CN103958552B

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

Info

Publication number: CN103958552B
Application number: CN201280055963.0A
Authority: CN
Inventors: 尾添真治; 山野井健; 山野井健一; 松永秀秋
Original assignee: Tosoh Organic Chemical Co Ltd
Current assignee: Tosoh Organic Chemical Co Ltd
Priority date: 2011-11-16
Filing date: 2012-08-31
Publication date: 2016-11-16
Anticipated expiration: 2032-08-31
Also published as: TWI573781B; WO2013073259A1; JPWO2013073259A1; JP5954798B2; TW201335125A; CN103958552A

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 system of kayexalate Make method

Technical field

The present invention relates to high-purity p styrene sulfonic acid (salt), employ its polystyrolsulfon acid through structure control (salt) and as dispersant purposes and use its nano-carbon material manufactured and the aqueous dispersion of electric conductive polymer, Further relate to the manufacture method of this polystyrolsulfon acid (salt).

Background technology

CNT (hereinafter referred to as CNT) due to have light weight high intensity, high abrasion resistance, high-termal conductivity, high-melting-point, The characteristics such as high conductivity, semiconduction, high-specific surface area, hollow structure, high gas adsorbability, biocompatibility, it is therefore contemplated that Have towards high-strength material, high conductivity material, conductive material, LSI distribution, micromechanics (micro machine), titanium dioxide Carbon fixation material, hydrogen occlusion material, electromagnetic shielding material, catalyst bearing material, nanofilter, biosensor, Delivery system, electrochemical appliance (fuel cell, secondary cell, capacitor, transistor, Field Emission Display, Electronic Paper, Thin film organic solar battery, DSSC, organic EL, contact panel, various electrode) etc. application.

But, CNT easily condenses because of molecular separating force, and this character becomes the practical maximum barrier in above-mentioned field Hinder.Accordingly, strongly seek not make CNT cohesion be allowed to stably carry out nano-dispersed in solvent or various polymeric matrix Technology.

Such as, to the making of the fine distribution of the integrated circuit utilizing ink jet printing mode to carry out, utilize half tone to print The manufacture in the field-transmitting cathode source that brush mode is carried out and flat faced display carry out applied research, therefore divide for required CNT aqueous The manufacture method of a prose style free from parallelism, it is proposed that kinds of schemes.Such as, it has been disclosed that employ the anionic surface work with steroid skeleton The manufacture method (see, for example patent documentation 1) of the CNT aqueous dispersion of property agent, and it is disclosed in dispersant employing 12 The manufacture method (see, for example patent documentation 2) of the CNT aqueous dispersion in alkyl itaconic acid.Additionally it has been disclosed that it is hydrophilic to have The triphenylene derivatives of base irradiates the ultrasound wave of height output as dispersant, limit, and limit manufactures the method (ginseng of CNT aqueous dispersion As usual such as patent documentation 3), or employ the cellulose derivative with particular functional group autofrettage (see, for example patent literary composition Offer 4).But, any of the above-described method all may not disclosure satisfy that dispersion effect, and has the problem using dispersant etc. costly.

On the other hand, the method that make use of styrene sulfonic acid is also known.Such as, it has been disclosed that employ polystyrene sulphur The manufacture method (see, for example patent documentation 5 and patent documentation 6) of the CNT aqueous dispersion of hydrochlorate (homopolymer).Additionally it has been disclosed that Employ the manufacture method (see, for example patent documentation 7) of the CNT aqueous dispersion of styrenesulfonic-maleic acid copolymer salt.This Though a little polystyrolsulfon acid polymer salts can, lower cost ground industrialized production high with safety, but dispersion effect can not be said to be Sufficiently, therefore it is required that the further of dispersion effect is improved.

On the other hand, with regard to polythiophene class, multi-metal polypyrrole, polyaniline compound, polyphenylenevinylene (Polyphenylene Vinylene) the organic conductive polymer (hereinafter referred to as electric conductive polymer) such as class, polyphenylene (Polyphenylene) class For, from the viewpoint of electric conductivity, flexibility, light weight, as antistatic coating, solid electrolytic capacitor electrode, electromagnetism Wave screen covers material, starter motor (actuator), collection of energy (energy harvesting) (generating) material, and lithium secondary electricity Pond, sodium rechargeable battery, organic thin film solar cell, DSSC, organic el display, Electronic Paper, touch-control The component of panel etc., the succedaneum of ITO (tin indium oxide) transparency electrode and expected.But, above-mentioned electric conductive polymer by In identical with CNT, for insoluble and do not melt, therefore, it is difficult to coating processing.Therefore, electric conductive polymer is had with microgranular being scattered in Type in machine solvent or aqueous solvent has become the main flow of exploitation, and the most commercially available.

In order to manufacture the aqueous dispersion of electric conductive polymer, need in order to make electric conductive polymer with micropartical or nanometer Particle shape is the dispersant of stabilisation in water, but main flow now is polystyrolsulfon acid (see, for example patent documentation 8,9).Poly- Styrene sulfonic acid (hereinafter referred to as PSS) is strong electrolyte polymeric thing, not only plays the effect as dispersant, also plays to open up The effect of the adulterant of the electric conductivity of existing electric conductive polymer.

But, conventional electric conductive polymer aqueous dispersion is as ito transparent electrode succedaneum or electromagnetic wave shielding During material, electric conductivity is the most not enough, it addition, stability, resistance to water and the adaptation to various base materials such as aluminum, tantalum, glass, polyester films Difference, therefore expects the improvement to these strongly.Above-mentioned low conductivity, stability, resistance to water and adaptation it is said that with as point The remaining PSS of powder function has much relations.

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2009-242126 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2010-13312 publication

Patent documentation 3: Japanese Unexamined Patent Publication 2009-190940 publication

Patent documentation 4: Japanese Unexamined Patent Publication 2011-127041 publication

Patent documentation 5: Japanese Unexamined Patent Publication 2005-263608 publication

Patent documentation 6: Japanese Unexamined Patent Publication 2010-254546 publication

Patent documentation 7: Japanese Unexamined Patent Application Publication 2006-525220 publication

Patent documentation 8: Japanese Unexamined Patent Publication 7-90060 publication

Patent documentation 9: Japanese Unexamined Patent Publication 2004-59666 publication

Summary of the invention

The present invention completes in view of above-mentioned problem, its object is to provide a kind of as in order to manufacture CNT, Graphene (graphene), the nano-carbon material such as fullerene and polythiophene class, multi-metal polypyrrole, polyaniline compound, polyphenylenevinylene class, poly- The PSS through structure control that the dispersant of the aqueous dispersion of the electric conductive polymers such as phenylene class is useful or its salt are (the most also It is referred to as " PSS (salt) ").

The present inventor etc. actively study for solving above-mentioned problem, found that become through the PSS (salt) of structure control For for nano-carbon material and polythiophene class, multi-metal polypyrrole, polyaniline compound, polyphenylene Asia second such as CNT, Graphene, fullerenes The physical property of the aqueous dispersion of the electric conductive polymers such as alkenes, polyphenylene class improves useful dispersant, thus completes this Bright.

The present invention relates to a kind of high-purity p styrene sulfonic acid or its salt (hereinafter also referred to " p styrene sulfonic acid (salt) "), Wherein, as in p styrene sulfonic acid (salt) sometimes with (a) adjacent styrene sulphur of the major impurity being derived from Materials Styrene Styrene sulfonic acid (salt) between acid (salt), (b) β-bromo ethyl phenenyl sulfonic acid (salt), (c), (d) bromstyrol sulfonic acid (salt) with efficiently The peak area benchmark that liquid chromatography (hereinafter referred to as HPLC) is tried to achieve containing ratio be respectively (a)≤0.20%, (b)≤ 0.50%, (c)≤3.00% and (d)≤0.10% (wherein, p styrene sulfonic acid (salt) and the summation of (a)～(d) peak area It is 100).

Then, the present invention relates to a kind of polystyrolsulfon acid or its salt (hereinafter also referred to " polystyrolsulfon acid (salt) "), It uses above-mentioned high-purity p styrene sulfonic acid (salt) to manufacture, and has following constitutional repeating unit A, or has following heavy Complex structure unit A and following constitutional repeating unit B,

[in constitutional repeating unit A, B, M represent sodium cation, lithium cation, potassium cationic, ammonium cation, quaternary ammonium sun from Son or proton, Q represents free radical polymerization monomer residue, and n represents the integer of more than 1, and m represents the integer of more than 0].

The polystyrolsulfon acid (salt) of the present invention preferably has the poly-of at least any structure in following formula (I)～(III) Styrene sulfonic acid (salt),

[in formula (I)～(III), M represent sodium cation, lithium cation, potassium cationic, ammonium cation, quaternary ammonium cation or Proton, Q represents other free radical polymerization monomer residue, and n and n ' represents the integer of more than 1, m and m ' represent more than 0 whole Number].

Herein, the weight tried to achieve with gel permeation chromatography (hereinafter referred to as GPC) of the polystyrolsulfon acid (salt) of the present invention Average molecular weight preferably 2,000～1,000,000, weight average molecular weight is excellent with the ratio (=weight-average molecular weight/number-average molecular weight) of number-average molecular weight Choosing is less than 2.0.

It addition, as the Q in above-mentioned constitutional repeating unit B and above-mentioned (I)～(III), be preferably selected from styrene residue, Styrene derivative residue, methacrylic acid residue, 2-hydroxyethyl methacrylate residue, glycidyl methacrylate Residue, (methyl) acrylamide residue, NVP residue, N-phenylmaleimide residue, maleic anhydride are residual More than one free radical polymerization monomer residue in base.

Then, the present invention relates to more than one and state polystyrolsulfon acid (salt) as the dispersant of effective ingredient and electric conductivity Polymer-doped dose.

Moreover, it relates to a kind of nano-sized carbon using above-mentioned polystyrolsulfon acid (salt) to be fabricated by as dispersant Material aqueous dispersion, and use the conductive poly that above-mentioned polystyrolsulfon acid (salt) is fabricated by as dispersant and adulterant Compound aqueous dispersion.

Then, the present invention relates to above-mentioned high-purity p styrene sulfonic acid (salt) is carried out in aqueous solvent radical polymerization Or the manufacture method of the above-mentioned polystyrolsulfon acid (salt) of active free radical polymerization.

Moreover, it relates to the manufacture method of a kind of above-mentioned polystyrolsulfon acid (salt), wherein will in aqueous solvent After free radical polymerization monomer carries out active free radical polymerization, add above-mentioned p styrene sulfonic acid (salt), be further continued for activity freely Base is polymerized, or after this p styrene sulfonic acid (salt) being carried out active free radical polymerization in aqueous solvent, adds radical polymerization Conjunction property monomer, is further continued for active free radical polymerization.

Herein, active free radical polymerization initiator used in the present invention preferably has with pushing away that following formula (IV) represents The compound of geodesic structure,

[in formula (IV), R₃、R₄、R₅Represent the alkyl or phenyl of straight-chain or the branch-like being substituted, R independently of one another₃、 R₄、R₅Can be identical, it is possible to different, R₁And R₂The univalent perssad of the expression free radical corresponding to being produced by free-radical generating agent, but that This is identical, it is possible to different].

Use the PSS through structure control (salt) that the high-purity p styrene sulfonic acid (salt) of the present invention is fabricated by aqueous In medium, make the nano-carbon materials such as CNT, Graphene, fullerene and polythiophene class, multi-metal polypyrrole, polyaniline compound, polyphenylene Asia The ability that the electric conductive polymers such as vinyl, polyphenylene class are scattered in aqueous medium is high, and can be used for improving electric conductivity The conductivity of aqueous polymer dispersion, stability and resistance to water.

Accompanying drawing explanation

Fig. 1 is the HPLC chromatogram of the high-purity p styrene sulfonic acid salt of embodiment 1, and in Fig. 1, the longitudinal axis represents peak intensity (absorption intensity of detector, unit is any), transverse axis represents dissolution time (unit for minute).(a), (b) in Fig. 1, (c), (d) represent respectively styrene sulfonic acid (salt) between (a) adjacent styrene sulfonic acid (salt), (b) β-bromo ethyl phenenyl sulfonic acid (salt), (c), The intensity of (d) bromstyrol sulfonic acid (salt).

Fig. 2 is the HPLC chromatogram of the high-purity p styrene sulfonic acid salt of embodiment 2.Other is identical with the explanation of Fig. 1.

Fig. 3 is the HPLC chromatogram of the low-purity p styrene sulfonic acid salt of comparative example 1.Other is identical with the explanation of Fig. 1.

Detailed description of the invention

The present invention for as in p styrene sulfonic acid (salt) sometimes with (a) of the major impurity being derived from Materials Styrene Styrene sulfonic acid (salt), (d) bromstyrol sulfonic acid between adjacent styrene sulfonic acid (salt), (b) β-bromo ethyl phenenyl sulfonic acid (salt), (c) The peak area benchmark tried to achieve with HPLC of (salt) containing ratio be respectively (a)≤0.20%, (b)≤0.50%, (c)≤ 3.00% and the high-purity of (d)≤0.10% (that is, the summation of p styrene sulfonic acid (salt) and (a)～(d) peak area is 100) P styrene sulfonic acid (salt), and use what it manufactured to have above-mentioned constitutional repeating unit A or above-mentioned constitutional repeating unit A And following constitutional repeating unit B and there is the PSS or its salt [PSS of at least any structure in the most above-mentioned formula (I)～(III) (salt)].

The PSS (salt) of the present invention is not limited in PSS (salt) homopolymer, as long as i.e. having above-mentioned constitutional repeating unit A, or Above-mentioned constitutional repeating unit A and B, is just not particularly limited, it is possible to for random copolymer or block copolymer.Block described herein Copolymer is polymer chain (the above-mentioned constitutional repeating unit that PSS (salt) chain (above-mentioned constitutional repeating unit A) is different from PSS (salt) B) form via covalent bond mutual block bonding, the type such as including diblock, three blocks, many block types.The present invention's is upper That states block copolymer preferably illustrates the block copolymer that can list the structure with above-mentioned formula (I)～(III).

It addition, in above-mentioned constitutional repeating unit A～B and above-mentioned formula (I)～(III), n and n ' is the integer of more than 1, preferably Being the integer of 10～5000, m and m ' is the integer of more than 0, the integer of preferably 0～5000.

It is a feature of the present invention that PSS (salt) through structure control, structure control referred to herein has three kinds of implications.

First implication is monomer [p styrene sulfonic acid (the salt)] high purity making to use in the manufacture of PSS (salt), explanation Under in.

P styrene sulfonic acid (salt) typically manufactures with following method, cannot avoid unreacted halogenide, different in preparation method The impurity such as structure thing, metal halide produce as by-product or are mixed into.

Labor p styrene sulfonic acid (salt), result is judged as main impurity, including being derived from benzene feedstock second Styrene sulfonic acid (salt), (d) bromstyrol between the adjacent styrene sulfonic acid (salt) of (a) of alkene, (b) β-bromo ethyl phenenyl sulfonic acid (salt), (c) Sulfonic acid (salt).The present inventor etc. utilize p styrene sulfonic acid (salt) side of recrystallization purification from aqueous solution containing above-mentioned impurity Method or the manufacturing condition by control reaction temperature etc., containing of these impurity of the peak area benchmark that manufacture is tried to achieve with HPLC Ratio is respectively the high-purity of (a)≤0.20%, (b)≤0.50%, (c)≤3.00% and (d)≤0.10% to styrene sulphur Acid (salt), and use this high-purity p styrene sulfonic acid (salt), utilize conventional radical polymerization to manufacture high-purity PSS (salt).It is used to manufacture CNT aqueous dispersion or poly-(the 3,4-Asia second as representative electric conductive polymer in dispersant Propylenedioxythiophene) aqueous dispersion of (hereinafter referred to as PEDOT), found that compared with the situation using conventional PSS, dispersion The stability of body improves.And then, find that the conductivity of the film obtained by PEDOT aqueous dispersion improves.

Though reason is indefinite, but the stability about dispersion improves, it is believed that be because of the minimizing of the isomeric compounds such as meta body Improve the reason of the stability of PSS (salt).About the raising of conductivity, the most do not mention the PSS in this purposes The regular report example of (salt), but think and be perhaps because regular raising of PSS (salt) and make the doping rate of PEDOT is carried High.

Make above-mentioned high-purity p styrene sulfonic acid (salt) through free radical in aqueous solvent it addition, the present invention also refers to comprise High-purity PSS being polymerized and obtain or the solution of its salt.That is, (b) β-bromo ethyl phenenyl sulfonic acid (salt) in above-mentioned impurity is not due to Containing free-radical polymerised double bond, therefore it is not copolymerized in PSS (salt) skeleton, but be present in preparing in an aqueous medium In PSS (salt) solution.The purposes of such as aluminium electrolutic capacitor etc. uses containing as such in β-bromo ethyl phenenyl sulfonic acid (salt) During PSS (salt) aqueous solution of impurity, halogen is made to dissociate because of the decomposition of β-bromo ethyl phenenyl sulfonic acid (salt), the aluminum produced because of this halogen Electrochemical corrosion reaction when repeatedly occurring, cause capacitor faults.Therefore, the most also do one's utmost to reduce β-bromo ethyl phenenyl sulfonic acid (salt).

Secondary Meaning for make the molecular weight distribution of PSS (salt), the most so-called weight-average molecular weight/number-average molecular weight value narrow To less than 2.0.The present inventor etc. utilize living radical polymerization, and synthetic molecular weight is distributed the PSS (salt) less than 2.0, and will It is in dispersant, after manufacturing CNT aqueous dispersion or PEDOT aqueous dispersion, found that the PSS conventional with use Situation is compared, and the stability of dispersion improves, and the electric conductivity of PEDOT aqueous dispersion film improves.

It is considered the edge making to improve as the efficiency of dispersant due to the narrow molecular weight distribution by PSS (salt) Therefore.I.e., it is believed that relative to the particle diameter of dispersate, when the length of PSS (salt) is too short, PSS (salt) is easily from dispersate desorbing, phase Instead, time long, PSS (salt) makes dispersate bridge each other and condense.Though it addition, reason is indefinite, but thinking and divide in PEDOT aqueous After a prose style free from parallelism manufactures, it is difficult to cause the PSS (salt) desorbing from PEDOT particle surface, therefore make conductivity improve.

It addition, the molecular weight distribution of the PSS of the present invention (salt) is preferably smaller than 2.0.Molecular weight distribution is closer to representing single point 1.0 dissipated are the best, but when considering the productivity ratio of PSS (salt), cost, further preferred 1.0～1.8.In the present invention, in order to make The molecular weight distribution of PSS (salt) is less than 2.0, as described later, the high-purity p styrene sulfonic acid (salt) of the present invention is carried out activity Radical polymerization is now, as long as using the radical polymerization initiator represented with formula described later (IV) or common by having The PSS (salt) of molecular weight distribution, uses post to divide the PSS (salt) taking desired molecular weight.

3rd implication is that polymer and PSS (salt) that will be different from PSS (salt) links with block-wise that (so-called block is altogether Poly-).The present inventor etc. find to be gathered polymer lower than PSS (salt) with being considered hydrophilic for PSS (salt) by living radical Close and connect to block-wise, manufacture PSS (salt) block copolymer, and use it as dispersant to manufacture CNT or PEDOT aqueous Dispersion, result can further improve the stability of dispersion.It is considered the block owing to hydrophilic is low and is effectively adsorbed in CNT Or on the hydrophobic material such as PEDOT, or on the contrary, maintained dispersion stabilization by remaining PSS (salt) in the past, but The present invention is by the hydrophilic other block lower than PSS (salt) and decentralized stabilization.Furthermore, by PSS (salt) with heterogeneous Polymer blocks ground bonding, and have can improve in the past as the adaptation to base materials such as resin, glass, ITO of problem and other The probability of the intermiscibility of the polymer of kind.

For the weight average molecular weight tried to achieve with GPC of PSS (salt) of the present invention unrestricted, preferably 2,000～1,000,000, examine Consider the operability of aqueous dispersion such as viscosity, the PSS (salt) polymerization initiator amount etc. when manufacturing time, further preferred 5,000～60 Ten thousand.

This weight average molecular weight can be easily adjusted relative to the addition of monomer by polymerization initiator or chain-transferring agent.

Beyond the p styrene sulfonic acid (salt) used in the PSS (salt) of the present invention or PSS (salt) block copolymer Other monomer, as long as utilizing PSS (salt) free radical to carry out radical polymerization, or produces can become for p styrene sulfonic acid (salt) The free radical (in other words, can carry out radical copolymerization with p styrene sulfonic acid (salt)) of radical polymerization initiator, just without special Do not limit.Such as N-phenylmaleimide, N-(chlorphenyl) maleimide, N-(aminomethyl phenyl) maleimide can be listed Amine, N-(isopropyl phenyl) maleimide, N-(sulfur phenenyl) maleimide, N-methylphenylmaleimide, N-bromobenzene Base maleimide, N-naphthyl maleimide, N-hydroxyphenyl-maleimides, N-methoxyphenyl maleimide, N- Carboxyl phenyl maleimide, N-(nitrobenzophenone) maleimide, N-benzyl maleimide, N-(4-acetoxyl group-1-naphthalene Base) maleimide, N-(4-Oxy-1-naphthyl) maleimide, N-(3-fluoranthene base (fluoranthyl)) maleimide Amine, N-(5-fluorescein base (Fluoresceinyl)) maleimide, N-(1-pyrenyl) maleimide, N-(2,3 xylidine Base) maleimide, N-(2,4-xylyl) maleimide, N-(2,6-xylyl) maleimide, N-(aminobenzene Base) maleimide, N-(tribromo phenyl) maleimide, N-[4-(2-benzimidazolyl) phenyl] maleimide, N-(3, 5-dinitrophenyl) maleimide such as maleimide, N-(9-acridinyl) maleimide, dibutyl fumarate, richness The dimethyl ester classes such as horse acid dipropyl, DEF, fumaric acid dicyclohexyl maleate, fumaric acid butyl ester, propyl fumarate, richness The fumaric monoalkylester classes such as horse acetoacetic ester, the maleic acid diester class such as dibutyl maleate, dipropyl maleate, ethyl maleate., The maleic mono-ester classes such as butyl maleate, maleic acid propyl ester, ethyl maleate, dicyclohexyl maleate, maleic anhydride, citraconic acid The anhydride such as acid anhydride, maleimide, N-(sulfophenyl) maleimide, N-N-cyclohexylmaleimide, N-methylmaleimido, The maleimide of NEM etc., styrene, chlorostyrene, dichlorostyrene, bromstyrol, dibromobenzene second Alkene, fluorobenzene ethylene, trifluorostyrene, nitrostyrolene, cyano styrene, α-methyl styrene, p-chloromethyl styrene, to cyanogen Base styrene, to acetoxy-styrene, to styrenesulphonyl chloride, p styrene sulfonic acid ethyl ester, p styrene sulfonic acid methyl ester, right Styrene sulfonic acid propyl ester, to butyl phenyl ether ethylene, 4-vinyl benzoic acid, 3-isopropenyl-α, α '-dimethyl benzyl Carbimide. The phenylethylenes such as ester, IVE, ethyl vinyl ether, 2-phenyl vinyl alkyl ether, nitrobenzophenone vinyl ethers, The vinyl ethers such as cyano-phenyl vinyl ethers, chlorophenylethene ether, acrylic acid methyl ester., ethyl acrylate, propyl acrylate, Butyl acrylate, amyl acrylate, Hexyl 2-propenoate, decyl acrylate, lauryl acrylate, 1-Octyl acrylate, acrylic acid ten Dialkyl, stearyl acrylate acid esters, 2-EHA, cyclohexyl acrylate, acrylic acid norbornene ester, acrylic acid 2-second Epoxide ethyl ester, acrylic acid 2-butoxyethyl, acrylic acid 2-hydroxy methacrylate, tetrahydrofurfuryl acrylate, methoxyethyl second two Alcohol ester, acrylic acid ethyl carbitol ester, acrylic acid 2-hydroxy propyl ester, acrylic acid 4-hydroxybutyl, acrylic acid 3-(trimethoxy silicon Alkyl) propyl ester, polyalkylene glycol acrylate ester, glycidyl acrylate, 2-(acryloxy) ethyl phosphonic acid ester, acrylic acid 2, 2,3,3-tetrafluoro propyl ester, acrylic acid 2,2,2-trifluoro ethyl ester, acrylic acid 2,2,3,3,3-five fluorine propyl ester, acrylic acid 2,2,3,4,4, The esters of acrylic acids such as 4-hexafluoro butyl ester, the secondary butyl ester of methyl methacrylate, Tert-butyl Methacrylate, methacrylic acid, methyl Isobutyl 2-propenoate, isopropyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate, 2-Propenoic acid, 2-methyl-, octyl ester, Lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, methacrylic acid norbornene ester, first Base benzyl acrylate, phenyl methacrylate, glycidyl methacrylate, methacrylic acid macrogol ester, methyl-prop Olefin(e) acid 2-hydroxy methacrylate, tetrahydrofurfuryl methacrylate, methacrylic acid methoxyl group glycol ester, methacrylic acid ethyl card must Alcohol ester, methacrylic acid 2-hydroxy propyl ester, methacrylic acid 4-hydroxybutyl, 2-(methacryloxy) ethyl phosphonic acid ester, Methacrylic acid 2-(dimethylamino) ethyl ester, methacrylic acid 2-(lignocaine) ethyl ester, methacrylic acid 3-(dimethylamino) Propyl ester, methacrylic acid 2-(isothiocyanate) ethyl ester, methacrylic acid 2,4,6-tribromo-benzene, methacrylic acid 2,2,3,3-tetra- Fluorine propyl ester, methacrylic acid 2,2,2-trifluoro ethyl ester, methacrylic acid 2,2,3,3,3-five fluorine propyl ester, methacrylic acid 2,2,3, The methyl acrylic esters such as 4,4,4-hexafluoro butyl esters, 1,3-butadiene, 2-methyl isophthalic acid, 3-butadiene, chlorbutadiene, 2,3-bis-chloro-1,3-butadiene, 2-cyano group-1,3-butadiene, 1-chloro-1,3-butadiene, 2-(N-piperidino methyl)-1,3-fourth Diene, 2-triethoxy methyl isophthalic acid, 3-butadiene, 2-(N, N-dimethylamino)-1,3-butadiene, N-(2-methylene-3-fourth Enoyl-) the 1,3-butadiene class such as morpholine, 2-methylene-3-cyclobutenyl diethyl phosphate, it addition, list acrylamide, first Base acrylamide, sulfophenyl acrylamide, sulfophenyl clothing health acid imide, acrylonitrile, methacrylonitrile, flumaronitrile, acrylic acid α- Cyanaoethyl methacrylate, citraconic anhydride, vinyl acetic acid, propionate, new vinyl acetate acid, tertiary ethylene carbonate .beta.-methylacrylic acid, clothing health Acid, fumaric acid, phthalic acid list 2-(methacryloxy) ethyl ester, mono succinate 2-(methacryloxy) ethyl ester, Mono succinate 2-(acryloxy) ethyl ester, methacryloxypropyl trimethoxy silane, methacryloxypropyl Dimethoxysilane, acrylic aldehyde, diacetone acrylamide, ethenyl methyl ketone, vinyl ethyl ketone, methacrylic acid two acetone Ester, vinyl sulfonic acid, isoprene sulfonic acid, allyl sulphonic acid, 2-acrylamide-2-methyl propane sulfonic acid, 2-acrylamide-1- Pyrovinic acid, 2-Methacrylamide-2-methyl propane sulfonic acid, vinyl pyrrolidone, dehydroalanine, sulfur dioxide, different Butylene, N-vinyl carbitol, sub-ethylene dicyanide, to hydroquinone bismethane, chlorotrifluoroethylene, tetrafluoroethene, norborene, N-vinyl carbitol etc..Wherein, it is considered to during with p styrene sulfonic acid or the combined polymerization of salt, availability etc., optimization styrene, Styrene derivative, methacrylic acid, 2-hydroxyethyl methacrylate, glycidyl methacrylate, N-vinylpyridine Pyrrolidone, N-phenylmaleimide, maleic anhydride.

There is no particular restriction for the content of non-PSS (salt) composition in above-mentioned PSS (salt) block copolymer, as long as according to purpose Adjust content, but due to the lowest more than the hydrophilic of copolymer during 98 weight % and make to drop as the function of dispersant Low, below the most preferably 60 weight %.

Then, the manufacture method for the high-purity p styrene sulfonic acid (salt) of the present invention is illustrated.

There is no particular restriction for the manufacture method of high-purity p styrene sulfonic acid (salt), but can be by such as by impure right Styrene sulfonic acid (salt) puts in the mixed solvent of pure water or the water-soluble solvent such as acetone, isopropanol and water, adds at 40～70 DEG C After heat, dissolving, slowly cool to room temperature, make p styrene sulfonic acid (salt) recrystallization manufacture.By repeating this operation, one can be entered Step improves purity.This operation recrystallized is more than 1 time, if considering productivity ratio or cost, and the most preferably 1～3 time.

During the manufacture example of the further high-purity p styrene sulfonic acid (salt) of the particular instantiation present invention, such as by making benzene second Alkene sodium sulfonate is in methanol (generally at 40～50 DEG C about 10～60 minutes) and slow with 5～6 weight % concentration heating for dissolving Slowly it is cooled near room temperature～10 DEG C, after separating out the crystallization of sodium p styrene sulfonate, through filtering, being dried, high-purity can be obtained Sodium p styrene sulfonate.

Then, the manufacture method for the PSS (salt) of the present invention is illustrated.

There is no particular restriction for the manufacture method of PSS (salt), but illustrate the method utilizing general radical polymerization to carry out and make For first case.Such as, if by aqueous solvent and p styrene sulfonic acid or its salt and optionally can be with p styrene sulfonic acid Or the homogeneous solution of its salt monomer mixture of carrying out radical copolymerization puts in reaction vessel, optionally add molecular weight and adjust Joint agent, makes in system, after deoxidation, to be heated to set point of temperature, and limit is added radical polymerization initiator limit and is polymerized.Now, in order to Avoid the polymerization of fierceness, and when considering the molecular weight control in low-molecular-weight region, the most not by whole monomer mixing Thing puts in reaction vessel, but preferably by each monomer together with polymerization initiator or molecular weight regulator the most continuous Make an addition in reaction vessel.

There is no particular restriction for reaction dissolvent, but considers p styrene sulfonic acid or its salt and the dissolubility of comonomer, and During the manufacture of the nano-carbon material of CNT etc. and the aqueous dispersion of electric conductive polymer, preferably aqueous solvent, such as water and water-soluble The mixture of property solvent.As water-soluble solvent, as long as make p styrene sulfonic acid (salt) dissolve with the mixture of comonomer Composition i.e. unrestricted, can list such as acetone, oxolane, twoAlkane, methanol, ethanol, normal propyl alcohol, isopropanol, methoxy Base ethanol, ethoxy ethanol, butanol, ethylene glycol, propylene glycol, glycerol, dimethyl sulfoxide, dimethylformamide, N-methylpyrrole Alkanone etc..Be preferably acetone, oxolane, twoAlkane, dimethyl sulfoxide, N-Methyl pyrrolidone and dimethylformamide.

As the usage amount of aqueous solvent of reaction dissolvent relative to monomer total amount 100 weight portion, usually 150～2000 Weight portion.

There is no particular restriction for molecular weight regulator, but can list such as diisopropyl xanthic acid disulphide, diethyl Xanthic acid disulphide, diethyl thiuram disulfides, 2,2 '-dithiodipropionic acid, 3,3 '-dithiodipropionic acid, 4,4 '- Dithio two butanoic acid, 2, the disulfides such as double benzoic acid of 2 '-dithio, n-dodecyl mercaptan, octyl mercaptan, tert-butyl group sulfur Alcohol, thioglycolic acid, mercaptosuccinic acid., 2 mercaptopropionic acid, 3-mercaptopropionic acid, thiosalicylic acid, 3-mercaptobenzoic acid, 4-sulfydryl Benzoic acid, sulfur for malonic acid, dithio succinic acid, sulfur for maleic acid, sulfur for maleic anhydride, dithio maleic acid, sulfur generation penta 2 Acid, cysteine, homocysteine, 5-mercapto-tetrazole acetic acid, 3-sulfydryl-1-propane sulfonic acid, 3-thio propane-1,2-two Alcohol, mercaptoethanol, 1,2-dimethyl ethane thiol, 2-MEA hydrochlorate, 6-sulfydryl-1-hexanol, 2-sulfydryl-1-imidazoles, 3-sulfydryl-1,2,4-triazole, cysteine, N-acyl cysteine, glutathion, N-butylamino ethane thiol, N, N-bis- The thio-alcohols such as ethylamino-ethane mercaptan, the halogenated hydrocarbon such as iodoform (iodoform), diphenylethlene, p-dichlorobenzene base ethylene, right Cyanobiphenyl ethylene, α-methylstyrenedimer, dithio benzyl benzoate, dithiobenzoic acid 2-cyano group acrylate-2-base Ester, Organic Tellurium Compounds, sulfur, sodium sulfite, potassium sulfite, sodium sulfite, Potassium acid sulfite, sodium pyrosulfite, burnt sulfurous Acid potassium etc..

The usage amount of molecular weight regulator relative to monomer total amount 100 weight portion, usually 0.1～10 weight portion.

As above-mentioned radical polymerization initiator, such as di-tert-butyl peroxide, diisopropylbenzyl peroxide can be listed Compound, tert butyl isopropyl benzene peroxide, benzoyl peroxide, dilauryl peroxide, isopropyl benzene hydroperoxide, Tert-butyl hydroperoxide, 1,1-bis(t-butylperoxy)-3,5,5-trimethyl-cyclohexane, 1,1-bis(t-butylperoxy)- Hexamethylene, Cyclohexanone peroxides, peroxy t-butyl perbenzoate, peroxy tert-butyl isobutyrate, peroxy-3,5,5-front three Base hecanoic acid t-butyl ester, peroxy-2 ethyl hexanoic acid tert-butyl ester, peroxy isopropyl carboxylic acid tert-butyl ester, peroxy octanoic acid isopropylbenzene The peroxide of base ester, potassium peroxydisulfate, Ammonium persulfate., hydrogen peroxide etc., 2,2 '-azo double (4-methoxyl group-2,4-dimethyl Valeronitrile), 2,2 '-azo double (2,4-methyl pentane nitrile), 2,2 '-azo double (2-methyl propionitrile), double (the 2-methyl of 2,2 '-azo Butyronitrile), 1,1 '-azo double (hexamethylene-1-formonitrile HCN), 1-[(1-cyano group-1-Methylethyl) azo] Methanamide, 2,2 '-azo Double (2 Methylpropionic acid) dimethyl ester, 4,4 '-azo double (4-cyanopentanoic acid), 2,2 '-azo double (2,4,4-trimethylpentane), 2, Double { 2-(the 2-miaow of 2 '-azo double { 2-methyl-N-[1,1 '-bis-(hydroxymethyl)-2-hydroxyethyl] propionic acid amide. }, 2,2 '-azo Oxazoline-2-base) propane dihydrochloride, 2,2 '-azo double 2-(2-imidazoline-2-base) propane] di-sulfate dihydrate, 2, Double { 2-[1-(2-the hydroxyethyl)-2-imidazoline-2-base] propane } dihydrochloride of 2 '-azo, 2,2 '-azo double (1-imino group- 1-pyrrolidinyl-2-methylpropane) dihydrochloride, double (the 2-methyl-prop amidine) dihydrochloride of 2,2 '-azo, the double [N-of 2,2 '-azo (2-carboxy ethyl)-2-methyl-prop amidine] azo-compound etc. such as tetrahydrate.It addition, also can be optionally and with ascorbic acid, different The organic system reducing agents etc. such as ascorbic acid, aniline, tertiary amine.

The usage amount of radical polymerization initiator relative to monomer total amount 100 weight portion, usually 0.1～10 weight portion.

There is no particular restriction for polymerizing condition, as long as under non-active gas atmosphere, heats 4～50 hours at 40～120 DEG C As long as suitably adjusting according to polymer solvent, monomer composition and polymerization initiator species.

The PSS (salt) of the present invention also can be manufactured by above-mentioned general radical polymerization, but in order to make molecular weight distribution Narrow or in order to manufacture block copolymer, preferably living polymerization, for such as the polarity of p styrene sulfonic acid or its salt etc Monomer, more preferably living radical polymerization.It addition, use the p styrene sulfonic acid ester generation high to the dissolubility of various solvents During for p styrene sulfonic acid (salt), it is possible to manufactured by ionic polymerization.

As living radical polymerization, can list such as atom transfer polymerization method, stablize nitroxyl mediated polymerization, Reversible addition cracking transfer polymerization method, organic tellurium mediated polymerization method (macromolecule collection of thesis, vol.64, No.6, pp.329,2007 Year), iodine transfer polymerization method (Japanese Unexamined Patent Publication 2007-92014 publication；Macromolecule collection of thesis, vol.59, No.10, page 798, 2010), use the polymerization (Japanese Unexamined Patent Publication 2006-233012 publication) of the coordination compound of phosphine and Carbon bisulfide, use three alkane The method (engaging, volume 50, No. 4, page 23,2006) of base borine, method (the Japan spy of use α-methylstyrenedimer Open 2000-169531 publication), these methods may be applicable in the present invention.

The concrete example of active free radical polymerization carries out activity certainly for making other free radical polymerization monomer in aqueous solvent After being polymerized by base, add the high-purity p styrene sulfonic acid (salt) of the present invention, be further continued for active free radical polymerization, or in aqueous After solvent makes this p styrene sulfonic acid (salt) active free radical polymerization, add other free radical polymerization monomer, be further continued for living Free love base is polymerized.Such as, by this active free radical polymerization, it is thus achieved that have such as particular instantiation in above-mentioned formula (I)～(III) The polystyrolsulfon acid (salt) of structure.

Herein, the kind of aqueous solvent etc. are identical with above-mentioned radical polymerization.

As ionic polymerization, the anionic polymerization (Polymer such as using amines can be listed Preprints, Japan, Vol.59, No.1,2010 year, page 565；Japan rubber association will, volume 74, No. 7, calendar year 2001, the Page 254), if using p styrene sulfonic acid ester, then it is equally applicable in the present invention.

It addition, in above-mentioned living radical polymerization, it is considered to for p styrene sulfonic acid or its salt the suitability be polymerized Simplicity time, the polymerization of the coordination compound of phosphine and Carbon bisulfide is preferably used, i.e. use the supposition structure with following formula (IV) Radical polymerization initiator (controlling agent).

[in formula (IV), R₃、R₄、R₅Represent the straight-chain that can be substituted or the alkyl or phenyl of branch-like independently of one another, R₃、R₄、R₅May be the same or different, R₁And R₂The univalent perssad of the expression free radical corresponding to being produced by free-radical generating agent, can Mutually the same also can be different].

There is no particular restriction for active free radical polymerization condition, but as its concrete example, puts into benzene second in reaction vessel Alkene sulfonic acid or its salt and depend on the needs can carry out comonomer uniform of radical polymerization with p styrene sulfonic acid (salt) Solution, makes in system after deoxidation, adds above-mentioned radical polymerization initiator (working as initiator molecular weight regulator of holding concurrently), It is heated to set point of temperature, is polymerized, thus can manufacture the PSS (salt) of sharp molecular weight distribution.Herein, after manufacturing PSS (salt), Can add under deoxygenated state and can carry out other monomer of radical polymerization with p styrene sulfonic acid (salt), carry out reheating poly- Close, thus manufacture PSS (salt) block copolymer.Or, the list of radical copolymerization can be carried out with p styrene sulfonic acid (salt) The solution of body puts in reaction vessel, after making internal system deoxidation, adds above-mentioned radical polymerization initiator, is heated to regulation temperature Degree, is polymerized, and thus manufactures the polymer of sharp molecular weight distribution, then add under deoxygenated state p styrene sulfonic acid or Its salt, carries out reheating polymerization, the most also can manufacture PSS (salt) block copolymer.It addition, by repeating these operations, can make Make PSS (salt) copolymer of many block types.

The R of above-mentioned formula (IV)₃、R₄、R₅It is each independently the alkyl or phenyl of straight-chain or the branch-like that can be substituted, But preferably carbon number is the alkyl of 1～18, it is considered to during to the dissolubility of solvent, more preferably ethyl, propyl group, isopropyl, positive fourth Base, primary butyl, the tert-butyl group.

R₁、R₂Represent the univalent perssad produced by radical polymerization initiator, but consider that polymerization initiator is to aqueous solvent During dissolubility, preferably there is hydrophilic.Such as, as this radical polymerization initiator, can list 2,2 '-azo is double Double (2-aminopropane) nitrate of (2-amidine propane) hydrochlorate, 2,2 '-azo, 2,2 '-azobisisobutylonitrile base amide, 4,4 '- Double-4-the cyanopentanoic acids of azo etc..

Structure (V) or (VI) of the most following supposition it is considered to have by the PSS (salt) of above-mentioned acquisition.

R in above-mentioned formula (V) and (VI)₁～R₅With the R in formula (IV)₁～R₅Each identical, n, m and above-mentioned repetitive structure list N, m in A, B or logical formula (I) of unit～(III) are identical.In above-mentioned PSS (salt), though comprising the initiator part of formula (IV), but Can by make initiator part acid or aqueous alkali in hydrolysis and by removing.

Other method of the PSS (salt) manufacturing sharp molecular weight distribution is also contemplated for making to divide with the molecular weight of living polymerization manufacture The narrow polystyrene of cloth is in the halogenated solvents such as dichloroethanes, by the method for the sulfonation such as anhydrous slufuric acid.In this case, if sulphur The selectivity of the para-position in change reaction is sufficiently high, is used as the most in the present invention.

The PSS (salt) of the present invention also can optionally and with can be with other of p styrene sulfonic acid or its salt radical copolymerization Monomer carries out random copolymerization.Though be not particularly restricted, but can list and such as be remembered in the explanation of PSS (salt) block copolymer The monomer carried.When being more particularly described, such as, in the case of being intended to improve the adsorptivity to carbon nanomaterial, N-benzene can be listed Base maleimide, N-(chlorphenyl) maleimide, N-methylphenylmaleimide, N-bromophenyl maleimide, N- Naphthyl maleimide, N-hydroxyphenyl-maleimides, N-methoxyphenyl maleimide, N-carboxyl phenyl maleimide Amine, N-(nitrobenzophenone) maleimide, N-benzyl maleimide, N-(4-acetoxyl group-1-naphthyl) maleimide, N- (4-Oxy-1-naphthyl) maleimide, N-(3-fluoranthene base) maleimide, N-(5-fluorescein base) maleimide, N- (1-pyrenyl) maleimide, N-(2,3 xylidine base) maleimide, N-(2,4-xylyl) maleimide, N- (2,6-xylyl) maleimide, N-(aminophenyl) maleimide, N-(tribromo phenyl) maleimide, N-[4- (2-benzimidazolyl) phenyl] maleimide, N-(3,5-dinitrophenyl) maleimide, N-(9-acridinyl) maleoyl The aromatic series maleimides such as imines.

Additionally, the PSS of the present invention (salt) or PSS (salt) solution are due to containing from used monomer and polymerization initiator Impurity, the most also can pass through after ion exchange, dialysis, ultrafiltration etc. remove, to be polymerized for CNT or electric conductivity In the manufacture of thing dispersion.

Then, the manufacture method for the aqueous dispersion of the nano-carbon materials such as CNT, Graphene, fullerene is illustrated.

Herein, becoming the CNT of object of the present invention, Graphene, fullerene etc. as nano-carbon material is in chemistry Identical meanings.Nano-carbon material for carbon atom gathers with the general name of material with carbon element obtained by nanometer (nm) unit structure.Cause This, CNT (Carbon nanotube is called for short CNT) becomes monolayer for the hexatomic ring network (graphene film) formed by carbon Or the material of the coaxial tubular of multilamellar.There is also a kind of situation being classified into fullerene for the isomer of carbon.Separately Outward, so-called Graphene (graphene), is the sp of the thickness of 1 atom²The thin slice of bonding carbon atom.Take by carbon atom and its The hexagonal lattice structure of the Nidus Vespae that key-like becomes etc.Additionally, fullerene (fullerene) is to be constituted minimum with multiple carbon atoms The general name of the cluster of structure.From structure to start be that the Graphene of the diamond of 14 and 6 is different, for by dozens of number The carbon isomer that atom starts.

There is no particular restriction for the manufacture method of the aqueous dispersion of above-mentioned nano-carbon material, can apply known method (such as, Japanese Unexamined Patent Publication 2009-190940 publication, Japanese Unexamined Patent Publication 2010-13312 publication).Such as, receiving CNT etc. while stirring Rice material with carbon element is added in the aqueous solvent of the PSS (salt) containing the present invention, by ball mill, homogenizer and/or ultrasonic irradiation And make CNT disperse.Now, in order to improve the wettability of the nano-carbon materials such as CNT, it is possible to adding relative to water is 0.5～30 The water-soluble solvent of weight % and/or anionic emulsifier, nonionic emulsifier, cationic emulsifier, both sexes emulsifying Agent.

There is no particular restriction for above-mentioned water-soluble solvent, be illustrated as acetone, methanol, ethanol, propanol, butanol, oxolane, twoAlkane, ethoxy ethanol, methyl cellosolve, glycerol, propylene glycol, ethylene glycol, butanediol, acetic acid, propanoic acid etc..

As mentioned emulsifier, there is no particular restriction, but as anionic emulsifier, can list such as rosin acid Salt, soap, alkenyl succinate, alkyl ether carboxy acid salt, alkyl diphenyl base ether disulfonate, alkyl sulfonate, alkylated salicylamide Acid ester sulfonates, polyoxyethylene polycycle phenyl ether sulfuric acid, alpha-alkene sulfonate, alkylbenzenesulfonate, naphthalene sulfonate first Aldehyde condensate, taurine derivatives, polystyrolsulfon acid, polystyrolsulfon acid methacrylic acid copolymer, polystyrolsulfon acid Acrylic copolymer, polystyrolsulfon acid acrylate copolymer, styrene sulfonic acid maleic acid, styrene sulfonic acid propylene Amide copolymer, styrene sulfonic acid methacrylamide copolymer, styrene sulfonic acid 2-hydroxyethyl methacrylate copolymer, Polyvinyl sulfonic acid copolymer, polyvinyl sulfonic acid copolymer, polyisoprene sulfonic acid copolymer, polyacrylate acrylic acid copolymer Thing, polymethacryl methyl acrylic copolymer, polyacrylamide acrylic copolymer, PMAm methyl-prop Olefin(e) acid copolymer, alkyl sulfo succinate, alkyl sulfate salt, alkyl ether sulphate salts, alkyl base phenol polycyclic oxygen second The sulfuric acid of alkane addition product, the sulfuric acid of allyl alkyl phenol polyethylene oxide adducts, alkyl phosphate salt, polyoxygenated Ethylidene alkyl ether phosphate salt, the sulfonate of higher fatty acid amides, the sulfuric acid etc. of higher fatty acids hydroxyalkyl amide, As nonionic emulsifier, such as polyoxyalkylene alkylamine amine, alkylalkanol amide, amine oxide system nonionic can be listed Emulsifying agent, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyalkylene polycycle phenyl ether, alkane Base propenyl phenol polyethylene oxide adducts, allyl alkyl phenol polyethylene oxide adducts, polyoxyethylene fatty acid esters, Polyethylene oxide sorbitan fatty acid ester, sorbitan fatty acid ester, fatty acid glyceride, alkyl poly glucoside, sugarcane Sugar fatty acid ester, polyethylene oxide polyoxypropylene glycol, polyvinyl alcohol, carboxymethyl cellulose, polyvinylpyrrolidone, ethoxy Cellulose, polyacrylamide, PMAm, polymethylacrylic acid dimethylaminoethyl, polyacrylic acid dimethylamino second Ester, polymethylacrylic acid lignocaine ethyl ester, polyacrylic acid lignocaine ethyl ester, polymethylacrylic acid t-butylethyl amino second Ester, polyacrylic acid t-butylaminoethyl, polymethylacrylic acid dimethylaminoethyl/methylmethacrylate copolymer, poly-third Olefin(e) acid dimethylaminoethyl/methylmethacrylate copolymer, polymethylacrylic acid dimethylaminoethyl/butyl acrylate copolymerization Thing, polyacrylic acid dimethylaminoethyl/ethyl acrylate copolymers etc., as cationic emulsifier, can list such as alkane Base amine salt, alkyl type quaternary ammonium salt, fatty acid amide amine salt, alkylaminoacid salts etc., as amphoteric emulsifier, can list such as Alkyl-dimethyl oxyneurine, alkyl-dimethyl sultaines, alkyl sulfo betaines etc..

The PSS (salt) of the present invention is the novel PSS (salt) through structure control, the most useful CNT, Graphene, richness In the manufacture of the aqueous dispersion strangling the nano-carbon materials such as alkene, become very useful dispersant.It addition, the CNT etc. of the present invention receives The aqueous dispersion of rice material with carbon element also can optionally contain pH regulator, defoamer, preservative, viscosity modifier, chelating agen etc..

Herein, in the aqueous dispersion of the nano-carbon material of the present invention, the carbon nanomaterial such as CNT, Graphene, fullerene with The ratio of the aqueous mediums such as water is, nano-carbon material concentration in an aqueous medium is 0.05～10 weight %, preferably 0.1～ 5 weight %.During less than 0.05 weight %, the carbon nanomaterial network in aqueous dispersion film is formed and becomes insufficient, has Cannot fully obtain the situation of electric conductivity.On the other hand, during more than 10 weight %, have the nano-carbon materials such as CNT and the most fully divide Situation about dissipating, it addition, the situation of the corresponding electric conductivity of amount having the nano-carbon material that cannot obtain and used.

It addition, in the aqueous dispersion of the nano-carbon material of the present invention, with regard to the PSS of the nano-carbon materials such as CNT Yu the present invention For the ratio of (salt), the weight ratio of nano-carbon material/PSS (salt) is 1/10～10/1 times, preferably 3/10～10/3 times.Little In 1/10 times time, PSS (salt) amount becomes many relatively, has the feelings of the corresponding effect of amount of the PSS (salt) that cannot obtain be added Condition.On the other hand, during more than 10/1, owing to PSS (salt) is insufficient relative to the amount of nano-carbon material, therefore there is nano-carbon material The situation in the aqueous mediums such as water cannot be well-dispersed in.

It addition, the PSS of the present invention (salt) also can be expected to as carbon pigment, C.I. pigment yellow 74, C.I. pigment yellow 109, C.I. the AZOpigments such as pigment Yellow 12 8, C.I. pigment yellow 151, C.I. pigment Yellow 14, C.I. pigment yellow 16, C.I. pigment yellow 17, Phthualocyanine pigment, the C.I. face such as copper phthalocyanine blue or derivatives thereof (C.I. pigment blue 15: 3, C.I. alizarol saphirol: 15:4), aluminum phthalocyanine Material is purple 48, C.I. pigment violet 49, C.I. pigment violet 1 22, C.I. pigment violet 1 92, C.I. pigment violet 202, C.I. pigment violet 206, C.I. the quinacridone pigment such as pigment violet 207, C.I. pigment violet 209, C.I. pigment violet 19, C.I. pigment violet 42, Yi Jiyi Indolinone pigment, twoPiperazine pigment, pigment, purple cyclic ketones pigment, thioindigo color, anthraquinone pigment, quinophthalone (quinophthalone), indanthrene series pigments, diketopyrrolo-pyrrole series pigments, Aniline black pigment, hetero ring type Huang system face The purposes of the dispersant of material etc..

Then, conduct electricity for polythiophene class, multi-metal polypyrrole, polyaniline compound, polyphenylenevinylene class, polyphenylene class etc. The manufacture method of the aqueous dispersion of property polymer is illustrated.There is no particular restriction for this manufacture method, can apply known method (such as Japanese Unexamined Patent Publication 7-90060 publication, Japanese Unexamined Patent Publication 2004-59666 publication, Japanese Unexamined Patent Publication 2010-40770 public affairs Report, Japanese Unexamined Patent Publication 2011-102376 publication).

Such as, make the monomer dispersion of supply electric conductive polymer in the aqueous solvent containing PSS (salt), add oxidant and Carry out oxidation polymerization, thus can manufacture the aqueous dispersion of electric conductive polymer.Now, in order to generate finer dispersible granule Son, it is possible to ultrasound wave is irradiated on limit, while carry out oxidation polymerization.Subsequently, it is possible to by ion exchange, dialysis, ultrafiltrationmembrane process and Reprecipitation purification etc. removes the impurity of oxidant etc..Or, it is possible to make the monomer dispersion of supply electric conductive polymer in containing In the aqueous solvent of the above-mentioned adulterant beyond PSS (salt), after interpolation oxidant carries out oxidation polymerization, add ethanol, methanol etc. Poor solvent, makes electric conductive polymer separate out, not make water that electric conductive polymer dissolves or alcohol clean after removing impurity, with After, add PSS (salt) aqueous solution, be allowed to redispersion with emulsifier units such as homogenizers.

Herein, as oxidant, the over cure acids such as persulfuric acid, potassium peroxydisulfate, Ammonium persulfate., sodium peroxydisulfate can be listed, The organic acid ferrum (III) such as benzenesulfonic acid ferrum (III), p-methyl benzenesulfonic acid ferrum (III), DBSA ferrum, iron chloride (III), The mineral acid ferrum such as ferric nitrate (III), iron sulfate (III), ammonium ferric sulfate (III), ferric perchlorate (III), Tetrafluoroboric acid ferrum (III) (III), oxygen etc..

In the aqueous dispersion of the electric conductive polymer of the present invention, the aqueous medium such as the electric conductive polymer such as PEDOT and water Ratio be that the concentration of conductive polymer material in an aqueous medium is 0.1～20 weight %, preferably 1～10 weights Amount %.During less than 0.1 weight %, the network of the electric conductive polymer from the film that aqueous dispersion obtains is formed and becomes not fill Point, have the situation that cannot obtain electric conductivity fully.On the other hand, during more than 10 weight %, have and PEDOT etc. cannot be made to lead The situation that conductive polymers is fully dispersed, leads it addition, the amount that has the electric conductive polymer that cannot obtain and used is corresponding Electrical situation.

It addition, in the aqueous dispersion of the electric conductive polymer of the present invention, the electric conductive polymer such as PEDOT is with the present invention's The ratio of PSS (salt) is, the weight ratio of electric conductive polymer/PSS (salt) is 1/10～10/1 times, preferably 3/10～10/3 Times.During less than 1/10, PSS (salt) amount is the most, has and cannot obtain the painting obtained from dispersion because of remaining PSS (salt) The situation of the conductivity of film.On the other hand, during more than 10/1, owing to PSS (salt) is insufficient relative to the amount of electric conductive polymer, Therefore the situation that electric conductive polymer is not well-dispersed in the aqueous mediums such as water is had.

As above aqueous solvent (aqueous medium), preferably water, but alternatively water and the mixed stocker of water-soluble solvent.Make For water-soluble solvent, can list acetone, methanol, ethanol, propanol, butanol, ethoxy ethanol, methyl cellosolve, glycerol, the third two Alcohol, ethylene glycol, butanediol, acetic acid, propanoic acid, N,N-dimethylformamide, dimethyl sulfoxide, acetonitrile etc..

It addition, for the dispersibility improving electric conductive polymer, it is possible to auxiliarily add a small amount of surfactant.Though it is not special Do not limit, but be usable in the manufacture example of nano-carbon material aqueous dispersion the surfactant enumerated.

Additionally, as becoming the oxygen compound of adulterant, the preferably PSS (salt) of the present invention, but also can and with Loprazolam, Benzenesulfonic acid, p-methyl benzenesulfonic acid, LOMAR PWA EINECS 246-676-2,2-LOMAR PWA EINECS 246-676-2,10-camphorsulfonic acid, 4-hydroxy benzenesulfonic acid, nitrobenzene-sulfonic acid, Camphora sulphur Acid, 2-anthraquinone sulfonic acid, 1,5-anthraquinone disulfonic acid, 2,6-anthraquinone disulfonic acid, poly-(2-acrylamide-2-propane sulfonic acid), lignin Sulfonic acid, phenol sulfonic acid novolac resin, sulfonated polyester, polyvinyl sulfonic acid, polyisoprene sulfonic acid, polymethyl epoxide benzene sulphur Sour, double (trifluoromethane sulfonyl group) acid imide sour, double (perfluoroalkanesulfonyl) acid imide, polyacrylic acid Loprazolam etc. are sulfonated Compound, polyacrylic acid, polymethylacrylic acid, poly-aspartate, poly, polyvinyl benzoic acid, acetic acid, maleic acid, carboxylic Carboxylic acid compound, the polyphosphoric acid etc. such as base phenol, phthalic acid aldehyde, carboxyl phenol, carboxyl cresol, carboxyl naphthalene, dicarboxyl naphthalene.

It addition, improve conductivity to promote the rearrangement of electric conductive polymer chain, it is possible in the conduction of above-mentioned manufacture The aqueous dispersion of property polymer adds the dimethyl sulfoxide as secondary doping agent, ethylene glycol, diethylene glycol, glycerol, γ- The sugar alcohol such as butyrolactone, sulfolane, N-Methyl pyrrolidone, dimethyl sulfone and erythritol, tetramethylolmethane, Sorbitol.

It addition, for improving the film that is made up of electric conductive polymer to the adaptation of various base materials or the mesh of mechanics physical property , it is possible in the aqueous dispersion of the electric conductive polymer of above-mentioned manufacture, add aqueous solution or the dispersion of other polymer. Such as polyester resin, acrylic resin, polyurethane resin, celluosic resin, butyral resin, polyamide can be listed Resin, polyimide resin, polystyrene resin, polyether resin, gelatin, casein, starch, arabic gum, poly-(vinyl alcohol), PVP, cellulose family, poly alkylene glycol etc..

During it addition, consider the burn into of coating machine etc. to the harmful effect of base material, it is possible in the conductive poly of above-mentioned manufacture The aqueous dispersion of compound adds ammonia, amine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, Lithium hydrate, sodium phosphate etc. PH regulator.

The PSS through structure control (salt) manufactured in the present invention except available as receiving in order to manufacturing the carbon of described above Beyond the dispersant of rice material or electric conductive polymer aqueous dispersion etc., it is possible to expect the interlayer towards solid electrolytic capacitor Adaptation improves agent, lithium secondary battery or the electrode protective membrane of sodium rechargeable battery or distance piece, solid electrolyte, photoresistance acid generation Agent, ion exchange resin, anaphylactogen agent for capturing, water treatment agent, quasiconductor or the abluent of hard disk manufacturing, the changing of emulsion coatings Matter agent, emulsion polymerization or the purposes of the dispersant of suspension polymerization, antistatic additive etc..

Embodiment

By following example, it is more particularly described the present invention, but the present invention is not by any restriction of these embodiments.

Should illustrate, in following example, p styrene sulfonic acid salt, PSS salt, CNT and PEDOT aqueous dispersion point Analyse, prepare and evaluate and implement with following condition.

＜ utilizes mensuration ＞ of the impurity in the p styrene sulfonic acid salt that HPLC is carried out

Dissolving p styrene sulfonic acid salt sample with following eluent A, preparation concentration is the solution of 0.5mg/ml, carries out HPLC Analyze.Condition is the most following.

The LC-8020 that type=TOSOH manufactures

(degasser: SD-8022, pump: CCPM-II, thermocolumn case: CO-8020, UV-visible detector: UV- 8020)

Post=TSKgel ODS-80TsQA (4.6mm × 25cm)

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

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

Gradient condition=and it was A liquid 100% to 55 minutes, 55 minutes～95 minutes is B liquid 100%

Flow=0.8ml/min, UV testing conditions=230nm, column temperature=room temperature, injection rate=20 μ l

It addition, identify with following method in advance with each peak of HPLC detection.

Divide and take with each composition of HPLC detection, with ion exchange resin treatment, make p styrene sulfonic acid salt be converted into sulfonic acid After type, make sulfonic group carry out esterification with Azimethylene., carry out the gas chromatography mass analysis (M-that Hitachi manufactures 80B), fourier transform infrared analysis (System 2000 that Perkin Elmer company manufactures), organic element analysis (the CHN Coder MT-3 that YANACO manufactures) and nuclear magnetic resonance spectroscopy (VXR-300 that BALIAN company manufactures), determine knot Structure.

Mensuration ＞ of the polymerisation conversion of ＜ p styrene sulfonic acid salt

In following GPC measures, calculate from the absorption peak strength of residual monomer.

Mensuration ＞ of the polymerisation conversion of ＜ hydrophobic monomer

After methanol dilution polymeric solution, gas chromatograph (G-17A, Shimadzu Seisakusho Ltd. manufactures) is used to measure in supernatant Hydrophobic monomer (post=NEUTRA BOND-5, after heating schedule=50～200 DEG C × 10 minutes keep, rises with 5 DEG C/min Temperature is to 300 DEG C, and standard curve=using 1-methyl naphthalene as internal standard uses and forms).

Mensuration ＞ of ＜ GPC molecular weight

Molecular weight and the molecular weight distribution of PSS salt measure with following condition.

The LC-8020 that type=TOSOH manufactures

(degasser: SD-8022, pump: DP-8020, thermocolumn case: CO-8020, UV-visible detector: UV- 8020)

Post=TSK guard column α+tsk gel α-6000+TSK gel α-3000

Eluent=phosphate buffer (pH=7) and the solution that volume ratio is 9: 1 of acetonitrile

(above-mentioned phosphate buffer is by the KH of 0.08 mole₂PO₄With the Na of 0.12 mole₂HPO₄It is dissolved in pure water and adjusts Making total amount is obtained by 1L)

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

Detector=UV detector (wavelength 230nm), injection rate=100 μ l

Standard curve=wound and the polystyrene standard sodium sulfonate of science

The molecular weight of PSS salt-polystyrene block copolymer is in above-mentioned condition, is changed to following by eluent composition Form and measure.

Eluent=aqueous sodium persulfate solution (0.05mol/L) and the solution that volume ratio is 65: 35 of acetonitrile

The elementary analysis ＞ of ＜ (co) polymer

About carbon, hydrogen, nitrogen, it is to make to be dried sample [to make (co) polymer solution after 100 DEG C of vacuum drying 3 hours, will do Dry polymer puts in the acetone of 100 times amount of its weight, stirring at normal temperature 24 hours, undissolved thing is recovered by filtration, 50 DEG C vacuum drying 1 hour, has removed unreacted hydrophobic monomer] after crushed, manufacture with Perkin Elmer 2400II elementary analysis meter measures.

In elementary analysis, about sulfur, it is the sample precision of above-mentioned drying, pulverizing to be weighed and burns with oxygen flask combustion After absorption, with ion-chromatographic determination.

Condition determination with the chromatography of ions is as follows.

Post=tsk gel Super IC-AP, eluent=2.7mM sodium bicarbonate+1.8mM sodium carbonate, column temperature=40 DEG C, Flow=0.8ml/min, detector=electric conductivity

The FT-IR of ＜ (co) polymer analyzes ＞

Make sample with KBr pressed disc method, use Perkin Elmer system 2000 to measure.Total range of wavelength be 4000～ 400cm^-1, measuring number of times is 16 times.

＜ CNT and particle size determination ＞ of PEDOT aqueous dispersion

By the visualization of aqueous dispersion and Nanotrac UPA-UT151 in terms of dynamic light scattering formula particle size distribution The particle size determination that (Nikkiso Company Limited's manufacture) is carried out evaluates dispersibility and stability.Use D50% particle diameter (median particle diameter) As mean diameter, it is set to the standard of dispersion.

＜ precipitates ＞

Use centrifugal separator NT-8 on the table that MICROTEC NITION Co., Ltd. manufactures, by aqueous dispersion with 3500rpm centrifugal treating 30 minutes, visualization, with or without precipitation, will be evaluated as zero entirely without the aqueous dispersion of precipitation respectively, The aqueous dispersion of only a little precipitation is evaluated as △, the aqueous dispersion that precipitation is many is evaluated as ×.

The electric conductivity measuring ＞ of ＜ electric conductive polymer

Drip the aqueous dispersion of the electric conductive polymer of 100 μ l on a glass, after being coated with No.8 rod coating device, Temperature chamber is dried 10 minutes at 80 DEG C, and then is dried 30 minutes at 150 DEG C, make electroconductive polymer film.Subsequently, with number Word micron meter (MDC-25NJ that MITUTOYO manufactures) measures thickness, uses the resistrivity meter [LORESTA-that Mitsubishi Chemical manufactures GP (MCP-T600)], measure sheet resistance (Ω/) and conductivity in room temperature according to JIS-K7194.

The estimation of stability ＞ of ＜ electric conductive polymer aqueous dispersion

After being preserved 7 days in the temperature chamber of 50 DEG C by aqueous dispersion, method described above measures particle diameter and conductivity, and comments Valency stability.

Manufacture example 1 [synthesis of radical polymerization initiator (radical polymerization controlling agent)]

Under nitrogen atmosphere, by (pure with light to methanol 24ml, Carbon bisulfide 4.21g (55.31mmol), azo initiator V-50 Medicine industrial group manufactures) 1.00g (3.69mmol) and tri-n-butyl phosphine 3.73g (18.44mmol) puts into the anti-of pressure glass Answer in container, under nitrogen atmosphere, while stir with Magnetitum agitator, while react 72 hours at 50 DEG C.After reaction, decompression evaporates except methanol With unreacted Carbon bisulfide, it is thus achieved that active free radical polymerization controlling agent.

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

(manufacture of high-purity PSSNa)

By commercially available sodium p styrene sulfonate (the SPINOMAR NaSS that TOSOH organic chemistry company manufactures) 1000g, pure Water 950g, sodium hydroxide 40g, sodium nitrite 1g put in the removable flask of 2L, 60 DEG C of heating 1 hour, the most completely Dissolve.Subsequently, it is cooled to 10 DEG C with the 1 hour speed of 10 DEG C, separates out crystallization, reclaim p styrene sulfonic acid by centrifugal filtration Sodium.Precision weighs a small amount of sample, the weight after being vacuum dried 6 hours at 50 DEG C, after calculating moisture, be 9.2 weight %.With from The sodium bromide that sub-chromatograph measures is 0.19 weight %, and sodium sulfate is 0.04 weight %.That is, β-bromo ethyl phenenyl sodium sulfonate it is added with Monomer component be 90.57 weight %.

Analyze the organic impuritiess such as isomer contained in above-mentioned sodium p styrene sulfonate with HPLC, result be (a) 0.16%, (b) 0.43%, (c) 2.65%, (d) 0.04% (HPLC collection of illustrative plates shown in Fig. 1).

Then, the 1L glass flask being mounted with reflux cooling pipe, nitrogen ingress pipe, paddle stirrer puts into pure water 100.00g, heats with the oil bath of 85 DEG C under nitrogen atmosphere.The p styrene sulfonic acid prepared separately is dripped wherein with 104 minutes Sodium water solution [is that the aqueous high-purity sodium p styrene sulfonate 223.00g graded of above-mentioned acquisition is dissolved in pure water 884.00g In], with 113 minutes dropping initiator solution (be to be dissolved in Ammonium persulfate. 2.77g in pure water 121.00g to form ), it is polymerized.After starting polyase 13 hour, make oil bath temperature be warming up to 90 DEG C, be further continued for polyase 13 hour, it is thus achieved that polyphenyl second Alkene sodium sulfonate aqueous solution.

Number-average molecular weight Mn of the kayexalate tried to achieve with GPC is for 57000, and weight average molecular weight Mw is 160000 (Mw/Mn=2.81).This polymer is set to PSS-1.

(manufacture of CNT aqueous dispersion)

The vacuum drying thing 0.1g of the poly styrene sulfonate of above-mentioned acquisition is dissolved in the mixed of pure water 8ml and acetone 2ml In bonding solvent (0.1 weight % solution).Add wherein 0.1g multi-layer C NT (Tokyo chemical conversion industrial group manufacture, diameter 20～ 40nm, length 1～2 μm) after, process 1 hour with ultrasonic emulsator (US-600T of Japan's essence mechanism) dispersion, it is thus achieved that CNT water Property dispersion (CNT concentration 1 weight %, CNT/ poly styrene sulfonate weight ratio=1).Now, liquid temperature is maintained at less than 40 DEG C.

By composition and the evaluation result (average particle after after just manufacturing and preserving at 50 DEG C × 14 days of CNT aqueous dispersion Footpath and pH) it is shown in table 1.Compare with comparative example 1 described later, it is known that be respectively provided with the storage stability of excellence.

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

(manufacture of high-purity PSSLi)

In embodiment 1, p styrene sulfonic acid lithium (LiSS that TOSOH organic chemistry company manufactures) and Lithium hydrate are used Replace sodium p styrene sulfonate and sodium hydroxid, be repeated twice recrystallization purification same as in Example 1, it is thus achieved that impurity content (a) 0.14%, (b) 0.04%, (c) 0.01%, the high-purity p styrene sulfonic acid lithium of (d) 0.09%.This product shown in Fig. 2 HPLC collection of illustrative plates.

Then, in addition to using this p styrene sulfonic acid lithium 205.00g, enter with condition identical with embodiment 1 Row polymerization, it is thus achieved that polystyrolsulfon acid lithium aqueous solution.

Number-average molecular weight Mn of the polystyrolsulfon acid lithium tried to achieve with GPC is for 59000, and weight average molecular weight Mw is 156000 (Mw/Mn=2.64).This polymer is set to PSS-2.

(manufacture of CNT aqueous dispersion)

In addition to using the vacuum drying thing of the poly styrene sulfonate of above-mentioned acquisition, with identical with embodiment 1 Condition obtain CNT aqueous dispersion.

Embodiment 3 (the manufacture example of PSSLi Yu the CNT aqueous dispersion of high-purity and narrow molecular weight distribution)

(manufacture of the PSSLi of high-purity and narrow molecular weight distribution)

The 1L glass flask being mounted with reflux cooling pipe, nitrogen ingress pipe, paddle stirrer puts in embodiment 2 and obtains High-purity p styrene sulfonic acid lithium [impurity content (a) 0.14%, (b) 0.04%, (c) 0.01%, (d) 0.09%] 205.00g, pure water 800.00g, under nitrogen atmosphere, with 40 DEG C of heating, stirring 5 minutes, be allowed to dissolve.Add wherein and manufacture example The active free radical polymerization initiator 3.02g obtained in 1, is polymerized 12 hours oil bath temperature 65 DEG C, it is thus achieved that polystyrolsulfon acid Lithium aqueous solution.

The number-average molecular weight of the polystyrolsulfon acid lithium tried to achieve with GPC is for 127000, and weight average molecular weight is 165000 (Mw/ Mn=1.30).This polymer is set to PSS-3.

(manufacture of CNT aqueous dispersion)

By composition and the evaluation result (average particle after after just manufacturing and preserving at 50 DEG C × 14 days of CNT aqueous dispersion Footpath and pH) it is shown in table 1.Compare with comparative example 1 described later, it is known that be respectively provided with the storage stability of excellence.Further, since dispersibility More excellent, it is taken as that make the sharp molecular weight distribution of PSS bring impact than embodiment 1,2.

Embodiment 4 (high-purity and narrow molecular weight Distribution PS SLi (low molecule of PSS-3 quantifies) and CNT aqueous dispersion Manufacture)

(high-purity and the manufacture of narrow molecular weight Distribution PS SLi)

In embodiment 3, except the addition manufacturing the active free radical polymerization initiator obtained in example 1 is changed to Beyond 5.00g, remaining is polymerized with condition identical with embodiment 3, it is thus achieved that polystyrolsulfon acid lithium aqueous solution.

Number-average molecular weight Mn of the polystyrolsulfon acid lithium tried to achieve with GPC is for 73000, and weight average molecular weight Mw is 94000 (Mw/Mn=1.29).This polymer is set to PSS-4.

(manufacture of CNT aqueous dispersion)

By composition and the evaluation result (average particle after after just manufacturing and preserving at 50 DEG C × 14 days of CNT aqueous dispersion Footpath and pH) it is shown in table 1.Compare with comparative example 1, it is known that be respectively provided with the storage stability of excellence.Further, since dispersibility is than implementing Example 1,2 is more excellent, it is taken as that make the sharp molecular weight distribution of PSS bring impact.

Embodiment 5 (N-phenylmaleimide random copolymer and the manufacture of narrow molecular weight distribution and CNT aqueous dispersion The manufacture example of body)

(manufacture of random copolymer)

The 1L glass flask being mounted with reflux cooling pipe, nitrogen ingress pipe, paddle stirrer puts in embodiment 1 and obtains High-purity sodium p styrene sulfonate [impurity content (a) 0.16%, (b) 0.43%, (c) 2.65%, (d) 0.04%] 35.00g, pure water 282.00g, under nitrogen atmosphere, heat with the oil baths of 40 DEG C, stir 5 minutes and dissolve.Add N-benzene wherein The acetone soln (dissolving N-phenylmaleimide 7.00g in acetone 254.00g) of base maleimide, and with the oil of 65 DEG C After bath heats up, add and manufacture the active free radical polymerization initiator 4.00g obtained in example 1, be polymerized 12 when the temperature of 65 DEG C little Time.

Polymeric solution is transparent, in analytical solution residual monomer concentration, result sodium p styrene sulfonate, N-phenyl horse Carry out acid imide and be < 0.1 weight %.

The elemental analysis value of vacuum dried polymer is carbon 45.8 weight %, hydrogen 3.20 weight %, nitrogen 1.3 weight Amount %, sulfur 10.7 weight % are the most consistent with the monomer composition put into, although and containing the N-of water fast of 17 weight % Phenyl maleimide composition, but copolymer is still water solublity, in FT-IR spectrum, see be derived from N-phenylmaleimide with Absworption peak (the respectively 1707cm-of sodium p styrene sulfonate¹And 1040cm-¹), therefore this polymer is judged as having benzene Vinyl sulfonic acid sodium residue: N-phenylmaleimide residue=80: the copolymer of the composition of 20 moles of %.With being total to that GPC tries to achieve Number-average molecular weight Mn of polymers is 19000, and weight average molecular weight Mw is 26000 (Mw/Mn=1.37).This polymer is set to PSS- 5。

(manufacture of CNT aqueous dispersion)

By composition and the evaluation result (average particle after after just manufacturing and preserving at 50 DEG C × 14 days of CNT aqueous dispersion Footpath and pH) it is shown in table 1.Compare with comparative example 1, it is known that be respectively provided with the storage stability of excellence.Further, since dispersibility is than implementing Example 1～4 is more excellent, it is taken as that import the strong N-phenylmaleimide of the adsorptivity to CNT in PSS skeleton can bring shadow Ring.

Embodiment 6 (methacrylic acid block copolymer and the manufacture example of CNT aqueous dispersion)

(manufacture of methacrylic acid block copolymer)

In the 1L glass flask being mounted with reflux cooling pipe, nitrogen ingress pipe, paddle stirrer, under nitrogen atmosphere, put into High-purity Sodium styrene sulfonate [impurity content (a) 0.16%, (b) 0.43%, (c) 2.65%, (d) obtained in embodiment 1 0.04%] 120.00g, pure water 546.00g, with the oil bath heated and stirred of 40 DEG C, makes sodium p styrene sulfonate dissolve.Make oil bath liter After warm to 65 DEG C, add rapidly and manufacture the active free radical polymerization initiator 2.00g obtained in example 1, add thermal polymerization 10 hours.

Extract the polymeric solution of 0.5ml with syringe out, measure through GPC, result p styrene sulfonic acid concentration < 0.1 weight %, number Average molecular weight Mn is 109000, and weight average molecular weight Mw is 136000 (Mw/Mn=1.25).

Make bath temperature be maintained at 65 DEG C, add methacrylic acid sodium water solution 69.04g (by methacrylic acid 13.00g, hydrogen-oxygen Change the solution that sodium 6.04g and pure water 50.00g is constituted), continue polymerization 12 hours.

Number-average molecular weight Mn of the copolymer tried to achieve with GPC is for 121000, and weight average molecular weight Mw is 164000 (Mw/Mn= 1.36) peak of the kayexalate, being initially polymerized is towards the displacement of high molecular side.Metering system acid concentration in polymeric solution < 0.1 weight %.

The elemental analysis value of vacuum dried polymer is carbon 48.1 weight %, hydrogen 3.4 weight %, sulfur 13.2 weight Amount %, due to the most consistent with the monomer composition put into, is therefore judged as having kayexalate by this polymer: poly-first The block copolymer of the composition of base acrylic acid=79:21 mole of %.This polymer is set to PSS-6.

(manufacture of CNT aqueous dispersion)

The composition of CNT aqueous dispersion and the evaluation result (mean diameter after after just manufacturing and preserving at 50 DEG C × 14 days With pH) it is shown in table 1.Compare with comparative example 1, it is known that be respectively provided with the storage stability of excellence.Further, since dispersibility compares embodiment 1～4 is more excellent, it is taken as that the one-tenth branch linking hydrophilic lower than p styrene sulfonic acid on PSS brings impact.

Embodiment 7 (styrene block copolymer and the manufacture example of CNT aqueous dispersion)

(manufacture of styrene block copolymer)

The 1L glass flask being mounted with reflux cooling pipe, nitrogen ingress pipe, paddle stirrer puts in embodiment 1 and obtains High-purity Sodium styrene sulfonate [impurity content (a) 0.16%, (b) 0.43%, (c) 2.65%, (d) 0.04%] 35.00g with Pure water 280g, with the oil bath heated and stirred of 40 DEG C, makes sodium p styrene sulfonate dissolve.After making oil bath be warming up to 65 DEG C, add rapidly Add and manufacture the active free radical polymerization initiator 0.88g obtained in example 1, add thermal polymerization 12 hours.

Extract the polymeric solution of 0.5ml with syringe out, measure as a result, concentration < 0.1 weight of p styrene sulfonic acid through GPC Amount %, number-average molecular weight Mn is 73000, and weight average molecular weight Mw is 91000 (Mw/Mn=1.25).

Making bath temperature be maintained at 65 DEG C, (be made up of styrene 2.00g and acetone 230g is molten to add styrene solution 232g Liquid), continue polymerization 24 hours.

Polymeric solution is transparent, concentration of styrene < 0.1 weight % in solution.

The elemental analysis value of vacuum dried polymer is carbon 44.3 weight %, hydrogen 3.4 weight %, sulfur 13.8 weight Amount %, due to the most consistent with the monomer composition put into, although the styrene of the water fast therefore containing 5 weight % becomes Point, but copolymer is still water solublity, this polymer is judged as have kayexalate residue: styrene residue=90: The copolymer of the composition of 10 moles of %.Number-average molecular weight Mn of the copolymer tried to achieve with GPC is for 77000, and weight average molecular weight Mw is 116000 (Mw/Mn=1.51).This polymer is set to PSS-7.

(manufacture of CNT aqueous dispersion)

By composition and the evaluation result (average particle after after just manufacturing and preserving at 50 DEG C × 14 days of CNT aqueous dispersion Footpath and pH) it is shown in table 1.Compare with comparative example 1 described later, it is known that be respectively provided with the storage stability of excellence.Further, since dispersibility It is more excellent than embodiment 1～4, it is taken as that the polystyrene linking hydrophobicity higher on PSS can bring impact.

Comparative example 1 (using the example of 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%, the low-purity of (d) 0.06% Beyond sodium p styrene sulfonate 223.00g, it is polymerized with condition identical with embodiment 1, it is thus achieved that polystyrolsulfon acid Sodium water solution.

Number-average molecular weight Mn of the kayexalate tried to achieve with GPC is for 52000, and weight average molecular weight Mw is 161000 (Mw/Mn=3.10).This polymer is set to PSS-8.It addition, above-mentioned low-purity sodium p styrene sulfonate shown in Fig. 3 HPLC collection of illustrative plates.

(manufacture of CNT aqueous dispersion)

The composition of CNT aqueous dispersion and the evaluation result (mean diameter after after just manufacturing and preserving at 50 DEG C × 14 days With pH) it is shown in table 1.Compare with embodiment, though particle diameter immediately after preparation has not seen significant difference, but be clearly seen from through time point Dissipate stability to decline or pH decline.

Embodiment 8～13 (manufacture of electric conductive polymer dispersion and evaluation)

First, remove, according to the method for Japanese Laid-Open Patent Publication 60-15408 publication, the polyphenyl obtained in embodiment 1～4,6,7 Unwanted ion contained in hexenoic acid saline solution.That is, by be filled with anion exchange resin [Amberlite IRA- 410 (with sodium hydroxide regeneration resins)] post process poly styrene sulfonate solution, remove bromine, sulfate ion etc. the moon from After son, by being filled with the cation exchange resin [Amberlite RB-120 (tree with regeneration of hydrochloric acid that Organo company manufactures Fat)] post and remove the cation such as sodium, lithium.Subsequently, solid constituent (measuring after being vacuum dried 3 hours at 100 DEG C) is adjusted to 10.00 weight %.

At room temperature by above-mentioned PSS saline solution 20.00g and 3,4-Ethylenedioxy Thiophene (Tokyo chemical conversion industrial group system The reagent made) 1.00g puts in pure water 100ml, is stirred vigorously 30 minutes with stirring vane.Then, in room temperature, the condition of stirring The 20 weight % ammonium persulfate aqueous solutions of lower interpolation 1ml, as oxidant, start oxidation polymerization.Subsequently, added at interval of 10 minutes Add the 20 weight % ammonium persulfate aqueous solution 7 times (adding up to 8ml) of 1ml, stir limit polymerization in 60 hours on room temperature limit.

Subsequently, at normal temperatures through 10 minutes ultrasonic irradiations (US-600T that Japan's essence machine manufactures), so that above-mentioned acquisition PEDOT dispersion particle diminishes.

Subsequently, [the Amberlite RB-120 that Organo company manufactures is (with hydrochloric acid for the cation exchange resin of interpolation 5ml The resin of regeneration)], the anion exchange resin of 7ml [Amberlite IRA-410 (with the resin of sodium hydroxide regeneration)], Room temperature is slowly stirred 2 hours.Subsequently, by filtering cation exchange resin and anion exchange resin, it is thus achieved that solid constituent 1.9 The PEDOT of weight %.And then, add sub-relative to the dimethyl that PEDOT composition is 5 weight % in PEDOT aqueous dispersion Sulfone, evaluates the physical property of dispersion.Using the character of the kind of PSS salt used as dispersant and dispersion (after just manufacturing and 50 DEG C × 7 days preserve after mean diameter and conductivity) be shown in table 2.

Compare with comparative example 2 described later, it is known that conductivity is the most excellent with storage stability.It addition, understand at styrene sulphur In hydrochlorate homopolymer, molecular weight distribution the narrowest (employing PSS-3, the embodiment 10,11 of 4), then conductivity is the most excellent.

Comparative example 2

In embodiment 8～13, except using the poly styrene sulfonate solution obtained in comparative example 1 to replace embodiment Beyond the poly styrene sulfonate solution obtained in 1～4,6,7, to obtain PEDOT with the identical condition of embodiment 8～13 Aqueous dispersion.

Using the character of the kind of PSS salt used as dispersant and dispersion (after just manufacturing and after within 50 DEG C × 7 days, preserving Mean diameter and conductivity) be shown in table 2.Though particle diameter immediately after preparation has not seen notable difference, but be clearly seen from through time Conductivity and the decline of stability.

Probability is utilized in industry

Utilize the present invention through the polystyrolsulfon acid of structure control or the nano-carbon material of its salt and conductive poly The aqueous dispersion of compound can be used for conductive coating paint, LSI distribution, electromagnetic shielding material, electrochemical appliance (fuel cell, Secondary cell, capacitor, Field Emission Display, transistor, solaode, various electrode), antistatic coating, organic EL, touch In the purposes of control panel, the industrialization of nano-carbon material or electric conductive polymer can be brought contribution.

Symbol description

(a): the absorption intensity of adjacent styrene sulfonate

The absorption intensity of (b): β-bromo ethyl phenenyl sulfonate

(c): the absorption intensity of a styrene sulfonate

(d): the absorption intensity of bromstyrol sulfonate

Claims

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.