CN103958552B - The manufacture method of high-purity sodium p styrene sulfonate and the manufacture method of kayexalate - Google Patents

Abstract

The present invention provides a kind of novel polyphenyl vinyl sulfonic acid (salt) useful as the dispersant of the aqueous dispersion in order to manufacture the electric conductive polymers such as nano-carbon material and polythiophene class, multi-metal polypyrrole, polyaniline compound, polyphenylenevinylene class, polyphenylene class such as CNT, Graphene (graphene), fullerene.The present invention relates to use the polystyrolsulfon acid through structure control (salt) of high-purity p styrene sulfonic acid (salt), the nano-carbon material as the dispersant of effective ingredient, employing this dispersant using it and the aqueous dispersion of electric conductive polymer that the impurity such as isomeric compound is few, further relate to the manufacture method of this polystyrolsulfon acid (salt).

Description

The manufacture method of high-purity sodium p-styrene sulfonate and the preparation of polystyrene sodium sulfonate manufacturing method

technical field

The present invention relates to high-purity p-styrenesulfonic acid (salt), structure-controlled polystyrenesulfonic acid (salt) using it, its use as a dispersant, and nano-carbon material and conductive polymer produced using it The aqueous dispersion of, and further relate to the manufacture method of this polystyrene sulfonic acid (salt).

Background technique

Carbon nanotubes (hereinafter referred to as CNTs) are lightweight, high-strength, high wear resistance, high thermal conductivity, high melting point, high conductivity, semiconductivity, high specific surface area, hollow structure, high gas adsorption, biological Compatibility and other properties, so it is expected to be used for high-strength materials, high thermal conductivity materials, conductive materials, LSI wiring, micro machines (micro machines), carbon dioxide fixation materials, hydrogen storage materials, electromagnetic wave shielding materials, catalyst loading materials, nanofilters, biosensors, drug delivery systems, electrochemical devices (fuel cells, secondary batteries, capacitors, transistors, field emission displays, electronic paper, thin-film organic solar cells, dye-sensitized solar cells, organic EL, touch Control panel, various electrodes) and other applications.

However, CNTs tend to aggregate due to intermolecular forces, and this property is the biggest obstacle to practical use in the above-mentioned fields. Accordingly, a technique for stably nanodispersing CNTs in solvents or various polymer matrices without agglomerating them has been strongly sought.

For example, applied research is being carried out on the manufacture of fine wiring of integrated circuits by inkjet printing, the manufacture of field emission cathode sources by screen printing, and flat panel displays. Therefore, for the manufacture of the required CNT aqueous dispersion method, a variety of options have been proposed. For example, a method for producing an aqueous CNT dispersion using an anionic surfactant having a steroid skeleton has been disclosed (see, for example, Patent Document 1), and an aqueous CNT dispersion using dodecyl itaconic acid as a dispersant has been disclosed. A method for producing a dispersion (see, for example, Patent Document 2). In addition, it has been disclosed that a triphenylene derivative having a hydrophilic group is used as a dispersant, and a method of producing a CNT aqueous dispersion is irradiated with high-output ultrasonic waves (see, for example, Patent Document 3), or a fiber having a specific functional group is used A method for producing a ketone derivative (see, for example, Patent Document 4). However, none of the above-mentioned methods can necessarily satisfy the dispersion effect, and there are problems such as using a relatively expensive dispersant.

On the other hand, a method using styrenesulfonic acid is also known. For example, a method for producing a CNT aqueous dispersion using polystyrene sulfonate (homopolymer) has been disclosed (see, for example, Patent Document 5 and Patent Document 6). In addition, a method for producing a CNT aqueous dispersion using a styrenesulfonic acid-maleic acid copolymer salt has been disclosed (see, for example, Patent Document 7). Although these polystyrene sulfonic acid polymer salts can be industrially produced with high safety and relatively low cost, the dispersion effect cannot be said to be sufficient, and further improvement of the dispersion effect is required.

On the other hand, organic conductive polymers such as polythiophenes, polypyrroles, polyanilines, polyphenylenevinylenes, and polyphenylenes (hereinafter referred to as conductive polymers) ), from the viewpoint of conductivity, flexibility, and lightness, as antistatic coatings, solid electrolytic capacitor electrodes, electromagnetic wave shielding materials, actuators, and energy harvesting (power generation) materials, As well as components of lithium secondary batteries, sodium secondary batteries, organic thin film solar cells, dye-sensitized solar cells, organic EL displays, electronic paper, touch panels, etc., and ITO (indium tin oxide) transparent electrode substitutes are expected . However, since the above-mentioned conductive polymer is insoluble and infusible like CNT, it is difficult to coat and process. Therefore, the type in which a conductive polymer is dispersed in an organic solvent or an aqueous solvent in the form of fine particles has become the mainstream of development and has been commercially available.

In order to produce an aqueous dispersion of a conductive polymer, a dispersant for stabilizing the conductive polymer in water in the form of microparticles or nanoparticles is required, but the current mainstream is polystyrene sulfonic acid (see, for example, Patent Document 8, 9). Polystyrene sulfonic acid (hereinafter referred to as PSS) is a strong electrolyte polymer, and functions not only as a dispersant but also as a dopant for developing the conductivity of a conductive polymer.

However, when the conventional conductive polymer aqueous dispersion is used as an ITO transparent electrode substitute or electromagnetic wave shielding material, the conductivity is not enough. In addition, the stability, water resistance, and resistance to aluminum, tantalum, glass, polyester film, etc. Since the adhesiveness of various base materials is poor, improvement to these is strongly desired. The aforementioned low electrical conductivity, stability, water resistance, and adhesiveness are said to be largely related to the remaining PSS functioning as a dispersant.

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2009-242126

Patent Document 2: Japanese Patent Laid-Open No. 2010-13312

Patent Document 3: Japanese Patent Laid-Open No. 2009-190940

Patent Document 4: Japanese Patent Laid-Open No. 2011-127041

Patent Document 5: Japanese Patent Laid-Open No. 2005-263608

Patent Document 6: Japanese Patent Laid-Open No. 2010-254546

Patent Document 7: Japanese PCT Publication No. 2006-525220

Patent Document 8: Japanese Patent Application Laid-Open No. 7-90060

Patent Document 9: Japanese Patent Laid-Open No. 2004-59666

Contents of the invention

The present invention is accomplished in view of the above-mentioned problems, and its object is to provide a kind of nano-carbon materials such as CNT, graphene (graphene), fullerene and polythiophenes, polypyrroles, polyanilines, polyalkylenes, etc. Structure-controlled PSS or its salt (hereinafter also referred to as "PSS (salt)") is useful as a dispersant for aqueous dispersions of conductive polymers such as phenylvinylenes and polyphenylenes.

The inventors of the present invention have conducted active research to solve the above-mentioned problems, and found that PSS (salt) controlled by structure has become an effective solution for nanocarbon materials such as CNT, graphene, and fullerene, as well as polythiophenes, polypyrroles, polyanilines, polythiophenes, polypyrroles, polyanilines, The present invention has been accomplished by providing a dispersant useful for improving the physical properties of aqueous dispersions of conductive polymers such as polyphenylene vinylenes and polyphenylenes.

The present invention relates to a high-purity p-styrenesulfonic acid or its salt (hereinafter also referred to as "p-styrenesulfonic acid (salt)"), wherein, as p-styrenesulfonic acid (salt) sometimes contained The main impurities of styrene are (a) o-styrenesulfonic acid (salt), (b) β-bromoethylbenzenesulfonic acid (salt), (c) m-styrenesulfonic acid (salt), (d) bromobenzene The content ratios of ethylenesulfonic acid (salt) based on the peak area obtained by high performance liquid chromatography (hereinafter referred to as HPLC) are (a) ≤ 0.20%, (b) ≤ 0.50%, (c) ≤ 3.00%, respectively , and (d)≤0.10% (wherein, the sum of the peak areas of p-styrenesulfonic acid (salt) and (a) to (d) is 100).

Next, the present invention relates to a polystyrenesulfonic acid or a salt thereof (hereinafter also referred to as "polystyrenesulfonic acid (salt)"), which is produced using the above-mentioned high-purity p-styrenesulfonic acid (salt) and has The following repeating structural unit A, or having the following repeating structural unit A and the following repeating structural unit B,

[in repeating structural unit A, B, M represents sodium cation, lithium cation, potassium cation, ammonium cation, quaternary ammonium cation or proton, Q represents free radical polymerizable monomer residue, n represents an integer greater than 1, m represents 0 integer above].

Polystyrene sulfonic acid (salt) of the present invention preferably has the polystyrene sulfonic acid (salt) of at least any structure in following formula (I)～(III),

[in formula (I)～(III), M represents sodium cation, lithium cation, potassium cation, ammonium cation, quaternary ammonium cation or proton, Q represents other radical polymerizable monomer residues, and n and n' represent 1 The above integers, m and m' represent 0 or more integers].

Here, the polystyrenesulfonic acid (salt) of the present invention has a weight-average molecular weight of preferably 2,000 to 1,000,000 as determined by gel permeation chromatography (hereinafter referred to as GPC), and the ratio of the weight-average molecular weight to the number-average molecular weight ( =weight average molecular weight/number average molecular weight) is preferably less than 2.0.

In addition, Q in the above-mentioned repeating structural unit B and the above-mentioned (I) to (III) is preferably selected from styrene residues, styrene derivative residues, methacrylic acid residues, and 2-hydroxyethyl methacrylates. One of ester residue, glycidyl methacrylate residue, (meth)acrylamide residue, N-vinylpyrrolidone residue, N-phenylmaleimide residue, maleic anhydride residue More than one radically polymerizable monomer residue.

Next, the present invention relates to a dispersant and a conductive polymer dopant containing the above-mentioned polystyrenesulfonic acid (salt) as an active ingredient.

In addition, the present invention relates to an aqueous dispersion of carbon nanomaterials manufactured using the above-mentioned polystyrene sulfonic acid (salt) as a dispersant, and the preparation of the above-mentioned polystyrene sulfonic acid (salt) as a dispersant and a dopant. Aqueous dispersions of conductive polymers.

Next, the present invention relates to a method for producing the above-mentioned polystyrenesulfonic acid (salt) by performing radical polymerization or living radical polymerization of the above-mentioned high-purity p-styrenesulfonic acid (salt) in an aqueous solvent.

In addition, the present invention relates to a method for producing the above-mentioned polystyrenesulfonic acid (salt), wherein the radical polymerizable monomer is subjected to living radical polymerization in an aqueous solvent, and then the above-mentioned p-styrenesulfonic acid (salt) is added, The living radical polymerization is continued, or the p-styrenesulfonic acid (salt) is subjected to living radical polymerization in an aqueous solvent, then a radical polymerizable monomer is added, and the living radical polymerization is continued.

Here, the living radical polymerization initiator used in the present invention is preferably a compound having a presumed structure represented by the following formula (IV),

[In formula (IV), R ₃ , R ₄ , and R ₅ each independently represent a substituted linear or branched alkyl or phenyl group, and R ₃ , R ₄ , and R ₅ can be the same or different, R ₁ and R ₂ represent a monovalent group corresponding to a free radical generated by a free radical generator, and may be the same as or different from each other].

Using the structure-controlled PSS (salt) manufactured by the high-purity p-styrenesulfonic acid (salt) of the present invention, in an aqueous medium, nano-carbon materials such as CNT, graphene, and fullerene, and polythiophenes, poly Conductive polymers such as pyrroles, polyanilines, polyphenylene vinylenes, and polyphenylenes have a high ability to disperse in aqueous media, and can be used to improve the conductivity of conductive polymer aqueous dispersions, Stability and water resistance.

Description of drawings

Fig. 1 is the HPLC chromatogram of the high-purity p-styrene sulfonate of embodiment 1, and among Fig. 1, vertical axis represents peak intensity (the absorption intensity of detector, unit is arbitrary), and horizontal axis represents stripping time (unit is minute ). (a), (b), (c), and (d) in Fig. 1 represent (a) o-styrenesulfonic acid (salt), (b) β-bromoethylbenzenesulfonic acid (salt), (c ) intensity of m-styrenesulfonic acid (salt), (d) bromostyrenesulfonic acid (salt).

Fig. 2 is the HPLC chromatogram of the high-purity p-styrene sulfonate of embodiment 2. Others are the same as the description of FIG. 1 .

Fig. 3 is the HPLC chromatogram of the low-purity p-styrene sulfonate of Comparative Example 1. Others are the same as the description of FIG. 1 .

detailed description

The present invention relates to (a) o-styrenesulfonic acid (salt), (b) β-bromoethylbenzenesulfonic acid (salt), which are main impurities derived from raw material styrene that are sometimes contained in p-styrenesulfonic acid (salt). ), (c) m-styrenesulfonic acid (salt), and (d) bromostyrenesulfonic acid (salt), the content ratios based on the peak area obtained by HPLC are respectively (a) ≤ 0.20%, (b) ≤ 0.50%, (c)≤3.00%, and (d)≤0.10% (that is, the sum of the peak areas of p-styrenesulfonic acid (salt) and (a)~(d) is 100) high-purity p-styrenesulfonate Acid (salt), and the PSS produced by using it has the above-mentioned repeating structural unit A, or the above-mentioned repeating structural unit A and the following repeating structural unit B, and has, for example, at least any structure in the above-mentioned formulas (I) to (III) or a salt thereof [PSS (salt)].

The PSS (salt) of the present invention is not limited to the PSS (salt) homopolymer, that is, as long as it has the above-mentioned repeating structural unit A, or the above-mentioned repeating structural unit A and B, there is no special limitation, and it can also be a random copolymer or a block copolymer. segment copolymers. The block copolymer described here is a PSS (salt) chain (the above-mentioned repeating structural unit A) and a polymer chain (the above-mentioned repeating structural unit B) different from the PSS (salt), which are mutually block-bonded through a covalent bond. , including di-block, tri-block, multi-block and other types. Preferable examples of the block copolymer of the present invention include block copolymers having structures of the above formulas (I) to (III).

In addition, in the above-mentioned repeating structural units A to B and the above-mentioned formulas (I) to (III), n and n' are integers of 1 or more, preferably integers of 10 to 5000, and m and m' are integers of 0 or more, preferably It is an integer from 0 to 5000.

The present invention is characterized in that the PSS (salt) is structurally controlled, and the structural control referred to herein has three meanings.

The first meaning is to highly purify the monomer [p-styrenesulfonic acid (salt)] used in the production of PSS (salt), which will be described below.

p-Styrenesulfonic acid (salt) is generally produced by the following method, and impurities such as unreacted halides, isomers, and metal halides cannot be avoided as by-products or mixed in.

As a result of detailed analysis of p-styrenesulfonic acid (salt), it was determined that the main impurities included (a) o-styrenesulfonic acid (salt) and (b) β-bromoethylbenzenesulfonic acid derived from styrene as a raw material (salt), (c) m-styrenesulfonic acid (salt), (d) bromostyrenesulfonic acid (salt). The inventors of the present invention produced these impurities based on the peak area obtained by HPLC by recrystallizing and purifying p-styrenesulfonic acid (salt) containing the above impurities from an aqueous solution, or by controlling production conditions such as reaction temperature. Containing high-purity p-styrenesulfonic acid (salt) with ratios of (a)≤0.20%, (b)≤0.50%, (c)≤3.00%, and (d)≤0.10%, respectively, and using the high-purity p-styrenesulfonic acid (salt) Styrene sulfonic acid (salt) is produced with high purity PSS (salt) by the conventional radical polymerization method. Using it as a dispersant to produce an aqueous dispersion of CNT or poly(3,4-ethylenedioxythiophene) (hereinafter referred to as PEDOT), which is a representative conductive polymer, was found and used in the past Compared with the case of PSS, the stability of the dispersion is improved. Furthermore, it was found that the electrical conductivity of the coating film obtained from the PEDOT aqueous dispersion was improved.

Although the reason is not clear, the improvement in the stability of the dispersion is considered to be due to the improvement in the stability of PSS (salt) due to the reduction of isomers such as meta-forms. Regarding the improvement of electrical conductivity, there have been no reports about the regularity of PSS (salt) in this application so far, but it is considered that the doping rate of PEDOT may be increased due to the improvement of the regularity of PSS (salt). .

In addition, the present invention also refers to a solution containing high-purity PSS or a salt thereof obtained by radically polymerizing the above-mentioned high-purity p-styrenesulfonic acid (salt) in an aqueous solvent. That is, (b) β-bromoethylbenzenesulfonic acid (salt) among the above-mentioned impurities does not contain a radically polymerizable double bond, so it is not copolymerized in the PSS (salt) skeleton, but exists in the aqueous medium prepared PSS (salt) solution. When an aqueous solution of PSS (salt) containing impurities such as β-bromoethylbenzenesulfonic acid (salt) is used in applications such as aluminum electrolytic capacitors, the When the halogen is released, and the electrochemical corrosion reaction of aluminum due to the halogen occurs repeatedly, the capacitor fails. Therefore, it is also preferable to reduce β-bromoethylbenzenesulfonic acid (salt) as much as possible.

The second meaning is to narrow the molecular weight distribution of PSS (salt), that is, the value of the so-called weight average molecular weight/number average molecular weight to less than 2.0. The inventors of the present invention synthesized a PSS (salt) with a molecular weight distribution of less than 2.0 by living radical polymerization, and used it in a dispersant to manufacture a CNT aqueous dispersion or a PEDOT aqueous dispersion. As a result, they discovered and used the conventional PSS The stability of the dispersion is improved compared with the case of the PEDOT aqueous dispersion, and the conductivity of the PEDOT aqueous dispersion coating film is improved.

It is considered that the efficiency as a dispersant is improved by narrowing the molecular weight distribution of PSS (salt). That is, it is considered that when the length of the PSS (salt) is too short relative to the particle size of the dispersoid, the PSS (salt) is easily desorbed from the dispersoid, and conversely, when it is too long, the PSS (salt) bridges the dispersoids to aggregate. In addition, although the reason is not clear, it is considered that the desorption of PSS (salt) from the surface of the PEDOT particles is less likely to occur after the production of the PEDOT aqueous dispersion, thereby improving the electrical conductivity.

In addition, the molecular weight distribution of the PSS (salt) of the present invention is preferably less than 2.0. The closer the molecular weight distribution is to 1.0 indicating monodispersity, the better, but considering the productivity and cost of PSS (salt), it is more preferably 1.0 to 1.8. In the present invention, in order to make the molecular weight distribution of PSS (salt) less than 2.0, as described later, the high-purity p-styrenesulfonic acid (salt) of the present invention is carried out living radical polymerization, at this time, as long as the following formula is used The radical polymerization initiator represented by (IV) or PSS (salt) having a general molecular weight distribution may be used to fractionate PSS (salt) of a desired molecular weight using a column.

The third meaning is to connect a polymer different from PSS (salt) and PSS (salt) in a block form (so-called block copolymerization). The inventors of the present invention have found that PSS (salt) and a polymer considered to be less hydrophilic than PSS (salt) are connected in a block form by living radical polymerization to produce a PSS (salt) block copolymer, and use it As a dispersant to make CNT or PEDOT aqueous dispersion, the stability of the dispersion can be further improved as a result. It is considered that the block with low hydrophilicity is effectively adsorbed on hydrophobic materials such as CNT or PEDOT, or conversely, the dispersion stability has been maintained by the remaining PSS (salt) in the past, but the present invention uses the ratio of hydrophilicity to Dispersion stabilization by another block with low PSS (salt). Furthermore, by block-bonding PSS (salt) to heterogeneous polymers, it is possible to improve the adhesion to substrates such as resin, glass, and ITO, which have been the subject of the past, and the compatibility with other types of polymers. possibility of solubility.

The weight-average molecular weight of the PSS (salt) of the present invention obtained by GPC is not limited, but is preferably 2,000 to 1,000,000, considering the handling properties of aqueous dispersions such as viscosity, and the amount of polymerization initiator when producing the PSS (salt). , more preferably 5,000 to 600,000.

This weight average molecular weight can be adjusted easily by the addition amount of a polymerization initiator or a chain transfer agent with respect to a monomer.

As other monomers other than p-styrenesulfonic acid (salt) used in PSS (salt) or PSS (salt) block copolymer of the present invention, as long as utilize PSS (salt) free radical to carry out radical polymerization, or for Styrenesulfonic acid (salt) generates radicals that can be used as radical polymerization initiators (in other words, radical copolymerization with p-styrenesulfonic acid (salt) is possible), and there is no particular limitation. Examples include N-phenylmaleimide, N-(chlorophenyl)maleimide, N-(methylphenyl)maleimide, N-(isopropylphenyl) Maleimide, N-(thiophenyl)maleimide, N-methylphenylmaleimide, N-bromophenylmaleimide, N-naphthylmaleimide Amines, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-(nitrophenyl)maleimide , N-benzylmaleimide, N-(4-acetoxy-1-naphthyl)maleimide, N-(4-oxyl-1-naphthyl)maleimide, N-(3-fluoranthyl) maleimide, N-(5-fluoresceinyl (Fluoresceinyl)) maleimide, N-(1-pyrenyl) maleimide, N-(2,3-xylyl)maleimide, N-(2,4-xylyl)maleimide, N-(2,6-xylyl)maleimide , N-(aminophenyl)maleimide, N-(tribromophenyl)maleimide, N-[4-(2-benzimidazolyl)phenyl]maleimide, Maleimides such as N-(3,5-dinitrophenyl)maleimide, N-(9-acridyl)maleimide, dibutyl fumarate, fumarate Fumaric acid diesters such as dipropyl fumarate, diethyl fumarate, and dicyclohexyl fumarate, and fumaric acid monoesters such as butyl fumarate, propyl fumarate, and ethyl fumarate Classes, dibutyl maleate, dipropyl maleate, diethyl maleate and other maleic acid diesters, butyl maleate, propyl maleate, ethyl maleate, maleic acid Maleic acid monoesters such as dicyclohexyl acid, acid anhydrides such as maleic anhydride and citraconic anhydride, maleimide, N-(sulfophenyl)maleimide, N-cyclohexylmaleimide Amines, maleimides such as N-methylmaleimide and N-ethylmaleimide, styrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene , fluorostyrene, trifluorostyrene, nitrostyrene, cyanostyrene, α-methylstyrene, p-chloromethylstyrene, p-cyanostyrene, p-acetoxystyrene, p-styrene Sulfonyl chloride, ethyl p-styrenesulfonate, methyl p-styrenesulfonate, propyl p-styrenesulfonate, p-butoxystyrene, 4-vinylbenzoic acid, 3-isopropenyl-α,α Styrenes such as '-dimethylbenzyl isocyanate, isobutyl vinyl ether, ethyl vinyl ether, 2-phenyl vinyl alkyl ether, nitrophenyl vinyl ether, cyanophenyl vinyl ether Ether, chlorophenyl vinyl ether and other vinyl ethers, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, decyl acrylate, lauryl acrylate, octyl acrylate, Lauryl Acrylate, Stearyl Acrylate, 2-Ethylhexyl Acrylate, Cyclohexyl Acrylate, Bornyl Acrylate, 2-Ethoxyethyl Acrylate, 2-Butoxyethyl Acrylate, Acrylate 2 -Hydroxyethyl acrylate, tetrahydrofurfuryl acrylate, methoxyethylene glycol acrylate, ethyl carbitol acrylate, 2-hydroxypropyl acrylate ester, 4-hydroxybutyl acrylate, 3-(trimethoxysilyl)propyl acrylate, polyethylene glycol acrylate, glycidyl acrylate, 2-(acryloyloxy)ethyl phosphate, acrylate 2, 2,3,3-tetrafluoropropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2,2,3,4,4 acrylate, Acrylates such as 4-hexafluorobutyl, methyl methacrylate, tert-butyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate, isopropyl methacrylate, decyl methacrylate , lauryl methacrylate, octyl methacrylate, lauryl methacrylate, stearate methacrylate, cyclohexyl methacrylate, bornyl methacrylate, benzyl methacrylate, methyl phenyl acrylate, glycidyl methacrylate, polyethylene glycol methacrylate, 2-hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, methoxyethylene glycol methacrylate, Ethyl carbitol methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-(methacryloyloxy)ethyl phosphate, 2-(dimethyl methacrylate Amino) ethyl ester, 2-(diethylamino) ethyl methacrylate, 3-(dimethylamino) propyl methacrylate, 2-(isothiocyanate) ethyl methacrylate, 2-methacrylic acid ,4,6-Tribromobenzene, 2,2,3,3-tetrafluoropropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3 methacrylate, 3-pentafluoropropyl, methacrylates such as 2,2,3,4,4,4-hexafluorobutyl methacrylate, 1,3-butadiene, 2-methyl-1,3- Butadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 2-cyano-1,3-butadiene, 1-chloro-1, 3-butadiene, 2-(N-piperidinylmethyl)-1,3-butadiene, 2-triethoxymethyl-1,3-butadiene, 2-(N,N- Dimethylamino)-1,3-butadiene, N-(2-methylene-3-butenoyl)morpholine, 2-methylene-3-butenyl diethyl phosphate, etc. 1, 3-Butadiene, in addition, acrylamide, methacrylamide, sulfophenylacrylamide, sulfophenylitaconimide, acrylonitrile, methacrylonitrile, fumaronitrile, acrylic acid α-cyanide ethyl ethyl ester, citraconic anhydride, vinyl acetic acid, vinyl propionate, vinyl pivalate, vinyl tert-carbonate, crotonic acid, itaconic acid, fumaric acid, 2-(methyl propylene phthalate) Acyloxy)ethyl ester, 2-(methacryloxy)ethyl succinate, 2-(acryloxy)ethyl succinate, methacryloxypropyltrimethoxysilane, Methacryloxypropyldimethoxysilane, Acrolein, Diacetone Acrylamide, Vinyl Methyl Ketone, Vinyl Ethyl Ketone, Diacetone Methacrylate, Vinyl Sulfonic Acid, Isoprene Sulfonic acid, allylsulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, 2-acrylamide-1-methylsulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid acid, vinylpyrrolidone, dehydroalanine, sulfur dioxide, isobutylene, N-vinyl carbitol, vinylidene dicyanide, p-hydroquinodimethane, chlorotrifluoroethylene, tetrafluoroethylene, norbornene, N -Vinyl carbitol, etc. Among them, when copolymerizability with p-styrenesulfonic acid or salt, usability, etc. are considered, styrene, styrene derivatives, methacrylic acid, 2-hydroxyethyl methacrylate, glycidyl methacrylate, N - vinylpyrrolidone, N-phenylmaleimide, maleic anhydride.

The content of non-PSS (salt) components in the above-mentioned PSS (salt) block copolymer is not particularly limited, as long as the content can be adjusted according to the purpose, but the hydrophilicity of the copolymer is too low when it exceeds 98% by weight. Since the function as a dispersant decreases, it is preferably 60% by weight or less.

Next, the method for producing the high-purity p-styrenesulfonic acid (salt) of the present invention will be described.

The manufacture method of high-purity p-styrenesulfonic acid (salt) is not particularly limited, but for example, the p-styrenesulfonic acid (salt) containing impurities can be dropped into pure water or water-soluble solvents such as acetone, isopropanol and water In a mixed solvent, after heating and dissolving at 40-70°C, it is slowly cooled to room temperature, and p-styrenesulfonic acid (salt) is recrystallized to produce it. By repeating this operation, the purity can be further improved. This recrystallization operation is performed once or more, preferably 1 to 3 times in consideration of productivity and cost.

When further specifically illustrating the production example of the high-purity p-styrenesulfonic acid (salt) of the present invention, for example, sodium styrenesulfonate is heated and dissolved in methanol at a concentration of 5 to 6% by weight (usually at 40 to 50° C. for 10 ~ 60 minutes), and slowly cooled to room temperature ~ 10 ℃, after the crystallization of sodium p-styrene sulfonate is precipitated, filtered and dried to obtain high-purity sodium p-styrene sulfonate.

Next, the manufacturing method of the PSS (salt) of this invention is demonstrated.

The method for producing PSS (salt) is not particularly limited, but a method by general radical polymerization is exemplified as the first example. For example, as long as the homogeneous solution of the aqueous solvent and p-styrenesulfonic acid or its salt, and optionally a monomer mixture that can be radically copolymerized with p-styrenesulfonic acid or its salt is put into the reaction vessel, add Molecular weight regulator, after deoxidizing the system, heating to a predetermined temperature, and adding a radical polymerization initiator while polymerizing. At this time, in order to avoid violent polymerization, and when considering the molecular weight controllability in the low molecular weight region, it is preferable not to put all the monomer mixture into the reaction vessel at first, but to mix each monomer with a polymerization initiator or a molecular weight regulator. Together, they were continuously added to the reaction vessel in small amounts one at a time.

The reaction solvent is not particularly limited, but when considering the solubility of styrenesulfonic acid or its salt and comonomer, and the manufacture of aqueous dispersions of nano-carbon materials such as CNT and conductive polymers, aqueous solvents are preferred, such as Mixture of water and water-miscible solvents. The water-soluble solvent is not limited as long as it is a composition that dissolves a mixture of p-styrenesulfonic acid (salt) and a comonomer, and examples thereof include acetone, tetrahydrofuran, dihydrofuran, Alkanes, methanol, ethanol, n-propanol, isopropanol, methoxyethanol, ethoxyethanol, butanol, ethylene glycol, propylene glycol, glycerin, dimethyl sulfoxide, dimethylformamide, N-formaldehyde Base pyrrolidone etc. Preferred are acetone, tetrahydrofuran, di alkanes, dimethylsulfoxide, N-methylpyrrolidone, and dimethylformamide.

The usage-amount of the aqueous solvent used as a reaction solvent is 150-2000 weight part normally with respect to 100 weight part of monomer whole quantities.

The molecular weight regulator is not particularly limited, but examples include diisopropylxanthogen disulfide, diethylxanthogen disulfide, diethylthiuram disulfide, 2,2'-disulfide Thiodipropionic acid, 3,3'-dithiodipropionic acid, 4,4'-dithiodibutyric acid, 2,2'-dithiobisbenzoic acid and other disulfides, n-dodecanoic acid Alkyl mercaptan, octyl mercaptan, tert-butyl mercaptan, thioglycolic acid, thiomalic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiosalicylic acid, 3-mercaptobenzoic acid, 4-Mercaptobenzoic acid, thiomalonic acid, dithiosuccinic acid, thiomaleic acid, thiomaleic anhydride, dithiomaleic acid, thioglutaric acid, cysteine, homosemi Cystine, 5-mercaptotetrazolium acetic acid, 3-mercapto-1-propanesulfonic acid, 3-mercaptopropane-1,2-diol, mercaptoethanol, 1,2-dimethylmercaptoethane, 2-mercapto Ethylamine hydrochloride, 6-mercapto-1-hexanol, 2-mercapto-1-imidazole, 3-mercapto-1,2,4-triazole, cysteine, N-acylcysteine, gluten Thiols such as stathione, N-butylaminoethanethiol, and N,N-diethylaminoethanethiol, halogenated hydrocarbons such as iodoform, diphenylethylene, p-chlorodiphenyl Ethylene, p-cyanodilvin, α-methylstyrene dimer, benzyl dithiobenzoate, 2-cyanopropan-2-yl dithiobenzoate, organotellurium compounds, sulfur, Sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium pyrosulfite, potassium pyrosulfite, etc.

The usage-amount of a molecular weight modifier is 0.1-10 weight part normally with respect to 100 weight part of total monomers.

Examples of the radical polymerization initiator include di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide cumene hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-bis(tert- Butylperoxy)-cyclohexane, cyclohexanone peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisobutyrate, peroxy-3,5,5-trimethyl tert-butyl caproate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisopropylcarboxylate, cumyl peroxyoctanoate, potassium persulfate, ammonium persulfate, Peroxides such as hydrogen peroxide, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-bis Methylvaleronitrile), 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclo Hexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl)azo]formamide, dimethyl 2,2'-azobis(2-methylpropionate) , 4,4'-Azobis(4-cyanovaleric acid), 2,2'-Azobis(2,4,4-trimethylpentane), 2,2'-Azobis{2 -Methyl-N-[1,1'-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}, 2,2'-Azobis{2-(2-imidazolin-2-yl) Propane} dihydrochloride, 2,2'-Azobis{2-(2-imidazolin-2-yl)propane] disulfate dihydrate, 2,2'-Azobis{2-[1 -(2-Hydroxyethyl)-2-imidazolin-2-yl]propane} dihydrochloride, 2,2'-Azobis(1-imino-1-pyrrolidinyl-2-methylpropane ) dihydrochloride, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methyl Azo compounds such as propionamidine] tetrahydrate, etc. In addition, organic reducing agents such as ascorbic acid, erythorbic acid, aniline, and tertiary amines may be used in combination if necessary.

The usage-amount of a radical polymerization initiator is 0.1-10 weight part normally with respect to 100 weight part of total monomers.

The polymerization condition is not particularly limited, as long as it is heated at 40-120° C. for 4-50 hours under an inert gas atmosphere, and it can be adjusted appropriately according to the polymerization solvent, monomer composition and polymerization initiator type.

The PSS (salt) of the present invention can also be produced by the above-mentioned general free radical polymerization, but in order to make the molecular weight distribution narrow or in order to produce block copolymers, the living polymerization method is preferred. Polar monomers, more preferably living radical polymerization. In addition, when p-styrenesulfonic acid esters having extremely high solubility in various solvents are used instead of p-styrenesulfonic acid (salt), it can also be produced by ion polymerization.

Examples of living radical polymerization methods include atom transfer polymerization, stable nitroxyl-mediated polymerization, reversible addition-cleavage transfer polymerization, and organotellurium-mediated polymerization (Proceedings of Polymers, vol.64, No. 6, pp.329, 2007), iodine transfer polymerization (Japanese Patent Laid-Open No. 2007-92014; Polymer Papers, vol.59, No.10, p. 798, 2010), using phosphine and carbon disulfide Polymerization of complexes (Japanese Patent Laid-Open No. 2006-233012), method using trialkylborane (Jointing, Vol. 50, No. 4, p. 23, 2006), dimerization using α-methylstyrene methods (Japanese Patent Application Laid-Open No. 2000-169531), and these methods are applicable to the present invention.

A specific example of living radical polymerization is to carry out living radical polymerization of other radically polymerizable monomers in an aqueous solvent, then add the high-purity p-styrenesulfonic acid (salt) of the present invention, and then continue living radical polymerization, or After living radical polymerization of the p-styrenesulfonic acid (salt) in an aqueous solvent, other radical polymerizable monomers are added, and living radical polymerization is continued. For example, polystyrenesulfonic acid (salt) having a structure specifically exemplified in the above formulas (I) to (III) is obtained by this living radical polymerization.

Here, the type and the like of the aqueous solvent are the same as those in the radical polymerization described above.

As ionic polymerization, for example, the anionic polymerization method using an amine compound (Polymer Preprints, Japan, Vol. 254), if p-styrene sulfonate is used, it is also suitable for use in the present invention.

In addition, among the above-mentioned living radical polymerization methods, when considering the applicability to styrenesulfonic acid or its salt and the ease of polymerization, it is preferable to use a polymerization method using a complex of phosphine and carbon disulfide, that is, using the following formula (IV) The predicted structure of the radical polymerization initiator (controlling agent).

[In formula (IV), R ₃ , R ₄ , and R ₅ each independently represent a linear or branched alkyl or phenyl group that may be substituted, and R ₃ , R ₄ , and R ₅ may be the same or different, R ₁ and R ₂ represent a monovalent group corresponding to a radical generated by a radical generator, and may be the same as or different from each other].

Living radical polymerization conditions are not particularly limited, but as its specific example, drop into p-styrenesulfonic acid or its salt in reaction container, and can carry out radical polymerization with p-styrenesulfonic acid (salt) as required After deoxidizing the homogeneous solution of comonomers in the system, add the above-mentioned radical polymerization initiator (functioning as an initiator and molecular weight control agent), heat to a predetermined temperature, and polymerize, thereby producing PSS with a narrow molecular weight distribution (Salt). Here, after producing PSS (salt), another monomer capable of radical polymerization with p-styrenesulfonic acid (salt) is added in a deoxygenated state, and then polymerized by reheating to produce a PSS (salt) block copolymer . Alternatively, a solution of a monomer that can be radically copolymerized with p-styrenesulfonic acid (salt) is put into a reaction vessel, and after deoxidizing the inside of the system, the above-mentioned radical polymerization initiator is added, heated to a predetermined temperature, and polymerized. In this way, a polymer having a narrow molecular weight distribution is produced, and p-styrenesulfonic acid or its salt is added in a deoxygenated state, followed by reheating polymerization, whereby a PSS (salt) block copolymer can also be produced. In addition, by repeating these operations, a multi-block type PSS (salt) copolymer can be produced.

R ₃ , R ₄ , and R ₅ in the above formula (IV) are each independently a linear or branched alkyl group or phenyl group that may be substituted, but an alkyl group with 1 to 18 carbon atoms is preferred. In terms of solubility in solvents, ethyl, propyl, isopropyl, n-butyl, primary butyl, and tert-butyl are more preferred.

R ₁ and R ₂ represent a monovalent group generated by a radical polymerization initiator, but preferably have a hydrophilic substituent in consideration of the solubility of the polymerization initiator in an aqueous solvent. For example, examples of the radical polymerization initiator include 2,2'-azobis(2-amidinopropane) hydrochloride, 2,2'-azobis(2-aminopropane)nitrate, 2 , 2'-Azobisisobutylamide, 4,4'-Azobis-4-cyanovaleric acid, etc.

The PSS (salt) obtained above is considered to have, for example, the following presumed structure (V) or (VI).

R ₁ to R ₅ in the above formulas (V) and (VI) are the same as R ₁ to R ₅ in the formula (IV), and n and m are the same as A, B of the above-mentioned repeating structural unit or general formula (I) to n and m in (III) are the same. In the above-mentioned PSS (salt), although the initiator moiety of the formula (IV) is contained, it can be removed by hydrolyzing the initiator moiety in an aqueous acid or alkali solution.

As another method for producing PSS (salt) having a narrow molecular weight distribution, a method of sulfonating polystyrene having a narrow molecular weight distribution produced by living polymerization with anhydrous sulfuric acid in a halogenated solvent such as dichloroethane is also conceivable. In this case, if the para-selectivity in the sulfonation reaction is sufficiently high, it can also be used in the present invention.

The PSS (salt) of the present invention can also be randomly copolymerized with other monomers that are free-radically copolymerizable with p-styrenesulfonic acid or its salt, if desired. Although not particularly limited, examples thereof include monomers described in the description of the PSS (salt) block copolymer. When explaining more specifically, for example, in the case of intending to improve the adsorptivity to carbon nanomaterials, N-phenylmaleimide, N-(chlorophenyl)maleimide, N-methyl Phenylmaleimide, N-bromophenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide imine, N-carboxyphenylmaleimide, N-(nitrophenyl)maleimide, N-benzylmaleimide, N-(4-acetoxy-1-naphthalene base) maleimide, N-(4-oxy-1-naphthyl) maleimide, N-(3-fluoranthene) maleimide, N-(5-fluoresceinyl ) maleimide, N-(1-pyrenyl)maleimide, N-(2,3-xylyl)maleimide, N-(2,4-xylyl)maleimide Toimide, N-(2,6-xylyl)maleimide, N-(aminophenyl)maleimide, N-(tribromophenyl)maleimide, N -[4-(2-Benzimidazolyl)phenyl]maleimide, N-(3,5-dinitrophenyl)maleimide, N-(9-acridyl)maleimide Aromatic maleimides such as imides.

In addition, since the PSS (salt) or PSS (salt) solution of the present invention contains impurities from used monomers and polymerization initiators, it can also be used after removal by ion exchange, dialysis, ultrafiltration, etc. In the manufacture of carbon nanotube or conductive polymer dispersions.

Next, a method for producing an aqueous dispersion of carbon nanomaterials such as CNT, graphene, and fullerene will be described.

Here, CNT, graphene, fullerene, etc. which are objects of the present invention have the same chemical meaning as nanocarbon materials. Carbon nanomaterials are a general term for carbon materials that are aggregated and structured in nanometer (nm) units. Therefore, carbon nanotube (Carbon nanotube, CNT for short) is a six-membered ring network (graphene sheet) formed by carbon into a single-layer or multi-layer coaxial tubular substance. It may be classified as one type of fullerene as an isomer of carbon. In addition, graphene is a thin sheet of sp ² bonded carbon atoms with a thickness of 1 atom. Take a hexagonal lattice structure like a honeycomb of carbon atoms and their bonds. In addition, fullerene (fullerene) is a general term for atomic clusters having a minimum structure composed of a plurality of carbon atoms. Different from diamond and graphene whose structure starts with 14 and 6, it is a carbon allotrope starting with tens of atoms.

The method for producing the aqueous dispersion of carbon nanomaterials is not particularly limited, and known methods (for example, JP-A-2009-190940 and JP-A-2010-13312) can be applied. For example, carbon nanomaterials such as CNTs are added to an aqueous solvent containing the PSS (salt) of the present invention while stirring, and the CNTs are dispersed by a bead mill, a homogenizer, and/or ultrasonic irradiation. At this time, in order to improve the water wettability of carbon nanomaterials such as CNT, it is also possible to add a water-soluble solvent of 0.5 to 30% by weight relative to water, and/or an anionic emulsifier, a nonionic emulsifier, a cationic emulsifier, etc. agent, amphoteric emulsifier.

The above-mentioned water-soluble solvents are not particularly limited, and are exemplified by acetone, methanol, ethanol, propanol, butanol, tetrahydrofuran, dihydrofuran, alkanes, ethoxyethanol, methoxyethanol, glycerin, propylene glycol, ethylene glycol, butanediol, acetic acid, propionic acid, etc.

The above-mentioned emulsifier is not particularly limited, but examples of anionic emulsifiers include rosinate, fatty acid salt, alkenyl succinate, alkyl ether carboxylate, alkyl diphenyl ether disulfonate salt, alkane sulfonate, alkyl salicylate sulfonate, polyoxyethylene polycyclic phenyl ether sulfate, α-olefin sulfonate, alkylbenzene sulfonate, naphthalene sulfonate formaldehyde Condensate, taurine derivative, polystyrene sulfonic acid, polystyrene sulfonate methacrylic acid copolymer, polystyrene sulfonate acrylic acid copolymer, polystyrene sulfonate acrylate copolymer, styrene sulfonate horse Acrylic acid copolymer, styrene sulfonate acrylamide copolymer, styrene sulfonate methacrylamide copolymer, styrene sulfonate methacrylate 2-hydroxyethyl ester copolymer, polyethylene sulfonic acid copolymer, polyethylene sulfonate Acid copolymer, polyisoprene sulfonic acid copolymer, polyacrylate acrylic acid copolymer, polymethacrylate methacrylic acid copolymer, polyacrylamide acrylic acid copolymer, polymethacrylamide methacrylic acid copolymer, Alkyl Sulfosuccinates, Alkyl Sulfates, Alkyl Ether Sulfates, Sulfates of Alkyl Propylphenol Polyethylene Oxide Adducts, Allyl Alkylphenol Polyoxyethylene Sulfate salts of adducts, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphate ester salts, sulfonates of higher fatty acid amides, sulfate ester salts of higher fatty acid hydroxyalkylamides, etc., as nonionic Emulsifiers include, for example, polyoxyalkylene alkylamines, alkyl alkanolamides, amine oxide-based nonionic emulsifiers, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, Polyoxyalkylene polycyclic phenyl ether, alkyl acrylphenol polyethylene oxide adduct, allyl alkylphenol polyethylene oxide adduct, polyethylene oxide fatty acid ester, Polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, alkyl polyglycoside, sucrose fatty acid ester, polyethylene oxide polyoxypropylene glycol, polyvinyl alcohol, carboxylate Methyl cellulose, polyvinylpyrrolidone, hydroxyethyl cellulose, polyacrylamide, polymethacrylamide, polydimethylaminoethyl methacrylate, polydimethylaminoethyl acrylate, polymethacrylate diethylamino Ethyl esters, diethylaminoethyl polyacrylate, tert-butylethylaminoethyl polymethacrylate, tert-butylaminoethyl polyacrylate, polydimethylaminoethyl methacrylate/methyl methacrylate copolymer , polydimethylaminoethyl acrylate/methyl methacrylate copolymer, polydimethylaminoethyl methacrylate/butyl acrylate copolymer, polydimethylaminoethyl acrylate/ethyl acrylate copolymer, etc., as cationic Type emulsifiers include, for example, alkylamine salts, alkyl-type quaternary ammonium salts, fatty acid amide amine salts, alkyl amino acid salts, etc., as amphoteric emulsifiers, for example, alkyl dimethylaminoacetic acid betaine, alkyl Dimethylaminosulfobetaine, alkylsulfobetaine, etc.

The PSS (salt) of the present invention is a novel PSS (salt) whose structure is controlled, and is an extremely useful dispersant in the production of aqueous dispersions of nanocarbon materials such as CNT, graphene, and fullerene, which are industrially useful. In addition, the aqueous dispersion of carbon nanomaterials such as CNTs of the present invention may optionally contain a pH adjuster, an antifoaming agent, an antiseptic, a viscosity modifier, a chelating agent, and the like.

Here, in the aqueous dispersion of carbon nanomaterials of the present invention, the ratio of carbon nanomaterials such as CNT, graphene, and fullerene to aqueous media such as water is that the concentration of carbon nanomaterials in the aqueous medium is 0.05 to 10 wt. %, preferably 0.1 to 5% by weight. When it is less than 0.05% by weight, the carbon nanomaterial network formation in the aqueous dispersion coating film becomes insufficient, and sufficient electrical conductivity may not be obtained. On the other hand, when it exceeds 10% by weight, nanocarbon materials such as CNTs may not be sufficiently dispersed, and conductivity corresponding to the amount of nanocarbon materials used may not be obtained.

In addition, in the aqueous dispersion of the nanocarbon material of the present invention, in terms of the ratio of the nanocarbon material such as CNT to the PSS (salt) of the present invention, the weight ratio of the nanocarbon material/PSS (salt) is 1/10 to 10 /1 times, preferably 3/10 to 10/3 times. When it is less than 1/10 times, the amount of PSS (salt) increases relatively, and the effect corresponding to the amount of added PSS (salt) may not be acquired. On the other hand, when it exceeds 10/1, since the amount of PSS (salt) relative to the nanocarbon material is insufficient, the nanocarbon material may not be sufficiently dispersed in an aqueous medium such as water.

In addition, the PSS (salt) of the present invention can also be expected as carbon pigments, CI Pigment Yellow 74, CI Pigment Yellow 109, CI Pigment Yellow 128, CI Pigment Yellow 151, CI Pigment Yellow 14, CI Pigment Yellow 16, CI Pigment Yellow Azo pigments such as 17, copper phthalocyanine blue or its derivatives (CI pigment blue 15:3, CI pigment blue: 15:4), phthalocyanine pigments such as aluminum phthalocyanine, CI pigment violet 48, CI pigment violet 49, CI Pigment Violet 122, CI Pigment Violet 192, CI Pigment Violet 202, CI Pigment Violet 206, CI Pigment Violet 207, CI Pigment Violet 209, CI Pigment Violet 19, CI Pigment Violet 42 and other quinacridone pigments, and isoindol dorinone pigments, two Perazine pigments, perylene pigments, peroxide pigments, thioindigo pigments, anthraquinone pigments, quinophthalone (quinophthalone), indanthrene pigments, diketopyrrolopyrrole pigments, nigrosine pigments, heterocyclic yellow pigments Use as a dispersant for pigments, etc.

Next, a method for producing an aqueous dispersion of conductive polymers such as polythiophenes, polypyrroles, polyanilines, polyphenylenevinylenes, and polyphenylenes will be described. The production method is not particularly limited, and known methods can be applied (for example, JP-A No. 7-90060, JP-A No. 2004-59666, JP-A No. 2010-40770, JP-A No. 2011-102376) .

For example, an aqueous dispersion of a conductive polymer can be produced by dispersing a monomer supplying a conductive polymer in an aqueous solvent containing PSS (salt), and adding an oxidizing agent to carry out oxidative polymerization. At this time, in order to generate finer dispersed particles, oxidative polymerization may be performed while irradiating ultrasonic waves. Subsequently, impurities such as oxidizing agents can also be removed by ion exchange, dialysis, ultrafiltration membrane method, reprecipitation purification, and the like. Alternatively, the monomer supplying the conductive polymer may be dispersed in an aqueous solvent containing the above-mentioned dopant other than PSS (salt), and after adding an oxidizing agent to carry out oxidative polymerization, a poor solvent such as ethanol or methanol may be added to conduct conductive polymerization. After precipitation of the conductive polymer, wash with water or alcohol that does not dissolve the conductive polymer to remove impurities, then add an aqueous PSS (salt) solution, and redisperse it with an emulsifying device such as a homogenizer.

Here, examples of the oxidizing agent include persulfuric acid such as persulfuric acid, potassium persulfate, ammonium persulfate, and sodium persulfate, iron (III) benzenesulfonate, iron (III) p-toluenesulfonate, dodecylbenzene Iron (III) organic acid such as iron sulfonate, iron (III) chloride, iron (III) nitrate, iron (III) sulfate, iron ammonium sulfate (III), iron (III) perchlorate, iron tetrafluoroborate ( III) and other inorganic acids such as iron (III), oxygen, etc.

In the aqueous dispersion of the conductive polymer of the present invention, the ratio of the conductive polymer such as PEDOT to the aqueous medium such as water is such that the concentration of the conductive polymer material in the aqueous medium is 0.1 to 20% by weight, preferably 1 ~10% by weight. When it is less than 0.1% by weight, the network formation of the conductive polymer in the coating film obtained from the aqueous dispersion becomes insufficient, and sufficient conductivity may not be obtained. On the other hand, if it exceeds 10% by weight, conductive polymers such as PEDOT may not be sufficiently dispersed, and conductivity corresponding to the amount of the conductive polymer used may not be obtained.

In addition, in the aqueous dispersion of the conductive polymer of the present invention, the ratio of the conductive polymer such as PEDOT to the PSS (salt) of the present invention is such that the weight ratio of the conductive polymer/PSS (salt) is 1/10 to 1/10. 10/1 times, preferably 3/10 to 10/3 times. When it is less than 1/10, the amount of PSS (salt) is relatively large, and the electrical conductivity of the coating film obtained from the dispersion may not be obtained due to the remaining PSS (salt). On the other hand, when it exceeds 10/1, since the amount of PSS (salt) relative to the conductive polymer is insufficient, the conductive polymer may not be sufficiently dispersed in an aqueous medium such as water.

Water is preferable as the above aqueous solvent (aqueous medium), but a mixed system of water and a water-soluble solvent may also be used. Examples of water-soluble solvents include acetone, methanol, ethanol, propanol, butanol, ethoxyethanol, methoxyethanol, glycerin, propylene glycol, ethylene glycol, butylene glycol, acetic acid, propionic acid, N,N -Dimethylformamide, dimethylsulfoxide, acetonitrile, etc.

In addition, in order to improve the dispersibility of the conductive polymer, a small amount of surfactant may also be added in an auxiliary manner. Although not particularly limited, the surfactants listed in the production example of the carbon nanomaterial aqueous dispersion can be used.

In addition, as the oxygen compound used as a dopant, the PSS (salt) of the present invention is preferable, but methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, 2-naphthalenesulfonic acid, and 10-camphor may be used in combination. Sulfonic acid, 4-hydroxybenzenesulfonic acid, nitrobenzenesulfonic acid, camphorsulfonic acid, 2-anthraquinonesulfonic acid, 1,5-anthraquinonedisulfonic acid, 2,6-anthraquinonedisulfonic acid, poly(2 -acrylamide-2-propanesulfonic acid), lignosulfonic acid, phenolsulfonic acid novolak resin, sulfonated polyester, polyethylenesulfonic acid, polyisoprenesulfonic acid, polymethacryloxybenzenesulfonic acid , bis(trifluoromethanesulfonyl)imide acid, bis(perfluoroalkanesulfonyl)imide, polyacrylic acid methanesulfonic acid and other sulfonic acid compounds, polyacrylic acid, polymethacrylic acid, polyaspartic acid, Polymaleic acid, polyvinylbenzoic acid, acetic acid, maleic acid, carboxyphenol, phthalic aldehyde, carboxyphenol, carboxycresol, carboxynaphthalene, dicarboxynaphthalene and other carboxylic acid compounds, polyphosphoric acid, etc.

In addition, in order to promote the rearrangement of the conductive polymer chains and increase the conductivity, dimethyl sulfoxide, ethylene glycol, Diethylene glycol, glycerin, γ-butyrolactone, sulfolane, N-methylpyrrolidone, dimethyl sulfone, and sugar alcohols such as erythritol, pentaerythritol, and sorbitol.

In addition, for the purpose of improving the adhesion or mechanical properties of the coating film composed of the conductive polymer to various substrates, an aqueous solution of other polymers may be added to the aqueous dispersion of the conductive polymer produced above. or dispersion. Examples thereof include polyester resins, acrylic resins, polyurethane resins, cellulose resins, butyral resins, polyamide resins, polyimide resins, polystyrene resins, polyether resins, gelatin, casein , starch, gum arabic, poly(vinyl alcohol), poly(vinylpyrrolidone), cellulose, polyalkylene glycol, etc.

In addition, ammonia, amine, sodium hydroxide, potassium hydroxide, sodium carbonate, Potassium carbonate, lithium hydroxide, sodium phosphate and other pH regulators.

The structure-controlled PSS (salt) produced in the present invention can be used as a dispersant for producing the above-mentioned carbon nanomaterials or conductive polymer aqueous dispersions, etc., and can also be expected to face the interlayer of solid electrolytic capacitors. Adhesion enhancer, electrode protective film or separator for lithium secondary battery or sodium secondary battery, solid electrolyte, photoblock acid generator, ion exchange resin, allergen capture agent, water treatment agent, semiconductor or hard disk manufacturing Cleaning agent for emulsion paint, modifier for emulsion coating, dispersant for emulsion polymerization or suspension polymerization, antistatic agent, etc.

Example

The present invention is described more specifically through the following examples, but the present invention is not limited by these examples.

It should be noted that in the following examples, the analysis, preparation and evaluation of styrene sulfonate, PSS salt, CNT and PEDOT aqueous dispersions were carried out under the following conditions.

<Measurement of impurities in p-styrenesulfonate by HPLC>

A p-styrenesulfonate sample was dissolved in the following eluent A to prepare a solution with a concentration of 0.5 mg/ml, and HPLC analysis was performed. The conditions are as follows.

Model = LC-8020 manufactured by TOSOH

(Degasser: SD-8022, Pump: CCPM-II, Thermostat Oven: CO-8020, Ultraviolet Visible Light Detector: UV-8020)

Column = TSKgel ODS-80TsQA (4.6mm×25cm)

Eluent=A liquid) water/acetonitrile=95/5+0.1% trifluoroacetic acid

Liquid B) water/acetonitrile=80/20+0.1% trifluoroacetic acid

Gradient conditions = 100% of liquid A until 55 minutes, 100% of liquid B from 55 minutes to 95 minutes

Flow rate = 0.8ml/min, UV detection condition = 230nm, column temperature = room temperature, injection volume = 20μl

In addition, each peak detected by HPLC was previously identified by the following method.

The components detected by HPLC were separated and treated with ion exchange resin to convert the p-styrene sulfonate into sulfonic acid form, and then methylate the sulfonic acid group with diazomethane, and perform gas chromatography mass analysis (manufactured by Hitachi manufactured M-80B), Fourier transform infrared analysis (System 2000 manufactured by Perkin Elmer), organic element analysis (CHN Coder MT-3 manufactured by YANACO), and nuclear magnetic resonance analysis (VXR-300 manufactured by BALIAN Company), Decide on structure.

<Measurement of Polymerization Conversion Ratio of p-Styrene Sulfonate>

In the following GPC measurement, it calculates from the absorption peak intensity of a residual monomer.

<Measurement of Polymerization Conversion Rate of Hydrophobic Monomer>

After diluting the polymerization solution with methanol, use a gas chromatograph (G-17A, manufactured by Shimadzu Corporation) to measure the hydrophobic monomer in the supernatant (column = NEUTRA BOND-5, temperature program = 50 to 200° C. × 10 minutes After holding, the temperature was raised to 300° C. at 5° C./min, and the calibration curve = prepared using 1-methylnaphthalene as an internal standard).

<Determination of molecular weight by GPC>

The molecular weight and molecular weight distribution of the PSS salt were measured under the following conditions.

Model = LC-8020 manufactured by TOSOH

(Degasser: SD-8022, Pump: DP-8020, Thermostat Oven: CO-8020, Ultraviolet Visible Light Detector: UV-8020)

Column = TSK guard column α+TSK gel α-6000+TSK gel α-3000

Eluent = phosphate buffer (pH = 7) and acetonitrile with a volume ratio of 9:1

(The above phosphate buffer was prepared by dissolving 0.08 mol of KH ₂ PO ₄ and 0.12 mol of Na ₂ HPO ₄ in pure water and adjusting the total amount to 1 L)

Column temperature 40°C, flow = 0.6ml/min

Detector=UV detector (wavelength 230nm), injection volume=100μl

Standard curve = Sodium polystyrene sulfonate standard of Chuanghe Science

The molecular weight of the PSS salt-polystyrene block copolymer was measured within the above-mentioned conditions, changing the composition of the eluent to the following composition.

Eluent = aqueous solution of sodium sulfate (0.05mol/L) and acetonitrile with a volume ratio of 65:35

〈Elemental analysis of (co)polymers〉

Regarding carbon, hydrogen, and nitrogen, dry the sample [make the (co)polymer solution vacuum-dry at 100°C for 3 hours, put the dried polymer into acetone in an amount 100 times its weight, and stir at room temperature for 24 hours , undissolved matter was recovered by filtration, and vacuum-dried at 50° C. for 1 hour to remove unreacted hydrophobic monomer] After pulverization, it was measured with a 2400II elemental analyzer manufactured by Perkin Elmer.

In the elemental analysis, regarding sulfur, the above-mentioned dried and pulverized sample was accurately weighed, burned and absorbed by the oxygen bottle combustion method, and then determined by ion chromatography.

The measurement conditions by ion chromatography are as follows.

Column = TSK gel Super IC-AP, eluent = 2.7mM sodium bicarbonate + 1.8mM sodium carbonate, column temperature = 40°C, flow rate = 0.8ml/min, detector = conductivity

〈FT-IR analysis of (co)polymers〉

The samples were prepared by the KBr pellet method, and the Perkin Elmer system 2000 was used for measurement. The measurement wavelength range is 4000 to 400 cm ^-1 , and the number of measurements is 16 times.

<Particle size measurement of aqueous dispersions of CNT and PEDOT>

Dispersibility and stability were evaluated by visual observation of the aqueous dispersion and particle size measurement with a dynamic light scattering particle size distribution meter Nanotrac UPA-UT151 (manufactured by Nikkiso Co., Ltd.). D50% particle diameter (median particle diameter) was used as the average particle diameter, and it was set as the standard of dispersion degree.

<precipitation>

The aqueous dispersion was centrifuged at 3500 rpm for 30 minutes using a desktop centrifugal separator NT-8 manufactured by MICROTEC NITION Co., Ltd., and the presence or absence of precipitation was visually observed. The aqueous dispersions without precipitation were evaluated as ○ and only a little The aqueous dispersion that precipitated was evaluated as Δ, and the aqueous dispersion that precipitated was evaluated as ×.

<Measurement of Conductivity of Conductive Polymers>

Drop 100 μl of an aqueous dispersion of conductive polymer on a glass plate, apply it with a No. 8 bar coater, and then dry it in a constant temperature bath at 80°C for 10 minutes, and then dry it at 150°C for 30 minutes to make a conductive permanent polymer film. Subsequently, the film thickness was measured with a digital micrometer (MDC-25NJ manufactured by MITUTOYO), and the surface resistance (Ω/ ) and conductivity.

<Stability Evaluation of Conductive Polymer Aqueous Dispersion>

After storing the aqueous dispersion in a thermostat at 50° C. for 7 days, the particle size and electrical conductivity were measured by the above method, and the stability was evaluated.

Production Example 1 [Synthesis of Radical Polymerization Initiator (Radical Polymerization Controlling Agent)]

Under a nitrogen atmosphere, 24 ml of methanol, 4.21 g (55.31 mmol) of carbon disulfide, 1.00 g (3.69 mmol) of an azo initiator V-50 (manufactured by Wako Pure Chemical Industries, Ltd.), and 3.73 g (18.44 mmol) of tri-n-butylphosphine were mixed. The mixture was put into a reaction container made of pressure-resistant glass, and reacted at 50° C. for 72 hours while stirring with a magnet stirrer under a nitrogen atmosphere. After the reaction, methanol and unreacted carbon disulfide were distilled off under reduced pressure to obtain a living radical polymerization control agent.

Embodiment 1 (manufacture example of high-purity PSSNa and CNT dispersion)

(manufacture of high-purity PSSNa)

Put 1000 g of commercially available sodium p-styrene sulfonate (SPINOMAR NaSS manufactured by TOSOH Organic Chemicals Co., Ltd.), 950 g of pure water, 40 g of sodium hydroxide, and 1 g of sodium nitrite into a 2L detachable flask, and heat at 60° C. for 1 hour, Dissolve completely while stirring. Subsequently, it was cooled to 10° C. at a rate of 10° C. for 1 hour, crystals were precipitated, and sodium p-styrenesulfonate was recovered by centrifugal filtration. A small amount of sample was accurately weighed, and the water content was calculated from the weight after vacuum drying at 50° C. for 6 hours, and it was 9.2% by weight. Sodium bromide measured with an ion chromatograph was 0.19% by weight, and sodium sulfate was 0.04% by weight. That is, the monomer component to which sodium β-bromoethylbenzenesulfonate was added was 90.57% by weight.

Organic impurities such as isomers contained in the above-mentioned sodium p-styrene sulfonate were analyzed by HPLC, and the results were (a) 0.16%, (b) 0.43%, (c) 2.65%, (d) 0.04% (in Fig. 1 HPLC profile is shown).

Next, 100.00 g of pure water was poured into a 1 L glass flask equipped with a reflux cooling pipe, a nitrogen introduction pipe, and a paddle stirrer, and heated in an oil bath at 85° C. under a nitrogen atmosphere. Therein, a separately prepared aqueous solution of sodium p-styrenesulfonate [which was obtained by dissolving 223.00 g of high-purity sodium p-styrenesulfonate containing water and the like obtained above in 884.00 g of pure water] was added dropwise over 104 minutes, followed by Over 113 minutes, an aqueous initiator solution (dissolving 2.77 g of ammonium persulfate in 121.00 g of pure water) was added dropwise to perform polymerization. After 3 hours from the start of the polymerization, the temperature of the oil bath was raised to 90° C., and the polymerization was continued for 3 hours to obtain an aqueous solution of sodium polystyrene sulfonate.

The number average molecular weight Mn of sodium polystyrene sulfonate determined by GPC was 57,000, and the weight average molecular weight Mw was 160,000 (Mw/Mn=2.81). Let this polymer be PSS-1.

(Manufacture of CNT aqueous dispersion)

0.1 g of the vacuum-dried polystyrene sulfonate obtained above was dissolved in a mixed solvent of 8 ml of pure water and 2 ml of acetone (0.1% by weight solution). After adding 0.1g of multilayer CNT (manufactured by Tokyo Chemical Industry Co., Ltd., diameter 20-40nm, length 1-2μm), disperse treatment with ultrasonic emulsifier (Nippon Seiki US-600T) for 1 hour to obtain CNT aqueous dispersion body (CNT concentration 1% by weight, CNT/polystyrene sulfonate weight ratio = 1). At this time, the liquid temperature was kept below 40°C.

Table 1 shows the composition and evaluation results (average particle diameter and pH immediately after production and after storage at 50° C.×14 days) of the CNT aqueous dispersion. Compared with Comparative Example 1 described later, it can be seen that all have excellent storage stability.

Embodiment 2 (manufacture example of high-purity PSSLi and CNT dispersion)

(manufacture of high-purity PSSLi)

In Example 1, lithium p-styrenesulfonate (LiSS manufactured by TOSOH Organic Chemicals Co., Ltd.) and lithium hydroxide were used instead of sodium p-styrenesulfonate and sodium hydroxide, and the same recrystallization as in Example 1 was repeated twice. Purify to obtain high-purity lithium p-styrenesulfonate with impurity content of (a) 0.14%, (b) 0.04%, (c) 0.01%, (d) 0.09%. The HPLC profile of this product is shown in FIG. 2 .

Next, polymerization was carried out under exactly the same conditions as in Example 1 except that 205.00 g of this lithium p-styrenesulfonate was used to obtain an aqueous lithium polystyrenesulfonate solution.

The number average molecular weight Mn of lithium polystyrene sulfonate determined by GPC was 59000, and the weight average molecular weight Mw was 156000 (Mw/Mn=2.64). This polymer was set as PSS-2.

(Manufacture of CNT aqueous dispersion)

A CNT aqueous dispersion was obtained under exactly the same conditions as in Example 1, except that the vacuum-dried polystyrene sulfonate obtained above was used.

Table 1 shows the composition and evaluation results (average particle diameter and pH immediately after production and after storage at 50° C.×14 days) of the CNT aqueous dispersion. Compared with Comparative Example 1 described later, it can be seen that all have excellent storage stability.

Example 3 (Preparation of High Purity and Narrow Molecular Weight Distribution PSSLi and CNT Aqueous Dispersion)

(Manufacture of PSLi with high purity and narrow molecular weight distribution)

The high-purity p-styrene sulfonate lithium [impurity content (a) 0.14%, (b) 0.04%, ( c) 0.01%, (d) 0.09%] 205.00 g and 800.00 g of pure water were heated and stirred at 40° C. for 5 minutes under a nitrogen atmosphere to dissolve them. 3.02 g of the living radical polymerization initiator obtained in Production Example 1 was added thereto, and polymerized at an oil bath temperature of 65° C. for 12 hours to obtain an aqueous lithium polystyrenesulfonate solution.

The number-average molecular weight of lithium polystyrenesulfonate determined by GPC was 127,000, and the weight-average molecular weight was 165,000 (Mw/Mn=1.30). Let this polymer be PSS-3.

(Manufacture of CNT aqueous dispersion)

A CNT aqueous dispersion was obtained under exactly the same conditions as in Example 1, except that the vacuum-dried polystyrene sulfonate obtained above was used.

Table 1 shows the composition and evaluation results (average particle diameter and pH immediately after production and after storage at 50° C.×14 days) of the CNT aqueous dispersion. Compared with Comparative Example 1 described later, it can be seen that all have excellent storage stability. In addition, since the dispersibility is superior to Examples 1 and 2, narrowing the molecular weight distribution of PSS is considered to have an influence.

Example 4 (Manufacture of High Purity and Narrow Molecular Weight Distribution PSSLi (Molecular Weight Reduction of PSS-3) and CNT Aqueous Dispersion)

(Manufacture of PSLi with high purity and narrow molecular weight distribution)

In Example 3, except that the addition amount of the living radical polymerization initiator obtained in Production Example 1 was changed to 5.00 g, polymerization was carried out under exactly the same conditions as in Example 3 to obtain an aqueous lithium polystyrenesulfonate solution.

The number average molecular weight Mn of lithium polystyrene sulfonate determined by GPC was 73000, and the weight average molecular weight Mw was 94000 (Mw/Mn=1.29). This polymer was set as PSS-4.

(Manufacture of CNT aqueous dispersion)

A CNT aqueous dispersion was obtained under exactly the same conditions as in Example 1, except that the vacuum-dried polystyrene sulfonate obtained above was used.

Table 1 shows the composition and evaluation results (average particle diameter and pH immediately after production and after storage at 50° C.×14 days) of the CNT aqueous dispersion. Compared with Comparative Example 1, it can be seen that all have excellent storage stability. In addition, since the dispersibility is superior to that of Examples 1 and 2, narrowing the molecular weight distribution of PSS is considered to have an influence.

Example 5 (Manufacture of N-phenylmaleimide random copolymer with narrow molecular weight distribution and production example of CNT aqueous dispersion)

(manufacture of random copolymers)

Drop into the high-purity sodium p-styrenesulfonate obtained in Example 1 [impurity content (a) 0.16%, (b) 0.43%, ( c) 2.65%, (d) 0.04%] 35.00 g, and 282.00 g of pure water were dissolved by heating and stirring in an oil bath at 40° C. for 5 minutes under a nitrogen atmosphere. Add an acetone solution of N-phenylmaleimide (dissolve 7.00 g of N-phenylmaleimide in 254.00 g of acetone) therein, and after raising the temperature in an oil bath at 65° C., add 4.00 g of the obtained living radical polymerization initiator was polymerized at a temperature of 65° C. for 12 hours.

The polymerization solution was transparent, and the residual monomer concentration in the solution was analyzed, and the results showed that both sodium p-styrenesulfonate and N-phenylmaleimide were <0.1% by weight.

The elemental analysis values of the vacuum-dried polymer were 45.8% by weight of carbon, 3.20% by weight of hydrogen, 1.3% by weight of nitrogen, and 10.7% by weight of sulfur, which was almost identical to the composition of the input monomer, and although it contained 17% by weight of N-phenylmaleimide component, but the copolymer is still water-soluble, in the FT-IR spectrum, see the absorption peak ( 1707cm- ¹ and 1040cm- ¹ , respectively), so this polymer was judged to be a copolymer having a composition of p-styrenesulfonate sodium residue:N-phenylmaleimide residue=80:20 mol% . The number average molecular weight Mn of the copolymer determined by GPC was 19000, and the weight average molecular weight Mw was 26000 (Mw/Mn=1.37). This polymer was set as PSS-5.

(Manufacture of CNT aqueous dispersion)

A CNT aqueous dispersion was obtained under exactly the same conditions as in Example 1, except that the vacuum-dried polystyrene sulfonate obtained above was used.

Table 1 shows the composition and evaluation results (average particle diameter and pH immediately after production and after storage at 50° C.×14 days) of the CNT aqueous dispersion. Compared with Comparative Example 1, it can be seen that all have excellent storage stability. In addition, since the dispersibility is superior to that of Examples 1 to 4, it is considered that the introduction of N-phenylmaleimide, which has strong adsorption to CNTs, into the PSS skeleton has an influence.

Example 6 (Manufacture example of methacrylic acid block copolymer and CNT aqueous dispersion)

(Manufacture of methacrylic acid block copolymer)

In a 1L glass flask equipped with a reflux cooling pipe, a nitrogen introduction pipe, and a paddle stirrer, under a nitrogen atmosphere, drop into the high-purity sodium styrene sulfonate obtained in Example 1 [impurity content (a) 0.16%, (b ) 0.43%, (c) 2.65%, (d) 0.04%] 120.00g, pure water 546.00g, heated and stirred in an oil bath at 40°C to dissolve sodium p-styrenesulfonate. After raising the temperature of the oil bath to 65° C., 2.00 g of the living radical polymerization initiator obtained in Production Example 1 was quickly added, and heated and polymerized for 10 hours.

0.5ml of the polymerization solution was drawn out with a syringe, and measured by GPC, the concentration of p-styrenesulfonic acid was <0.1% by weight, the number average molecular weight Mn was 109000, and the weight average molecular weight Mw was 136000 (Mw/Mn=1.25).

The bath temperature was kept at 65°C, and 69.04 g of an aqueous sodium methacrylate solution (a solution consisting of 13.00 g of methacrylic acid, 6.04 g of sodium hydroxide, and 50.00 g of pure water) was added, and polymerization was continued for 12 hours.

The number average molecular weight Mn of the copolymer obtained by GPC was 121000, the weight average molecular weight Mw was 164000 (Mw/Mn=1.36), and the peak of the first polymerized sodium polystyrene sulfonate shifted to the high molecular weight side. The concentration of methacrylic acid in the polymerization solution is <0.1% by weight.

The elemental analysis value of the vacuum-dried polymer was 48.1% by weight of carbon, 3.4% by weight of hydrogen, and 13.2% by weight of sulfur. Since the composition of the monomer was almost the same as that of the charged monomer, the polymer was judged to contain sodium polystyrene sulfonate. : A block copolymer having a composition of polymethacrylic acid = 79: 21 mol%. This polymer was set as PSS-6.

(Manufacture of CNT aqueous dispersion)

A CNT aqueous dispersion was obtained under exactly the same conditions as in Example 1, except that the vacuum-dried polystyrene sulfonate obtained above was used.

Table 1 shows the composition and evaluation results (average particle diameter and pH immediately after production and after storage at 50° C.×14 days) of the CNT aqueous dispersion. Compared with Comparative Example 1, it can be seen that all have excellent storage stability. In addition, since the dispersibility is superior to that of Examples 1 to 4, it is considered that the linking of a component having a lower hydrophilicity than p-styrenesulfonic acid to PSS exerts an influence.

Example 7 (Manufacture example of styrene block copolymer and CNT aqueous dispersion)

(Manufacture of Styrene Block Copolymer)

Drop into the high-purity sodium styrene sulfonate obtained in embodiment 1 [impurity content (a) 0.16%, (b) 0.43%, (c) ) 2.65%, (d) 0.04%] 35.00 g and 280 g of pure water, heated and stirred in an oil bath at 40° C. to dissolve sodium p-styrenesulfonate. After raising the temperature of the oil bath to 65° C., 0.88 g of the living radical polymerization initiator obtained in Production Example 1 was quickly added, and heated and polymerized for 12 hours.

0.5ml of the polymerization solution was drawn out with a syringe and measured by GPC. As a result, the concentration of p-styrenesulfonic acid was <0.1% by weight, the number average molecular weight Mn was 73000, and the weight average molecular weight Mw was 91000 (Mw/Mn=1.25).

The bath temperature was kept at 65° C., 232 g of a styrene solution (a solution consisting of 2.00 g of styrene and 230 g of acetone) was added, and polymerization was continued for 24 hours.

The polymerization solution is transparent, and the styrene concentration in the solution is <0.1% by weight.

The elemental analysis value of the vacuum-dried polymer was 44.3% by weight of carbon, 3.4% by weight of hydrogen, and 13.8% by weight of sulfur. Since the composition of the polymer was almost the same as that of the charged monomer, it contained 5% by weight of styrene which was insoluble in water. , but the copolymer was still water-soluble, and the polymer was judged to be a copolymer having a composition of sodium polystyrenesulfonate residue:styrene residue=90:10 mol%. The number average molecular weight Mn of the copolymer determined by GPC was 77,000, and the weight average molecular weight Mw was 116,000 (Mw/Mn=1.51). This polymer was set as PSS-7.

(Manufacture of CNT aqueous dispersion)

A CNT aqueous dispersion was obtained under exactly the same conditions as in Example 1, except that the vacuum-dried polystyrene sulfonate obtained above was used.

Table 1 shows the composition and evaluation results (average particle diameter and pH immediately after production and after storage at 50° C.×14 days) of the CNT aqueous dispersion. Compared with Comparative Example 1 described later, it can be seen that all have excellent storage stability. In addition, since the dispersibility is superior to that of Examples 1 to 4, it is considered that the connection of polystyrene with high hydrophobicity to PSS has an influence.

Comparative Example 1 (example using low-purity sodium styrene sulfonate)

(Manufacture of low-purity PSSNa)

Except using commercially available impurity content (a) 0.38%, (b) 3.87%, (c) 7.77%, (d) 0.06% low-purity sodium p-styrene sulfonate 223.00g, with exactly the same as embodiment 1 Polymerization was carried out under certain conditions to obtain an aqueous solution of sodium polystyrene sulfonate.

The number average molecular weight Mn of sodium polystyrene sulfonate obtained by GPC was 52000, and the weight average molecular weight Mw was 161000 (Mw/Mn=3.10). This polymer was set as PSS-8. In addition, the HPLC chart of the above-mentioned low-purity sodium p-styrene sulfonate is shown in FIG. 3 .

(Manufacture of CNT aqueous dispersion)

A CNT aqueous dispersion was obtained under exactly the same conditions as in Example 1, except that the vacuum-dried polystyrene sulfonate obtained above was used.

Table 1 shows the composition and evaluation results (average particle diameter and pH immediately after production and after storage at 50° C.×14 days) of the CNT aqueous dispersion. Compared with the examples, although no significant difference was seen in the particle diameter immediately after preparation, a decrease in dispersion stability over time or a decrease in pH were clearly observed.

Examples 8-13 (manufacture and evaluation of conductive polymer dispersion)

First, unnecessary ions contained in the polystyrene acid salt solutions obtained in Examples 1-4, 6, and 7 were removed according to the method of JP-A-60-15408. That is, by treating polystyrene sulfonate solution with a column filled with anion exchange resin [Amberlite IRA-410 (resin regenerated with sodium hydroxide)] to remove anions such as bromine and sulfate ions, Resin [Organo Corporation Amberlite RB-120 (resin regenerated with hydrochloric acid)] was used to remove cations such as sodium and lithium. Subsequently, the solid content (measured after vacuum drying at 100° C. for 3 hours) was adjusted to 10.00% by weight.

20.00 g of the above-mentioned PSS saline solution and 1.00 g of 3,4-ethylenedioxythiophene (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.) were put into 100 ml of pure water at room temperature, and vigorously stirred with a stirring blade for 30 minutes. Next, 1 ml of a 20% by weight ammonium persulfate aqueous solution was added as an oxidizing agent under stirring conditions at room temperature to start oxidative polymerization. Then, 1 ml of 20% by weight ammonium persulfate aqueous solution was added 7 times (total 8 ml) every 10 minutes, and the mixture was polymerized while stirring at normal temperature for 60 hours.

Subsequently, ultrasonic irradiation (US-600T manufactured by Nippon Seiki) was performed at normal temperature for 10 minutes to make the PEDOT dispersion particles obtained above smaller.

Then, add 5 ml of cation exchange resin [Amberlite RB-120 manufactured by Organo (regenerated with hydrochloric acid)], 7 ml of anion exchange resin [Amberlite IRA-410 (regenerated with sodium hydroxide)], slowly Stir for 2 hours. Subsequently, the cation exchange resin and the anion exchange resin were filtered off to obtain PEDOT having a solid content of 1.9% by weight. Furthermore, 5% by weight of dimethyl sulfoxide was added to the PEDOT component in the PEDOT aqueous dispersion, and the physical properties of the dispersion were evaluated. Table 2 shows the type of PSS salt used as a dispersant and properties of the dispersion (average particle diameter and electrical conductivity immediately after production and after storage at 50° C.×7 days).

Compared with the comparative example 2 mentioned later, it turns out that it is excellent in both electrical conductivity and storage stability. In addition, it can be seen that in the styrene sulfonate homopolymer, the narrower the molecular weight distribution (Examples 10 and 11 using PSS-3 and 4), the better the electrical conductivity.

Comparative example 2

In Examples 8-13, except using the polystyrene sulfonate solution obtained in Comparative Example 1 to replace the polystyrene sulfonate solution obtained in Examples 1-4, 6, and 7, with the 8-13 The PEDOT aqueous dispersion was obtained under exactly the same conditions.

Table 2 shows the type of PSS salt used as a dispersant and properties of the dispersion (average particle diameter and electrical conductivity immediately after production and after storage at 50° C.×7 days). Although no significant difference was observed in the particle diameter immediately after preparation, a decrease in electrical conductivity and stability over time was clearly observed.

Industrial Utilization Possibility

Utilize the nano-carbon material and the aqueous dispersion of conductive polymer formed by structure-controlled polystyrene sulfonic acid or its salt of the present invention can be used for conductive paint, LSI wiring, electromagnetic wave shielding material, electrochemical device (fuel) Batteries, secondary batteries, capacitors, field emission displays, transistors, solar cells, various electrodes), antistatic coatings, organic EL, touch panels, can be used for the industrialization of nano-carbon materials or conductive polymers to contribute.

Symbol Description

(a): Absorption strength of o-styrene sulfonate

(b): Absorption intensity of β-bromoethylbenzenesulfonate

(c): Absorption strength of m-styrene sulfonate

(d): Absorption strength of bromostyrene sulfonate

Claims (2)

1. a manufacture method for high-purity sodium p styrene sulfonate, the condition that sodium p styrene sulfonate is existed sodium nitrite Under, at pure water or water-soluble solvent, the mixed solvent with water heats, then, slowly cool to room temperature, recrystallize and obtain Arrive so that as in sodium p styrene sulfonate sometimes with (a) adjacent styrene of the major impurity being derived from Materials Styrene Sodium styrene sulfonate between sodium sulfonate, (b) β-bromo ethyl phenenyl sodium sulfonate, (c), (d) bromstyrol sodium sulfonate with high-efficient liquid phase color The peak area benchmark that spectrometry is tried to achieve be respectively (a)≤0.20%, (b)≤0.50%, (c)≤3.00% and (d) containing ratio ≤ 0.10%, wherein, sodium p styrene sulfonate is 100 with the summation of (a)～(d) peak area.

2. a manufacture method for kayexalate, uses the high-purity sodium p styrene sulfonate system described in claim 1 Making, kayexalate is in an aqueous medium described high-purity sodium p styrene sulfonate to be carried out radical polymerization and obtains , described kayexalate has a following constitutional repeating unit A, or has following constitutional repeating unit A and following heavy Complex structure unit B, the weight average molecular weight tried to achieve with gel permeation chromatography i.e. GPC is 2,000～1,000,000, and weight average molecular weight with The ratio of number-average molecular weight is less than 2.0, the ratio=weight-average molecular weight/number-average molecular weight of this weight average molecular weight and number-average molecular weight,

In constitutional repeating unit A, B, M represents that sodium cation, Q represent other free radical polymerization monomer residue, and n represents more than 1 Integer, m represents the integer of more than 0.