer can be obtained by using a known polymerization method.

As the water-insoluble organic polymer compound having a protonic acid group, a commercially available water-insoluble pigment dispersant can also be used. The above-listed products include, for example, Dispervik 110, Day Supervik 111, Dispervik 171, Dispervik 174, BYK-P104 (manufactured by Big Chemie) Solsperse 2600, Solsperse 3200 (made by Abyssia), and the like. There is no particular limitation on the amount of the organic polymer compound having these protonic acids, but the amount of the protonic acid groups is preferably 0.05 to 20 mol per mol of aniline or a derivative thereof. Preferably, an organic polymer compound is used, more preferably 0.1 to 10 mol.

Examples of the molecular weight modifier used in the present invention include an aniline derivative having a substituent at the 4-position, a thiol compound, a disulfide compound, and / or a methylstyrene dimer.

An aniline derivative having a substituent X at the 4-position is represented by the formula (I):

The compound shown by these can be mentioned. In the formula (I), X represents an alkyl group, an alkenyl group, an alkoxyl group, an alkylthio group, an aryl group, an aryloxy group, an alkylaryl group, an arylalkyl group, an alkoxyalkyl group, or a halogen group. Y represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an alkylthio group, an aryl group, an aryloxy group, an alkylaryl group, an arylalkyl group, an alkoxyalkyl group, or a halogen group. , N represents an integer of 0 to 4. When n is an integer of 2 to 4, Y may be the same or different. Preferred substituent X is an alkyl group having 1 to 5 carbon atoms. , An alkoxy group, an alkoxyalkyl group, an aryl group having 6 to 10 carbon atoms, and a preferable substituent Y is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group, an alkoxyalkyl group, a carbon atom. It is an aryl group of the number 6 to 10.

The thiol compound and Z or disulfide compound used in the present invention include butyl mercaptan, octyl mercaptan, dodecyl mercaptan, hexadecyl mercaptan, tetradecyl mercaptan, 2,2,4,6,6-pentapentamer Thornole compounds such as methylheptane_4-methylentienoole, anolequinoresulfides such as cetinoresin sulfide and dibutyl disulfide, and aromatic disulfides such as dipheninoresis sulfide and dipendinoresolenolide And xanthogen disulfides such as dimethinolexan togen disosulfide, ethynolexantogen diisnosulfide, and thiuram disulfide such as tetramethylthiuram disulfide and tetraethylthiuram disulfide of Disulfide compounds can be given. These are known compounds, many of which are generally commercially available. Not particularly limited to the amount of molecular weight modifier, but Aniri down or Ri-induced body 1 molar equivalent thereof ^{5. 0 X 1 0- 5 ~} 5. 0 X 1 0- 1 mol to use the better good Ku, 2 0 X 1 0 -. . 4 ~ 2 0 X 1 0- 1 mol more favorable preferable to use.

The phase transfer catalyst used in the preferred embodiment of the present invention is not particularly limited as long as it is generally used as a phase transfer catalyst. Specifically, benzyl triethylammonium Chloride, methyltrioctammonium chloride, tetral n—butynoleammonium bromide, tetral_n—butynoleammonium chloride, tetra-n-butylammonium chloride Tetraalkylammonium halides, etc .; tetrabutylammonium halides Tetraalkylammonium hydroxides such as thidroxide; tetraalkylphosphonium halides such as methyltriphenylphosphonium bromide; 12—crown 4, 15—crown Among them, crown ethers such as 5,18-crown-6 and the like are preferred. Of these, tetraalkylammonium halides are preferable in terms of ease of handling such as removal of the catalyst after the reaction, and particularly industrially Tetra n-butylammonium bromide or tetra-n-butylammonium chloride, which can be obtained at low cost, are preferred. In the present invention, if necessary, the amount of the phase transfer catalyst to be used is not particularly limited, but is preferably not less than 0.0001 mole times, more preferably, aniline or a derivative thereof. It is used in a molar amount of at least 0.05, but if the phase transfer catalyst is used excessively, the isolation and purification steps after the completion of the reaction become difficult. It is more preferably used in an equimolar amount or less.

With respect to the method of oxidatively polymerizing aniline or a derivative thereof according to the present invention, a conventional method can be employed except that the use of the above-mentioned reaction components is an essential requirement. As long as the stated purpose is not impaired, it may be the same as before. The polymerization medium of the present invention uses two types of liquid media, such as water and an organic solvent, as solvents. The organic solvent is not particularly limited as long as it dissolves aniline or a derivative thereof and is insoluble in water. Specific examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; and hexane. , Heptane, octane, etc .; aliphatic hydrocarbons; dichloroethane, chlorohonolem, 1,2-dichloroethane, chloro-open benzene, di-chloro benzene, etc. Etholeates, such as getyl ether, di-n-butyl mouth pinoreatenole, diisopropinoleatenole, di-n-butynoleatele, tert-butyl methinoleether; etyl acetate And esters such as n-propyl acetate, isopropyl acetate, and n-butyl acetate. Of these, aromatic hydrocarbons, aliphatic hydrocarbons, and lipogenated hydrocarbons are preferred. Particularly preferred are inexpensive and less toxic toluene and xylene. The above organic solvents may be used as a mixture of two or more kinds. The amount of the liquid medium used may be any amount that can be stirred, and is usually used in an amount of 1 to 500 times by weight, preferably 2 to 300 times by weight, based on aniline or a derivative thereof. It is. Here, the amount of the organic solvent used is 0.05 to 30 times by weight, preferably 0.1 to 10 times by weight, relative to water. However, it is preferably 110 to 80 ° C. Oxidative polymerization poly A according to the invention - Li down is rather very high yields, usually at 80% or more, the electrical conductivity is ¹ 0 _ ⁹ S cnf 1 or more.

Polyaniline stably dispersed in the organic solvent of the present invention can be isolated by performing the following operation.

(a) a method in which polyaniline is isolated by removing the organic solvent from the obtained reaction solution by evaporation or the like to precipitate poly-lin, and then removing water.

(b) Polyaniline dispersed in an organic solvent by adding water and / or a polar organic solvent to the obtained reaction solution and removing only the aqueous layer from the reaction solution separated into an organic layer and an aqueous layer A method of isolating,

(c) An excess amount of a polar organic solvent is added to the obtained reaction solution to precipitate polyaniline, and then the polyaurine is isolated by removing the solvent by filtration or decantation. how to

Of these, the preferred isolation methods are the methods (a) and (b), and more preferably the method (b). In addition, the poly (aniline) dispersion can be prepared by performing the following operation in addition to the method (b).

(d) A method in which the polyaniline isolated in (a) or (c) is dispersed in an organic solvent used for oxidative polymerization of aniline or an aniline derivative.

(e) A method in which the organic solvent used in preparing the dispersion and / or an organic solvent compatible with the organic solvent is added to the polyvinylamine dispersion prepared by the method (b).

When preparing the above-mentioned polyaniline dispersion, a dispersing machine such as a sand mill, a bead mill, a pole mill, a three-roll mill, a colloid dominore, an ultrasonic homogenizer, a Henschel mixer, a jet mill and the like may be used.

In the organic polymer composition according to the present invention, the conductive polyaniline is preferably used in an amount of 0.01 to 100 parts by weight, more preferably 0.1 to 100 parts by weight, based on 100 parts by weight of the organic polymer composition. 0 to 80 parts by weight. If the amount is too small, the conductivity of the organic polymer composition may be ^{10 to 12} Scm- ¹ or less. Conversely, if the amount is too large, an effect commensurate with the added amount may be obtained. May not be.

The organic polymer used in the organic polymer composition of the present invention is not particularly limited. Preferred examples include natural rubber, isoprene rubber, and nitrile rubber (for example, acrylonitrile-butadiene rubber, Ronitrile-styrene-butadiene rubber, hydrogenated nitrile rubber, butadiene rubber, styrene-butadiene rubber, butynole rubber, halogenated butyl rubber, ethylene- _α -olefin rubber (for example, ethylene-propylene rubber, ethylene-propylene rubber) (Non-conjugated gen rubber, ethylene non-conjugated gen rubber, etc.), polynorbornene rubber, acryle rubber, fluorine rubber, silicone rubber, ethylene monovinyl rubber Rubber, such as epichlorohydrin rubber, epichlorohydrin-ethylene oxide copolymer rubber, chlorinated polyethylene rubber, chloroprene rubber, and mouth-opening lossless polyethylene rubber, fluorinated rubber, and polyurethane rubber Polyethylene resin such as polyethylene, polypropylene, etc., Polyester resin such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, NIPPON 6 ゃ Nylon 6,6 Epoxy resin such as bisphenol A type epoxy resin and nopolak type epoxy resin, polyimide resin such as polyamide imide, polyamide acid, fluorine resin such as polyvinylidene fluoride , Modified PPE resin, polycarbonate resin, polyacetal resin, or A resin such as modified products thereof.

There is no particular limitation on the method of mixing these organic polymers with the conductive poly (aniline). For example, kneading the poly (vinyl alcohol) and the organic polymer isolated by the above-mentioned operation methods (a) and (c) is performed. And a method of mixing with a machine. The kneading machine includes a roll, a kneader, a bread palley mixer, a twin screw extruder and the like. Further, it can also be obtained by mixing an organic polymer with the polyaniline dispersion isolated in the above procedures (b), (d) and (e). The organic polymer to be mixed may be one previously dissolved or dispersed in a solvent or the like. The solvent is not particularly limited, but is preferably a solvent that is compatible with the solvent used when preparing the polyvinyl alcohol dispersion. The mixing method is not particularly limited as long as the polyaniline and the organic polymer can be efficiently mixed.A simple stirring method, a sand mill, a bead mill, a pole mill, a three-roll mill, a color mill, an ultrasonic homogenizer, etc. And a dispersing machine such as a Henschel mixer or a jet mill. When mixing a solid organic polymer and a polyaniline dispersion, the above kneader may be used. Further, the organic polymer composition of the present invention is obtained by the above method. Pre-mixed polyaurine and / or polyaniline dispersion and a plasticizer and process oil, which are generally used to improve the processability and flexibility of organic polymers, are mixed with the above organic polymer. It is also obtained by doing Further, the organic polymer composition of the present invention includes a polyaniline and a Z or polyaniline dispersion obtained by the above method and a car pump rack used as a reinforcing agent for the organic polymer. It can also be obtained by mixing a mixture obtained by previously mixing a filler such as silica or talc with the organic polymer. Further, the organic polymer composition of the present invention can also be obtained by mixing a surface treatment of the reinforcing agent with the polyaniline and / or the polyaniline dispersion obtained by the above method, and mixing with the organic polymer. .

Other components of the organic polymer composition according to the present invention include, for example, a reinforcing agent (filament) such as carbon black, silica, and talc, a vulcanizing or cross-linking agent, a vulcanizing or cross-linking accelerator, and silane coupling. Additives, oils, antioxidants, antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, plasticizers, etc. It can be optionally blended. The organic polymer composition according to the present invention may contain an ionic conductive agent and an electron conductive agent as other components. Examples of the ionic conductive agent include quaternary ammonium salts, borates, and surfactants. Examples of the electron conductive agent include conductive zinc oxide, conductive titanium oxide, conductive tin oxide, and graphite. Example

Hereinafter, the present invention will be described more specifically with reference to Examples, but it goes without saying that the present invention is not limited to these Examples. ϋExample Preparation of Polyaniline 1 (Conductive Polyaniline Dispersion) As shown in Table I, toluene 100 g, aniline 2 g, dodecyl benzenesulfonic acid 4.2 g, polyacrylic acid derivative (Soluspar 2600, manufactured by Abyssia) After dissolving 1.0 g and 0.03 g of 4-methylaniline, 50 g of distilled water in which 3.58 mL of 6 N hydrochloric acid was dissolved Was added. To this mixed solution was added 180 mg of tetrabutylammonium bromide, cooled to 5 ° C. or lower, and then 30 g of distilled water in which 5.4 g of ammonium persulfate was dissolved was added. After performing the oxidation polymerization at 5 ° C or lower for 5 hours, toluene was distilled off in vacuo. The polyaniline precipitate formed in the water was filtered and washed with water to obtain the desired polyaniline 1. After dispersing the obtained polyaniline in 150 g of toluene, the aqueous layer was removed to obtain a polyallyl toluene dispersion. When a portion of the poly (aniline) toluene dispersion was collected and toluene was distilled off in vacuo, the dispersion contained 4.1% by weight of solids (polyaniline content: 1.3% by weight). . When this dispersion was filtered through a filter having a pore size of 1.0 / zm, no clogging was observed, and this dispersion was stable without aggregation or precipitation even after 3 months at room temperature. From the elemental analysis, the molar ratio of dodecylbenzenesulfonic acid per aniline monomer unit was 0.45, and the yield of polyaniline was 97%. Further, the toluene was removed in vacuo from the dispersion, to produce a pellet in a compression molding machine, the 4-terminal method, it was the electrical conductivity was measured at room temperature 0.2 a 5 S cnt ^1.

Preparation of polyaniline 2

As shown in Table I in toluene 100 g, aniline 2 g, dodecyl benzenesulfonic acid 4.2 g, polyacrylic acid derivative (solspar 260,000, manufactured by Abyssia) 1.0 g, 4 g -Methylaniline (0.03 g) was dissolved, and 3.5 g of 6N hydrochloric acid was dissolved in distilled water (50 g). Was added. To this mixed solution, 180 mg of tetrabutylammonium bromide was added, and after cooling to 5 ° C. or lower, 30 g of distilled water in which 5.4 g of ammonium persulfate was dissolved was added. After performing the oxidation polymerization at 5 ° C. or lower for 5 hours, 50 g of toluene and then a mixed solvent of methanol and water (water / methanol = 2/3 (weight ratio)) were added, followed by stirring. After completion of the stirring, of the reaction solution separated into an organic (toluene) layer and an aqueous layer, only the aqueous layer was removed to obtain a poly (aluminate) dispersion. A portion of the toluene dispersion was collected and toluene was distilled off under vacuum. The dispersion contained 4.1% by weight of solids (polyaniline content: 1.3% by weight). I was When this dispersion was filtered with a filter having a pore size of 1.Ο μιη, no clogging was observed, and the dispersion was stable without aggregation and precipitation even after 3 months at room temperature. From the elemental analysis, the molar ratio of dodecylbenzenesulfonic acid to aniline monomer unit was 0.45, and the yield of polyaniline obtained was 96%. Toluene was distilled off from the poly (aluminum toluene dispersion) under vacuum, and a pellet was prepared using a compression molding machine.The electrical conductivity measured at room temperature by the four-terminal method was 0.26 S cnf ¹ . .

Preparation of polyaniline 3

A polyaniline toluene dispersion was obtained in the same manner as for polyaniline 2, except that 0.05 g of dodecantol was used instead of 4-methylaniline as a molecular weight modifier. When a portion of the toluene dispersion was collected and toluene was distilled off in vacuo, the dispersion contained 4.1% by weight of solids (polyaniline content: 1.3% by weight). I was When this dispersion was filtered with a filter having a pore size of 1.Ο μιη, no clogging was observed, and this dispersion was stable without aggregation or precipitation even after 3 months at room temperature. From elemental analysis, the molar ratio of dodecylbenzene sulfonic acid to aniline monomer unit was 0.45. The yield of polyaniline was 95%. Further, toluene was distilled off from the dispersion under vacuum, and a pellet was prepared using a compression molding machine. The electrical conductivity measured at room temperature by a four-terminal method was 0.25 Scm- ¹ .

Preparation of Polyaniline 4

A polyaniline toluene dispersion was obtained in the same manner as for polyaniline 2, except that 0.05 g of 1-methylstyrene dimer was used instead of 4-methylalanine as a molecular weight modifier. A portion of the polyaurine toluene dispersion was sampled and toluene was distilled off in vacuo, and it was found that the dispersion contained 4.1% by weight of solids (aniline content 1.3% by weight). Was. When this dispersion was filtered with a filter having a pore size of 1.0 / zm, no clogging was observed. The dispersion was stable without aggregation and precipitation even after 3 months at room temperature. From the elemental analysis, the molar ratio of dodecinolebenzenesnolefonic acid to aniline monomer unit was 0.45, and the yield of polyazirin was 96%. In addition, toluene was distilled off from the dispersion in vacuo, and a pellet was prepared using a compression molding machine. The electrical conductivity measured at room temperature by the four-terminal method was 0.25 S c ηΓ ^{1 and} was 7 times.

Preparation of Polyaniline 5

A polyaniline toluene dispersion was obtained in the same manner as for polyaniline 2 without using a polyacrylic acid derivative. When a portion of the poly (a-phenylene toluene) dispersion was collected and toluene was distilled off in vacuo, the dispersion contained 3.4% by weight of solids (polyaniline content: 1.3% by weight). Was. The dispersion was filtered with a filter having a pore size of ,, .μππ without clogging, and the dispersion was stable without aggregation and precipitation even after 3 months at room temperature. From the elemental analysis, the molar ratio of dodecyl benzene sulfonic acid to aniline monomerite was 0.45, and the yield of polyaniline was 96%. Also, from the dispersion The benzene was distilled off in vacuo, and a pellet was prepared using a compression molding machine. The electrical conductivity measured at room temperature by the four-terminal method was 0.25 Scm- ¹ .

Preparation of polyaniline 6

A polyaryne toluene dispersion was obtained in the same manner as for polyaniline 2 without using dodecylbenzenesulfonic acid. A portion of the polyaniline toluene dispersion was collected, and toluene was distilled off in vacuo. As a result, the solid content of the dispersion was 2.0% by weight (polyaniline content: 1.3% by weight). Was. The dispersion was filtered with a filter having a pore size of 1. 1 μm, without clogging, and the dispersion was stable without aggregation and precipitation even after 3 months at room temperature. Polyaniline yield was 96%. In addition, toluene was distilled off from the dispersion under vacuum, and a pellet was prepared using a compression molding machine. The electrical conductivity measured at room temperature by the four-terminal method was 0.21 Scnf ¹ .

Adjusting polyaniline 7

A polyaniline toluene dispersion was obtained in the same manner as for polyaniline 2 without using tetrabutylammonium bromide. When a part of the polyaniline toluene dispersion was collected and toluene was distilled off in vacuo, the dispersion contained 2.7% by weight of solids (polyaniline content 0.8% by weight). When this dispersion was filtered through a filter having a pore size of 1.0 zm, no clogging was observed. The dispersion was stable without aggregation and precipitation even after 3 months of room temperature. From the elemental analysis, the molar ratio of dodecylbenzenesulfonic acid to aniline monomerite was 0.45, and the yield of polyaniline was 60%. Further, toluene was distilled off from the dispersion under vacuum, and a pellet was prepared using a compression molding machine. The electrical conductivity measured at room temperature by a four-terminal method was 0.25 Scm " ¹ .

Preparation of polyaniline 8 4-A polyurin toluene dispersion was obtained in the same manner as for polyaniline 2 without using methinoleaniline and tetrabutylammonium bromide. When a portion of the poly (aniline) toluene dispersion was collected and toluene was distilled off in vacuo, the dispersion contained 2.7% by weight of solids (polyaniline content 0.7% by weight). . The dispersion was filtered with a filter having a pore size of 1.Ομππ, and clogged. When this dispersion was left at room temperature for 3 months, a precipitate of polyaniline was formed. From the elemental analysis, the molar ratio of dodecylbenzenesulfonic acid per unit of the monomer monomer was 0.45, and the yield of polyaniline was 55%. In addition, toluene was distilled off from the dispersion under vacuum, and a pellet was prepared using a compression molding machine. The electrical conductivity measured at room temperature by the four-terminal method was 0.2 ◦S cm- ¹ .

Table I Poly 2 Poly 2 Poly 2 Poly 2 Poly 2 Poly 2 Poly 2 Lin 1 Lin 2 Lin 3 Lin 4 Lin 5 Lin 6 Lin 7 Lin 8 Anilin 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Dodecinolebenzenesnolephonic acid 4.2 4.2 4.2 4.2 4.2 ― 4.2 4.2 Polyacrylic acid derivative 1.0 1.0 1.0 1.0 ― 1.0 1.0 1.0

4-Methylaniline "0.03 0.03 ― ― 0.03 0.03 0.03 Dodecanethiol ― ― ― 0.05 1 1 ― ― ― α-Methinolestyrene dimer * i ― ― 1 0.05 1 1 ― ― ― Tetrapylphane Nidium bromide * ² 0.18 0.18 0.18 0.18 0.18 0.18 11 Yield (%) 97 96 95 96 96 96 60 55 Dispersibility (% by weight) * ³ 4.1 (1.3) 4.1 (1.3) 4.1 (1.3) 4.1 (1.3) 3.4 (1.3) 2.0 (1.3) 2.7 (0.8) 2.7 (0.7) Dispersion stability * ⁴ 〇 O 〇〇〇. 〇〇 X conductivity (Scm— * ⁵ 0.25 0.26 0.25 0.25 0.25 0.21 0.25 0.20

* 1: Molecular weight regulator

* 2: Phase transfer catalyst

* 3: Shown by the solid content concentration (weight./.) In the polyaniline toluene dispersion (the content in parenthesis in the table is the polyaniline content)

(% By weight)).

* 4: The dispersion of the toluene dispersion was allowed to stand at room temperature for 3 months, and then visually judged.

Those that were not formed were marked as 〇.

* 5: Pellets produced by a compression molding machine were measured by the four-terminal method.

As shown in Table I, the polyanilines 1 to 6 of the present invention have the same yield and dispersibility and dispersibility in toluene, despite having conductivity equal to or higher than that of polyaniline 8 as a comparative example. It shows that the stability is excellent. In addition, although the yield of Polyaniline 7 is not always good, it is understood that the dispersibility and dispersion stability in toluene are excellent. Examples 1 and 2 and Comparative Example 1

As shown in Table II, poly (1,2,8) (0.05 g) and SBR (Nipol 1502, Nippon Zeon) (lg) were dissolved in 15 g of toluene. After that, toluene was distilled off in vacuo to obtain a poly (aniline) SBR complex. The conductivity of the obtained composite is as shown in Table II.

Table II Example 1 Example 2 Comparative Example 1 Formulation (parts by weight)

S B R 100 100 100 Polyaline 1 5 ― ―

Polyaniline 2 ― 5 ―

Poly A two Li down 8 one - fifth conductive (SCNT ¹⁾ It) - ⁵ 10 one ⁴ 10 one ^{1 2}氺1: 1 5 x 1 5 x 0 2 1 0 0 ° in cm of mold C 1 0 A rubber sheet was prepared by pressing for 1 minute, and the electrical conductivity was measured in accordance with JISK 719 (conditions: Loresta GP manufactured by Mitsubishi Chemical Corporation at room temperature).

Industrial applicability

As described above, according to the present invention, polyaniline that is conductive and can be stably dispersed in an organic solvent can be obtained in high yield. Since this conductive polyvinyl is stably dispersed in an organic solvent, a conductive film or a thin film can be easily formed by coating and drying on a substrate. The conductive film / thin film thus obtained is suitable for use as an antistatic material, a transparent conductive film, or the like. Furthermore, it can be converted to a conductive material by mixing with a general-purpose polymer material.

Claims

1. In the oxidative polymerization of aniline or a derivative thereof in the presence of at least one water-insoluble organic polymer compound having a sulfonic acid and a protonic acid group in a mixed layer composed of an aqueous layer and an organic layer, a molecular weight regulator and If necessary, an organic solvent can be added by coexisting a phase transfer catalyst.

A method for producing conductive polyaniline that is stably dispersed in a medium.

2. The method for producing a conductive polyaniline according to claim 1, wherein the sulfonic acid is a sulfonic acid having a hydrocarbon group having 7 or more carbon atoms.

3. The method for producing a conductive polyaniline according to claim 1, wherein the protonic acid group is a sulfonic acid group, a sulfonic acid group, a phosphoric acid group, or a sulfate group.

Enclosure

4. The conductive polymer according to any one of claims 1 to 3, wherein the molecular weight modifier is an aniline derivative having a substituent at the 4-position, a thiol compound, a disulfide compound, or a-methylstyrene dimer. Nirin production method.

5. The method for producing a conductive polyaniline according to any one of claims 1 to 4, wherein the thiol compound is a thiol compound having a hydrocarbon group having 4 or more carbon atoms.

6. The method for producing a conductive polyaniline according to any one of claims 1 to 4, wherein the disulfide compound is a disulfide compound having a hydrocarbon group having 2 or more carbon atoms.

7. The method for producing a conductive polyaniline according to any one of claims 1 to 6, wherein the phase transfer catalyst is a quaternary ammonium salt, a phosphonium salt, or a crown ether compound.

8. The method for producing a conductive polyvinyl according to any one of claims 1 to 7, wherein the oxidative polymerization is performed using a persulfate as an oxidizing agent.

9. The amount of sulfonic acid used is 1 mole equivalent of aniline or its derivative. The method for producing a conductive polyvinyl according to any one of claims 1 to 8, wherein the amount is 0.01 to 10 mol.

10. The use amount of the polymer compound having a protonic acid group is such that the amount of the protonic acid group is 0.05 to 20 mol per mol of aniline or a derivative thereof. 7. The method for producing a conductive polyline according to claim 1.

11. An organic polymer composition comprising a conductive polyaniline and an organic polymer produced by the method according to any one of claims 1 to 10.

12. The organic polymer composition according to claim 11, wherein the amount of the conductive polyaniline is 0.01 to 100 parts by weight based on 100 parts by weight of the organic polymer.

13. The method according to claim 11, wherein the organic polymer is at least one selected from rubber, polyolefin resin, polyester resin, polyamide resin, epoxy resin, polyimide resin and fluororesin. Organic polymer composition.