CN103958552A - High-purity parastyrene sulfonic acid (salt) - Google Patents

High-purity parastyrene sulfonic acid (salt) Download PDF

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CN103958552A
CN103958552A CN201280055963.0A CN201280055963A CN103958552A CN 103958552 A CN103958552 A CN 103958552A CN 201280055963 A CN201280055963 A CN 201280055963A CN 103958552 A CN103958552 A CN 103958552A
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salt
acid
sulfonic acid
radical polymerization
free radical
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CN103958552B (en
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尾添真治
山野井健一
松永秀秋
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Tosoh Organic Chemical Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01B32/00—Carbon; Compounds thereof
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints

Abstract

Provided is a novel polystyrene sulfonic acid (salt) which is useful as a dispersant for producing an aqueous dispersion of a nanocarbon material such as a carbon nanotube, graphene or fullerene or an aqueous dispersion of a conductive polymer such as a polythiophene, polypyrrole, polyaniline, polyphenylene vinylene or polyphenylene. A structure-controlled polystyrene sulfonic acid (salt) which is obtained using a high-purity parastyrene sulfonic acid (salt) that contains less impurities such as isomers; a dispersant which contains the polystyrene sulfonic acid (salt) as an active ingredient; an aqueous dispersion of a nanocarbon material or a conductive polymer, which is obtained using the dispersant; and a method for producing the polystyrene sulfonic acid (salt).

Description

High purity p styrene sulfonic acid (salt), used its polystyrolsulfon acid (salt) and used the manufacture method of dispersion agent, electric conductive polymer doping agent, nano-carbon material aqueous dispersion, electric conductive polymer aqueous dispersion and the polystyrolsulfon acid (salt) of polystyrolsulfon acid (salt)
Technical field
The present invention relates to high purity p styrene sulfonic acid (salt), used its polystyrolsulfon acid through structure control (salt) and as the purposes of dispersion agent and use the nano-carbon material of its manufacture and the aqueous dispersion of electric conductive polymer and then relate to the manufacture method of this polystyrolsulfon acid (salt).
Background technology
Carbon nanotube (being designated hereinafter simply as CNT) is owing to having light weight high strength, high abrasion resistance, high thermal conductivity, high-melting-point, high conductivity, semi-conductivity, high-specific surface area, hollow structure, high gas adsorbability, the characteristics such as biocompatibility, therefore expecting has towards high-strength material, high conductivity material, conductive material, LSI distribution, micromechanics (micro machine), carbon dioxide fixing material, hydrogen occlusion material, electromagnetic shielding material, catalyst loading material, nanofilter, biosensor, delivery system, electrochemical appliance (fuel cell, secondary cell, electrical condenser, transistor, Field Emission Display, Electronic Paper, thin film organic solar battery, dye sensitization solar battery, organic EL, contact panel, various electrodes) etc. application.
Yet CNT easily condenses because of intermolecular forces, this character becomes the practical biggest obstacle in above-mentioned field.Accordingly, strongly seek not make CNT cohesion and make it stably to carry out the technology of nano-dispersed in solvent or various polymeric matrix.
For example, to utilize the fine distribution of the unicircuit that ink jet printing mode carries out making, utilize manufacture and the flat-panel monitor in the field-transmitting cathode source that screen painting mode carries out to carry out applied research, therefore for the manufacture method of required CNT aqueous dispersion, kinds of schemes has been proposed.For example, openly use the manufacture method (reference example is as patent documentation 1) of the CNT aqueous dispersion of the aniorfic surfactant with steroid skeleton, and be disclosed in the manufacture method (reference example is as patent documentation 2) of having used the CNT aqueous dispersion of dodecyl methylene-succinic acid in dispersion agent.In addition, open using there is hydrophilic group triphenylenyl derivative as dispersion agent, the ultrasonic wave of high output is irradiated on limit, the method (reference example is as patent documentation 3) of CNT water dispersion is manufactured on limit, or has used the manufacturing process (reference example is as patent documentation 4) of the derivatived cellulose with particular functional group.Yet above-mentioned either method all may not meet dispersion effect, and there is the problem of more expensive dispersion agent of use etc.
On the other hand, it is also known having utilized the method for styrene sulfonic acid.For example, openly used the manufacture method (reference example is as patent documentation 5 and patent documentation 6) of the CNT water dispersion of poly styrene sulfonate (homopolymer).In addition, openly used the manufacture method (reference example is as patent documentation 7) of the CNT water dispersion of styrene sulfonic acid-maleic acid salt.Though these polystyrolsulfon acid polymer salts can be safe, lower cost ground suitability for industrialized production, dispersion effect can not say fully, so require the further raising of dispersion effect.
On the other hand, with regard to polythiophene class, polypyrrole class, polyaniline compound, sub-ethene (Polyphenylene vinylene) class of polyphenylene, the organic conductive polymkeric substance (hereinafter referred to as electric conductive polymer) such as polyphenylene (Polyphenylene) class, from electroconductibility, flexibility, the viewpoint of light weight is set out, as antistatic coating, solid electrolytic capacitor electrode, electromagnetic wave shielding material, starter motor (actuator), collection of energy (energy harvesting) (generating) material, and lithium secondary battery, sodium rechargeable battery, organic thin film solar cell, dye sensitization solar battery, OLED display, Electronic Paper, the member of contact panel etc., the substitute of ITO (tin indium oxide) transparency electrode and being expected.Yet above-mentioned electric conductive polymer, due to identical with CNT, for insoluble and not molten, is therefore difficult to apply processing.Therefore, electric conductive polymer has been become to the main flow of exploitation with the microgranular type being scattered in organic solvent or aqueous solvent, and commercially available.
In order to manufacture the aqueous dispersion of electric conductive polymer, need with so that the dispersion agent of electric conductive polymer stabilization in water with micropartical or nanoparticle shape, but main flow is now polystyrolsulfon acid (reference example is as patent documentation 8,9).Polystyrolsulfon acid (hereinafter referred to as PSS) is strong electrolyte polymkeric substance, not only brings into play the effect as dispersion agent, also brings into play to represent the effect of doping agent of the electroconductibility of electric conductive polymer.
Yet, electric conductive polymer aqueous dispersion is in the past when as ito transparent electrode substitute or electromagnetic wave shielding material, and electroconductibility is also not enough, in addition, stability, water tolerance and poor to the adaptation of the various base materials such as aluminium, tantalum, glass, polyester film, therefore expect the improvement to these strongly.Above-mentioned low electric conductivity, stability, water tolerance and adaptation it is said has much relations with the remaining PSS as dispersion agent performance function.
Patent documentation
Patent documentation 1: TOHKEMY 2009-242126 communique
Patent documentation 2: TOHKEMY 2010-13312 communique
Patent documentation 3: TOHKEMY 2009-190940 communique
Patent documentation 4: TOHKEMY 2011-127041 communique
Patent documentation 5: TOHKEMY 2005-263608 communique
Patent documentation 6: TOHKEMY 2010-254546 communique
Patent documentation 7: Japanese Unexamined Patent Application Publication 2006-525220 communique
Patent documentation 8: Japanese kokai publication hei 7-90060 communique
Patent documentation 9: TOHKEMY 2004-59666 communique
Summary of the invention
The present invention completes in view of above-mentioned problem, and its object is to provide a kind of conduct in order to manufacture the useful PSS through structure control or its salt (below also referred to as " PSS (salt) ") of dispersion agent of the aqueous dispersion of the electric conductive polymers such as the nano-carbon materials such as CNT, Graphene (graphene), soccerballene and polythiophene class, polypyrrole class, polyaniline compound, the sub-vinyl of polyphenylene, polyphenylene class.
The inventor etc. carry out active research for solving above-mentioned problem, found that the physical property that PSS (salt) through structure control becomes for the aqueous dispersion of the electric conductive polymers such as the nano-carbon materials such as CNT, Graphene, soccerballene and polythiophene class, polypyrrole class, polyaniline compound, the sub-vinyl of polyphenylene, polyphenylene class improves useful dispersion agent, thereby complete the present invention.
The present invention relates to a kind of high purity p styrene sulfonic acid or its salt (below also referred to as " p styrene sulfonic acid (salt) "), wherein, as (a) the adjacent styrene sulfonic acid (salt) that is derived from the cinnamic major impurity of raw material sometimes containing in p styrene sulfonic acid (salt), (b) β-bromo ethyl phenenyl sulfonic acid (salt), (c) styrene sulfonic acid between (salt), (d) ratio that contains of the peak area benchmark of trying to achieve with high performance liquid chromatography (hereinafter referred to as HPLC) of bromstyrol sulfonic acid (salt) is respectively (a)≤0.20%, (b)≤0.50%, (c)≤3.00%, and (d)≤0.10% (wherein, p styrene sulfonic acid (salt) with (a)～(d) summation of peak area is 100).
Then, the present invention relates to a kind of polystyrolsulfon acid or its salt (below also referred to as " polystyrolsulfon acid (salt) "), it is to use above-mentioned high purity p styrene sulfonic acid (salt) to manufacture, there is following repeated structural unit A, or there is following repeated structural unit A and following repeated structural unit B
[in repeated structural unit A, B, M represents sodium cation, lithium cation, potassium cationic, ammonium cation, quaternary ammonium cation or proton, and Q represents free radical polymerization monomer residue, and n represents more than 1 integer, and m represents more than 0 integer].
Polystyrolsulfon acid of the present invention (salt) preferably has the polystyrolsulfon acid (salt) of at least arbitrary structure in following formula (I)～(III),
[in formula (I)～(III), M represents sodium cation, lithium cation, potassium cationic, ammonium cation, quaternary ammonium cation or proton, Q represents other free radical polymerization monomer residue, and n and more than 1 integer of n ' expression, and m and m ' represent more than 0 integer].
Herein, the weight-average molecular weight of trying to achieve with gel permeation chromatography (hereinafter referred to as GPC) of polystyrolsulfon acid of the present invention (salt) preferably 2,000～1,000,000, weight-average molecular weight is preferably less than 2.0 with the ratio (=weight-average molecular weight/number-average molecular weight) of number-average molecular weight.
In addition, as the Q in above-mentioned repeated structural unit B and above-mentioned (I)～(III), be preferably more than one the free radical polymerization monomer residue being selected from vinylbenzene residue, styrene derivatives residue, methacrylic acid residue, 2-hydroxyethyl methacrylate residue, glycidyl methacrylate residue, (methyl) acrylamide residue, NVP residue, N-phenylmaleimide residue, maleic anhydride residue.
Then, the present invention relates to more than one and state polystyrolsulfon acid (salt) as dispersion agent and the electric conductive polymer doping agent of effective constituent.
In addition, the present invention relates to a kind of use above-mentioned polystyrolsulfon acid (salt) nano-carbon material aqueous dispersion that manufacture forms as dispersion agent, and the electric conductive polymer aqueous dispersion that uses above-mentioned polystyrolsulfon acid (salt) to form as dispersion agent and doping agent manufacture.
Then, the present invention relates to above-mentioned high purity p styrene sulfonic acid (salt) to carry out the manufacture method of the above-mentioned polystyrolsulfon acid (salt) of radical polymerization or active free radical polymerization in aqueous solvent.
In addition, the present invention relates to the manufacture method of a kind of above-mentioned polystyrolsulfon acid (salt), wherein in aqueous solvent, free radical polymerization monomer is carried out after active free radical polymerization, add above-mentioned p styrene sulfonic acid (salt), continue again active free radical polymerization, or in aqueous solvent, this p styrene sulfonic acid (salt) is carried out after active free radical polymerization, add free radical polymerization monomer, then continue active free radical polymerization.
Herein, active free radical polymerization initiator used in the present invention is preferably the compound with the supposition structure representing with following formula (IV),
[in formula (IV), R 3, R 4, R 5the straight chain shape that expression is substituted independently of one another or the alkyl or phenyl of branch-like, R 3, R 4, R 5can be identical, also can be different, R 1and R 2expression, can be mutually the same corresponding to the univalent perssad of the free radical being produced by free-radical generating agent, also can be different].
The PSS through structure control (salt) that uses high purity p styrene sulfonic acid of the present invention (salt) to manufacture to form is in aqueous medium, the ability that the electric conductive polymers such as the nano-carbon materials such as CNT, Graphene, soccerballene and polythiophene class, polypyrrole class, polyaniline compound, the sub-vinyl of polyphenylene, polyphenylene class are scattered in aqueous medium is high, and can be used for improving electric conductivity, stability and the water tolerance of electric conductive polymer aqueous dispersion.
Accompanying drawing explanation
Fig. 1 is the HPLC color atlas 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), and transverse axis represents dissolution time (unit for minute).(a) in Fig. 1, (b), (c), (d) represent respectively the intensity of styrene sulfonic acid (salt), (d) bromstyrol sulfonic acid (salt) between (a) adjacent styrene sulfonic acid (salt), (b) β-bromo ethyl phenenyl sulfonic acid (salt), (c).
Fig. 2 is the HPLC color atlas 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 color atlas of the low-purity p styrene sulfonic acid salt of comparative example 1.Other is identical with the explanation of Fig. 1.
Embodiment
The present invention is as (a) the adjacent styrene sulfonic acid (salt) that is derived from the cinnamic major impurity of raw material sometimes containing in p styrene sulfonic acid (salt), (b) β-bromo ethyl phenenyl sulfonic acid (salt), (c) styrene sulfonic acid between (salt), (d) ratio that contains of the peak area benchmark of trying to achieve with HPLC of bromstyrol sulfonic acid (salt) is respectively (a)≤0.20%, (b)≤0.50%, (c)≤3.00%, and (d)≤0.10% (, p styrene sulfonic acid (salt) with (a)～(d) summation of peak area is 100) high purity p styrene sulfonic acid (salt), and use the above-mentioned repeated structural unit A of having of its manufacture, or above-mentioned repeated structural unit A and following repeated structural unit B and there is PSS or its salt [PSS (salt)] of at least arbitrary structure in above-mentioned formula (I) for example～(III).
PSS of the present invention (salt) is not limited in PSS (salt) homopolymer, as long as there is above-mentioned repeated structural unit A, or above-mentioned repeated structural unit A and B, be just not particularly limited, also can be random copolymers or segmented copolymer.Segmented copolymer described herein is that PSS (salt) chain (above-mentioned repeated structural unit A) polymer chain (above-mentioned repeated structural unit B) Jie different from PSS (salt) is formed by the mutual block bonding of covalent linkage, comprises the types such as diblock, three blocks, many block types.The better illustration of above-mentioned segmented copolymer of the present invention can list has above-mentioned formula (I)～segmented copolymer of structure (III).
In addition, in above-mentioned repeated structural unit A～B and above-mentioned formula (I)～(III), n and n ' are more than 1 integer, are preferably 10～5000 integer, and m and m ' are more than 0 integer, are preferably 0～5000 integer.
The invention is characterized in that PSS (salt) is through structure control, alleged structure control herein has three kinds of implications.
Monomer [p styrene sulfonic acid (the salt)] high purity of the first implication for making to use in the manufacture of PSS (salt), is illustrated in down.
P styrene sulfonic acid (salt), generally with following method manufacture, cannot avoid the impurity such as unreacted halogenide, isomer, metal halide produce or sneak into as by product in method for making.
Detailed analysis p styrene sulfonic acid (salt), result is judged as main impurity, comprises and is derived from styrene sulfonic acid (salt), (d) bromstyrol sulfonic acid (salt) between raw material cinnamic (a) adjacent styrene sulfonic acid (salt), (b) β-bromo ethyl phenenyl sulfonic acid (salt), (c).The utilizations such as the inventor are by the method containing p styrene sulfonic acid (salt) recrystallize purifying from the aqueous solution of above-mentioned impurity or by controlling creating conditions of temperature of reaction etc., these impurity of the peak area benchmark that manufacture is tried to achieve with HPLC contain the high purity p styrene sulfonic acid (salt) that ratio is respectively (a)≤0.20%, (b)≤0.50%, (c)≤3.00% and (d)≤0.10%, and use this high purity p styrene sulfonic acid (salt), utilize radical polymerization in the past to manufacture high purity PSS (salt).In dispersion agent, use it and manufacture CNT aqueous dispersion or as poly-(3 of representative electric conductive polymer, 4-Ethylenedioxy Thiophene) aqueous dispersion of (hereinafter referred to as PEDOT), found that with using the situation of PSS in the past and compare, the stability of dispersion improves.And then, find that the electric conductivity of filming being obtained by PEDOT aqueous dispersion improves.
Though reason is indefinite, about the stability of dispersion, improve, think because of between the minimizing of the isomer such as a body improve the cause of the stability of PSS (salt).About the raising of electric conductivity, do not mention up to now the regular report example of the PSS (salt) in this purposes, but think it is perhaps because the regularity of PSS (salt) improves, to make the doping rate of PEDOT improve.
In addition, the present invention also refers to comprise and makes high purity PSS that above-mentioned high purity p styrene sulfonic acid (salt) obtains through radical polymerization in aqueous solvent or the solution of its salt.That is, (b) β-bromo ethyl phenenyl sulfonic acid (salt) in above-mentioned impurity is due to containing free-radical polymerised pair of key, therefore in PSS (salt) skeleton not by copolymerization, but be present in PSS (salt) solution making in aqueous medium.While using PSS (salt) aqueous solution containing the impurity such just like β-bromo ethyl phenenyl sulfonic acid (salt) in the purposes such as aluminium electrolutic capacitor etc., because the decomposition of β-bromo ethyl phenenyl sulfonic acid (salt) makes halogen free, when the galvanic corrosion reaction of the aluminium producing because of this halogen occurs repeatedly, cause capacitor faults.Therefore, preferably also do one's utmost to reduce β-bromo ethyl phenenyl sulfonic acid (salt).
Secondary Meaning for make PSS (salt) molecular weight distribution, be that the value of so-called weight-average molecular weight/number-average molecular weight is narrowed to and is less than 2.0.The inventor etc. utilize living radical polymerization, synthetic molecular weight distributes and is less than 2.0 PSS (salt), and use it in dispersion agent, manufacture after CNT aqueous dispersion or PEDOT aqueous dispersion, found that with using the situation of PSS in the past and compare, the stability of dispersion improves, and the electroconductibility that PEDOT aqueous dispersion is filmed improves.
Think because the narrow molecular weight distribution by PSS (salt) makes the cause as the efficiency raising of dispersion agent.That is, think particle diameter with respect to dispersate, when the length of PSS (salt) is too short, PSS (salt) is easily from dispersate desorb, and on the contrary, when long, PSS (salt) makes dispersate bridge joint and condensing each other.In addition, though reason is indefinite, think after PEDOT aqueous dispersion is manufactured, be difficult to cause that PSS (salt) is from the desorb of PEDOT particle surface, therefore make electric conductivity improve.
In addition, the molecular weight distribution of PSS of the present invention (salt) is preferably less than 2.0.It is better that molecular weight distribution approaches expression monodispersed 1.0, but while considering productivity, the cost of PSS (salt), and further preferably 1.0～1.8.In the present invention, in order to make the molecular weight distribution of PSS (salt) be less than 2.0, as described later, high purity p styrene sulfonic acid of the present invention (salt) is carried out to active free radical polymerization, now, as long as use the radical polymerization initiator representing with formula described later (IV), or by the PSS (salt) with common molecular weight distribution, use post to divide the PSS (salt) that gets desired molecular weight.
The 3rd implication be will be different from PSS (salt) polymkeric substance and PSS (salt) with block-wise, link (so-called block copolymerization).The discoveries such as the inventor connect to block-wise by PSS (salt) polymkeric substance lower than PSS (salt) with being considered to wetting ability by active free radical polymerization, manufacture PSS (salt) segmented copolymer, and with it, as dispersion agent, manufacture CNT or PEDOT aqueous dispersion, result can further improve the stability of dispersion.Think because the low block of wetting ability is adsorbed on the hydrophobic materials such as CNT or PEDOT effectively, or on the contrary, by remaining PSS (salt), kept dispersion stabilization in the past, but the present invention by wetting ability than the low other block of PSS (salt) and decentralized stabilization.Moreover, by PSS (salt) and heterogeneous polymer blocks ground bonding, and have can improve in the past as problem to the adaptation of the base materials such as resin, glass, ITO, with the possibility of the intermiscibility of the polymkeric substance of other kind.
For the weight-average molecular weight of trying to achieve with GPC of PSS of the present invention (salt) unrestricted, preferably 2,000～1,000,000, during polymerization starter amount when operability, the PSS (salt) that considers the aqueous dispersion such as viscosity manufactures etc., further preferably 5,000～600,000.
This weight-average molecular weight can easily be adjusted with respect to the addition of monomer by polymerization starter or chain-transfer agent.
As the p styrene sulfonic acid (salt) using in PSS of the present invention (salt) or PSS (salt) segmented copolymer other monomer in addition, as long as utilize PSS (salt) free radical to carry out radical polymerization, or produce and can become the free radical of radical polymerization initiator (in other words for p styrene sulfonic acid (salt), can carry out radical copolymerization with p styrene sulfonic acid (salt)), be just not particularly limited.Can list for example N-phenylmaleimide, N-(chloro-phenyl-) maleimide, N-(aminomethyl phenyl) maleimide, N-(isopropyl phenyl) maleimide, N-(sulfur phenenyl) maleimide, N-aminomethyl phenyl maleimide, N-bromophenyl Malaysia imide, N-naphthyl maleimide, N-hydroxy phenyl maleimide, N-p-methoxy-phenyl maleimide, N-carboxyl phenyl maleimide, N-(nitrophenyl) maleimide, N-benzyl maleimide, N-(4-acetoxyl group-1-naphthyl) maleimide, N-(4-Oxy-1-naphthyl) maleimide, N-(3-fluoranthene base (fluoranthyl)) maleimide, N-(5-fluorescein base (Fluoresceinyl)) maleimide, N-(1-pyrenyl) maleimide, N-(2,3-xylyl) maleimide, N-(2,4-xylyl) maleimide, N-(2,6-xylyl) maleimide, N-(aminophenyl) maleimide, N-(tribromo phenyl) maleimide, N-[4-(2-benzimidazolyl-) phenyl] maleimide, N-(3,5-dinitrophenyl) maleimide, the maleimides such as N-(9-acridyl) maleimide, dibutyl fumarate, fumaric acid dipropyl, DEF, the dimethyl ester classes such as fumaric acid two cyclohexyls, fumaric acid butyl ester, fumaric acid propyl ester, the fumaric monoalkylester classes such as ethyl fumarate, dibutyl maleinate, dipropyl maleate, the maleic acid diester classes such as ethyl maleate, toxilic acid butyl ester, toxilic acid propyl ester, ethyl maleate, the toxilic acid monoesters classes such as dicyclohexyl maleate, maleic anhydride, the acid anhydrides such as citraconic anhydride, maleimide, N-(sulfophenyl) maleimide, N-N-cyclohexylmaleimide, N-methyl maleimide, the maleimide of NEM etc., vinylbenzene, chloro-styrene, dichlorostyrene, bromstyrol, Dowspray 9, fluorobenzene ethene, trifluorostyrene, nitrostyrolene, cyano-styrene, alpha-methyl styrene, p-chloromethyl styrene, to cyano-styrene, to acetoxy-styrene, to vinylbenzene SULPHURYL CHLORIDE, p styrene sulfonic acid ethyl ester, p styrene sulfonic acid methyl esters, p styrene sulfonic acid propyl ester, to butyl phenyl ether ethene, 4-vinyl benzoic acid, 3-pseudoallyl-α, the styrenics such as α '-dimethylbenzyl based isocyanate, IVE, ethyl vinyl ether, 2-phenyl vinyl alkyl oxide, nitrophenyl vinyl ether, cyano-phenyl vinyl ether, the vinyl ethers such as chloro-phenyl-vinyl ether, methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, decyl acrylate, lauryl acrylate, Octyl acrylate, dodecylacrylate, stearyl acrylate acid esters, 2-EHA, cyclohexyl acrylate, vinylformic acid norbornene ester, vinylformic acid 2-ethoxy ethyl ester, vinylformic acid 2-butoxyethyl, vinylformic acid 2-hydroxy methacrylate, tetrahydrofurfuryl acrylate, vinylformic acid methoxyl group glycol ester, vinylformic acid ethyl carbitol ester, vinylformic acid 2-hydroxy propyl ester, vinylformic acid 4-hydroxyl butyl ester, vinylformic acid 3-(Trimethoxy silane base) propyl ester, polyalkylene glycol acrylate ester, glycidyl acrylate, 2-(acryloxy) ethyl phosphonic acid ester, vinylformic acid 2,2,3,3-tetrafluoro propyl ester, vinylformic acid 2,2,2-trifluoro ethyl ester, vinylformic acid 2,2,3,3,3-five fluorine propyl ester, vinylformic acid 2,2,3,4,4, the esters of acrylic acids such as 4-hexafluoro butyl ester, methyl methacrylate, Tert-butyl Methacrylate, the secondary butyl ester of methacrylic acid, Propenoic acid, 2-methyl, isobutyl ester, isopropyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate(LMA), Octyl methacrylate, lauryl methacrylate, methacrylic acid stearate, cyclohexyl methacrylate, methacrylic acid norbornene ester, benzyl methacrylate, phenyl methacrylate, glycidyl methacrylate, methacrylic acid macrogol ester, 2-hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, methacrylic acid methoxy ethyl glycol ester, methacrylic acid ethyl carbitol ester, methacrylic acid 2-hydroxy propyl ester, methacrylic acid 4-hydroxyl butyl ester, 2-(methacryloxy) ethyl phosphonic acid ester, methacrylic acid 2-(dimethylamino) ethyl ester, methacrylic acid 2-(diethylin) ethyl ester, methacrylic acid 3-(dimethylamino) propyl ester, methacrylic acid 2-(lsothiocyanates) ethyl ester, methacrylic acid 2,4,6-tribromo-benzene, methacrylic acid 2,2,3,3-tetrafluoro propyl ester, methacrylic acid 2,2,2-trifluoro ethyl ester, methacrylic acid 2,2,3,3,3-five fluorine propyl ester, the methyl acrylic esters such as methacrylic acid 2,2,3,4,4,4-hexafluroprobutyl alcohol, 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, chlorbutadiene, 2,3-, bis-chloro-1,3-butadienes, 2-cyano group-1,3-butadiene, 1-chloro-1,3-butadiene, 2-(N-piperidino methyl)-1,3-butadiene, 2-triethoxy methyl isophthalic acid, 3-divinyl, 2-(N, N-dimethylamino)-1,3-butadiene, N-(2-methylene radical-3-crotonoyl) morpholine, the 1,3-butadiene classes such as 2-methylene radical-3-butenyl diethyl phosphoric acid, in addition, list acrylamide, Methacrylamide, sulfophenyl acrylamide, sulfophenyl clothing health imide, vinyl cyanide, methacrylonitrile, flumaronitrile, vinylformic acid alpha-cyano ethyl ester, citraconic anhydride, vinylacetic acid, propionate, new vinyl acetate acid, tertiary ethylene carbonate, β-crotonic acid, methylene-succinic 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 dimethoxy silane, propenal, diacetone acrylamide, ethenyl methyl ketone, vinyl ethyl ketone, methacrylic acid dipropyl ketone ester, vinyl sulfonic acid, isoprene sulfonic acid, allyl sulphonic acid, 2-acrylamide-2-methyl propane sulfonic acid, 2-acrylamide-1-methylsulphonic acid, 2-Methacrylamide-2-methyl propane sulfonic acid, vinyl pyrrolidone, dehydroalanine, sulfurous gas, iso-butylene, N-vinyl Trivalin SF, sub-ethene dicyanide, to quinhydrones bismethane, chlorotrifluoroethylene, tetrafluoroethylene, norbornylene, N-vinyl Trivalin SF etc.Wherein, when the copolymerization of consideration and p styrene sulfonic acid or salt, operability etc., optimization styrene, styrene derivatives, methacrylic acid, 2-hydroxyethyl methacrylate, glycidyl methacrylate, NVP, N-phenylmaleimide, maleic anhydride.
There is no particular restriction for the content of non-PSS (salt) composition in above-mentioned PSS (salt) segmented copolymer, as long as adjust content according to object, but too low the making of wetting ability of multipolymer reduced as the function of dispersion agent owing to surpassing 98 % by weight, therefore preferably below 60 % by weight.
Then, the manufacture method for high purity p styrene sulfonic acid of the present invention (salt) is illustrated.
There is no particular restriction for the manufacture method of high purity p styrene sulfonic acid (salt), but can pass through such as impure p styrene sulfonic acid (salt) being dropped in the mixed solvent of the water-soluble solvents such as pure water or acetone, Virahol and water, after 40～70 ℃ of heating, dissolving, slowly cool to normal temperature, make p styrene sulfonic acid (salt) recrystallize and manufacture.By repeating this operation, can further improve purity.What this recrystallized is operating as more than 1 time, if consider productivity or cost, is preferably 1～3 time.
Further during the Production Example of particular instantiation high purity p styrene sulfonic acid of the present invention (salt), for example by make Sodium styrene sulfonate with 5～6 % by weight concentration heating for dissolving in methyl alcohol (conventionally at 40～50 ℃ about 10～60 minutes), and be cooled to lentamente near normal temperature～10 ℃, separate out after the crystallization of sodium p styrene sulfonate, after filtration, dry, can obtain high purity sodium p styrene sulfonate.
Then, the manufacture method for PSS of the present invention (salt) is illustrated.
There is no particular restriction for the manufacture method of PSS (salt), but the method that the general radical polymerization of illustration utilization is carried out is as first case.For example, as long as aqueous solvent and p styrene sulfonic acid or its salt and the homogeneous solution that can carry out the monomer mixture of radical copolymerization with p styrene sulfonic acid or its salt are optionally dropped in reaction vessel, optionally add molecular weight regulator, make after the interior deoxidation of system, be heated to specified temperature, the polymerization of radical polymerization initiator limit is added on limit.Now, for fear of fierce polymerization, and while considering the molecular weight control in lower molecular weight region, initial whole monomer mixtures is not dropped in reaction vessel, but preferably by each monomer together with polymerization starter or molecular weight regulator successively marginally continuous adding in reaction vessel.
There is no particular restriction for reaction solvent, but consider the solvability of p styrene sulfonic acid or its salt and comonomer, and during the manufacture of the nano-carbon material of CNT etc. and the aqueous dispersion of electric conductive polymer, preferably aqueous solvent, for example mixture of water and water-soluble solvent.As water-soluble solvent, so long as make p styrene sulfonic acid (salt) unrestricted with the composition of the mixture dissolving of comonomer, can list for example acetone, tetrahydrofuran (THF), two alkane, methyl alcohol, ethanol, n-propyl alcohol, Virahol, methyl cellosolve, ethoxy ethanol, butanols, ethylene glycol, propylene glycol, glycerine, dimethyl sulfoxide (DMSO), dimethyl formamide, N-Methyl pyrrolidone etc.Be preferably acetone, tetrahydrofuran (THF), two alkane, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone and dimethyl formamide.
As the usage quantity of the aqueous solvent of reaction solvent, with respect to monomer total amount 100 weight parts, be generally 150～2000 weight parts.
There is no particular restriction for molecular weight regulator, but can list for example di-isopropyl xanthogenic acid disulphide, auligen disulphide, diethyl thiuram disulphide, 2,2 '-dithiodipropionic acid, 3,3 '-dithiodipropionic acid, 4,4 '-dithio, two butyric acid, 2, the disulfides such as the two phenylformic acid of 2 '-dithio, n-dodecyl mercaptan, octyl mercaptan, tert-butyl mercaptan, thioglycolic acid, mercaptosuccinic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, thiosalicylic acid, 3-Thiosalicylic acid, 4-Thiosalicylic acid, sulfo-propanedioic acid, dithio succsinic acid, sulfo-toxilic acid, sulfo-maleic anhydride, dithio toxilic acid, sulfo-pentanedioic acid, halfcystine, homocysteine, 5-mercapto-tetrazole acetic acid, 3-sulfydryl-1-propane sulfonic acid, 3-sulfydryl propane-1,2-glycol, mercaptoethanol, 1,2-dimethyl ethane thiol, 2-MEA hydrochloride, 6-sulfydryl-1-hexanol, 2-sulfydryl-1-imidazoles, 3-sulfydryl-1,2,4-triazole, halfcystine, N-acyl group halfcystine, gsh, N-butyl ethylamine mercaptan, N, the thio-alcohols such as N-diethylamino ethane mercaptan, the halons such as iodoform (iodoform), diphenylethlene, p-dichlorobenzene base ethene, to cyano group diphenylethlene, α-methylstyrenedimer, dithio benzyl benzoate, dithiobenzoic acid 2-cyano group third-2-base ester, Organic Tellurium Compounds, sulphur, S-WAT, potassium sulfite, sodium bisulfite, Potassium hydrogen sulfite, Sodium Pyrosulfite, potassium pyrosulfite etc.
The usage quantity of molecular weight regulator, with respect to monomer total amount 100 weight parts, is generally 0.1～10 weight part.
As above-mentioned radical polymerization initiator, can list for example ditertiary butyl peroxide, diisopropylbenzyl superoxide, tert butyl isopropyl benzene peroxide, benzoyl peroxide, dilauryl superoxide, isopropyl benzene hydroperoxide, tertbutyl peroxide, 1,1-bis(t-butylperoxy)-3,5,5-trimethyl-cyclohexane, 1,1-bis(t-butylperoxy)-hexanaphthene, Cyclohexanone peroxides, peroxy t-butyl perbenzoate, peroxy tert-butyl isobutyrate, peroxy-3,5,5 Trimethylhexanoic acid tert-butyl ester, peroxy-2 ethyl hexanoic acid tert-butyl ester, peroxy sec.-propyl carboxylic acid tert-butyl ester, the sad cumyl ester of peroxy, Potassium Persulphate, ammonium persulphate, the peroxide of hydrogen peroxide etc., 2,2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile), 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (2-methyl propionitrile), 2,2 '-azo two (2-methylbutyronitrile), 1,1 '-azo two (hexanaphthene-1-formonitrile HCN), 1-[(1-cyano group-1-methylethyl) azo] methane amide, 2, two (2 Methylpropionic acid) dimethyl esters of 2 '-azo, 4,4 '-azo two (4-cyanopentanoic acid), 2,2 '-azo two (2,4,4-trimethylpentane), 2,2 '-azo two { 2-methyl-N-[1,1 '-bis-(hydroxymethyl)-2-hydroxyethyls] propionic acid amide }, 2, two { 2-(2-tetrahydroglyoxaline-2-yl) propane } dihydrochlorides of 2 '-azo, 2,2 '-azo two 2-(2-tetrahydroglyoxaline-2-yl) propane] di-sulfate dihydrate, 2,2 '-azo two { 2-[1-(2-hydroxyethyl)-2-tetrahydroglyoxaline-2-yl] propane } dihydrochloride, 2, two (1-imino--1-pyrrolidyl-2-methylpropane) dihydrochlorides of 2 '-azo, 2, two (the 2-methyl-prop amidine) dihydrochlorides of 2 '-azo, 2, the azo-compounds such as two [N-(2-the carboxy ethyl)-2-methyl-prop amidine] tetrahydrates of 2 '-azo etc.In addition, also can optionally and use the organic system reductive agents such as xitix, saccharosonic acid, aniline, tertiary amine etc.
The usage quantity of radical polymerization initiator, with respect to monomer total amount 100 weight parts, is generally 0.1～10 weight part.
There is no particular restriction for polymerizing condition, as long as under non-active gas atmosphere, 40～120 ℃ of heating 4～50 hours, as long as suitably adjust according to polymer solvent, monomer composition and polymerization starter kind.
PSS of the present invention (salt) also can manufacture by above-mentioned general radical polymerization, but in order to make molecular weight distribution narrow or in order to manufacture segmented copolymer, preferred living polymerization method, for as the polar monomer of p styrene sulfonic acid or its salt and so on, more preferably living radical polymerization.In addition, use when the high p styrene sulfonic acid ester of the solvability of all kinds of SOLVENTS is replaced to p styrene sulfonic acid (salt), also can manufacture by ionic polymerization.
As living radical polymerization, for example can list atom transfer polymerization method, stablize nitroxyl mediated polymerization, reversible addition cracking transfer polymerization method, organic tellurium mediation polymerization (polymer collection of thesis, vol.64, No.6, pp.329,2007), iodine transfer polymerization method (TOHKEMY 2007-92014 communique; Polymer collection of thesis, vol.59, No.10, the 798th page, 2010), use phosphine with the polymerization (TOHKEMY 2006-233012 communique) of the title complex of dithiocarbonic anhydride, the method for use trialkylborane (engages 50 volumes, No. 4, the 23rd page, 2006), use the method (TOHKEMY 2000-169531 communique) of α-methylstyrenedimer, these methods are all applicable in the present invention.
The concrete example of active free radical polymerization for to make other free radical polymerization monomer carry out after active free radical polymerization in aqueous solvent, add high purity p styrene sulfonic acid of the present invention (salt), continue again active free radical polymerization, or in aqueous solvent, make after this p styrene sulfonic acid (salt) active free radical polymerization, add other free radical polymerization monomer, then continue active free radical polymerization.For example, by this active free radical polymerization, obtain the polystyrolsulfon acid (salt) have as the structure of particular instantiation in above-mentioned formula (I)～(III).
Herein, kind of aqueous solvent etc. is identical with above-mentioned radical polymerization.
As ionic polymerization, can list the anionic polymerization (Polymer Preprints, Japan, Vol.59, No.1,, the 565th page in 2010 that for example use amine compound; Japan rubber association will, 74 volumes, No. 7, calendar year 2001, the 254th page), if use p styrene sulfonic acid ester, also applicable in the present invention.
In addition, in above-mentioned living radical polymerization, consideration is during for the suitability of p styrene sulfonic acid or its salt and the simplicity of polymerization, preferably use the polymerization of the title complex of phosphine and dithiocarbonic anhydride, that is, use the radical polymerization initiator (control agent) with the supposition structure of following formula (IV).
[in formula (IV), R 3, R 4, R 5the straight chain shape that expression can be substituted independently of one another or the alkyl or phenyl of branch-like, R 3, R 4, R 5can be identical also can be different, R 1and R 2expression is corresponding to the univalent perssad of the free radical being produced by free-radical generating agent, can be mutually the same also can be different].
There is no particular restriction for active free radical polymerization condition, but as its concrete example, in reaction vessel, drop into p styrene sulfonic acid or its salt and depend on the needs can carry out with p styrene sulfonic acid (salt) homogeneous solution of the comonomer of radical polymerization, make after the interior deoxidation of system, add above-mentioned radical polymerization initiator (working as the initiator molecular weight regulator of holding concurrently), be heated to specified temperature, carry out polymerization, can manufacture thus the narrow PSS of molecular weight distribution (salt)., manufacture after PSS (salt) herein, can under deoxidation state, add and can carry out other monomer of radical polymerization with p styrene sulfonic acid (salt), reheat polymerization, thereby manufacture PSS (salt) segmented copolymer.Or, the solution that can carry out the monomer of radical copolymerization with p styrene sulfonic acid (salt) drops in reaction vessel, make after internal system deoxidation, add above-mentioned radical polymerization initiator, be heated to specified temperature, carry out polymerization, manufacture thus the narrow polymkeric substance of molecular weight distribution, then under deoxidation state, add p styrene sulfonic acid or its salt, reheat polymerization, also can manufacture thus PSS (salt) segmented copolymer.In addition, by repeating these operations, can manufacture PSS (salt) multipolymer of many block types.
The R of above-mentioned formula (IV) 3, R 4, R 5be the straight chain shape that can be substituted or the alkyl or phenyl of branch-like independently of one another, but the alkyl that preferably carbonatoms is 1～18, while considering the solvability to solvent, more preferably ethyl, propyl group, sec.-propyl, normal-butyl, Bai Dingji, the tertiary butyl.
R 1, R 2the univalent perssad that expression is produced by radical polymerization initiator, but while considering polymerization starter to the solvability of aqueous solvent, preferably there is hydrophilic.For example, as this radical polymerization initiator, can list 2, two (2-amidine propane) hydrochlorides, 2 of 2 '-azo, two (2-aminopropane) nitrate, 2 of 2 '-azo, the two isobutyl-acid amides, 4 of 2 '-azo, 4 '-azo is two-4-cyanopentanoic acid etc.
PSS (salt) by above-mentioned acquisition is considered to have the structure (V) of for example following supposition or (VI).
Above-mentioned formula (V) and (VI) in R 1～R 5with the R in formula (IV) 1～R 5each is identical, and n, m in A, the B of n, m and above-mentioned repeated structural unit or general formula (I)～(III) are identical.In above-mentioned PSS (salt), though the initiator part that comprises formula (IV) can be removed it by initiator part is hydrolyzed in acid or alkali aqueous solution.
Other method of manufacturing the narrow PSS (salt) of molecular weight distribution also considers to make the narrow polystyrene of the molecular weight distribution manufactured with living polymerization in the halogenated solvents such as ethylene dichloride, by the method for the sulfonation such as anhydrous slufuric acid.In this case, if the selectivity of the contraposition in sulfonation reaction is enough high, also can use in the present invention.
PSS of the present invention (salt) also can be optionally and with can carry out random copolymerization with other monomer of p styrene sulfonic acid or its salt radical copolymerization.Though restriction especially, can not list the monomer of for example recording in the explanation of PSS (salt) segmented copolymer.While more specifically illustrating, for example, in the situation that be intended to improve the adsorptivity to carbon nanomaterial, can list N-phenylmaleimide, N-(chloro-phenyl-) maleimide, N-aminomethyl phenyl maleimide, N-bromophenyl Malaysia imide, N-naphthyl maleimide, N-hydroxy phenyl maleimide, N-p-methoxy-phenyl maleimide, N-carboxyl phenyl maleimide, N-(nitrophenyl) 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-xylyl) 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, the aromatic series maleimides such as N-(9-acridyl) maleimide.
In addition, PSS of the present invention (salt) or PSS (salt) solution are due to the impurity containing from used monomer and polymerization starter, therefore also can pass through after the removals such as ion exchange method, dialysis method, ultrafiltration process, for the manufacture of carbon nanotube or electric conductive polymer dispersion.
Then, the manufacture method for the aqueous dispersion of the nano-carbon materials such as CNT, Graphene, soccerballene is illustrated.
CNT, Graphene, soccerballene that becomes object of the present invention herein, etc. is being chemically identical meanings as nano-carbon material.The general name of the carbon material that nano-carbon material obtains with nanometer (nm) unit structure for carbon atom gathers.Therefore, carbon nanotube (Carbonnanotube, be called for short CNT) becomes the material of the coaxial tubulose of single or multiple lift for the six-ring network (graphene film) being formed by carbon.Also exist for the isomer of carbon and be classified into a kind of situation of soccerballene.In addition, so-called Graphene (graphene), is the sp of the thickness of 1 atom 2the thin slice of bonding carbon atom.Take the hexagonal lattice structure of honeycomb of being formed by carbon atom and its key and so on.In addition, soccerballene (fullerene) is with a plurality of carbon atoms, to form the general name of the cluster of minimal structure.From structure to start be that the diamond of 14 and 6 s' Graphene is different, the carbon isomer starting for the atom by dozens of number.
There is no particular restriction for the manufacture method of the aqueous dispersion of above-mentioned nano-carbon material, can application of known method (for example, TOHKEMY 2009-190940 communique, TOHKEMY 2010-13312 communique).For example, while stirring the nano-carbon material of CNT etc. is added on containing in the aqueous solvent of PSS of the present invention (salt), by ball mill, clarifixator and/or ultrasonic irradiation, CNT is disperseed.Now, in order to improve the wettability of the nano-carbon materials such as CNT, also can add with respect to water is the water-soluble solvent of 0.5～30 % by weight and/or anionic emulsifier, nonionic emulsifier, cationic emulsifier, amphoteric emulsifier.
There is no particular restriction for above-mentioned water-soluble solvent, is illustrated as acetone, methyl alcohol, ethanol, propyl alcohol, butanols, tetrahydrofuran (THF), two alkane, ethoxy ethanol, methyl cellosolve, glycerine, propylene glycol, ethylene glycol, butyleneglycol, acetic acid, propionic acid etc.
As mentioned emulsifier, there is no particular restriction, but as anionic emulsifier, can list for example sylvate, soap, alkenyl succinate, alkyl ether carboxy acid salt, alkyl diphenyl base ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, alkyl sulfonate, alkyl salicylate sulfonated ester, polyoxyethylene polycycle phenyl ether sulfuric acid, sulfonated α-olefin, alkylbenzene sulfonate, naphthalenesulfonate formaldehyde condensation compound, taurine derivatives, polystyrolsulfon acid, polystyrolsulfon acid Sipacril 2739OF, polystyrolsulfon acid acrylic copolymer, polystyrolsulfon acid acrylate copolymer, styrene sulfonic acid maleic acid, styrene sulfonic acid acrylamide copolymer, styrene sulfonic acid methacrylamide copolymer, styrene sulfonic acid 2-hydroxyethyl methacrylate multipolymer, polyvinyl sulfonic acid multipolymer, polyvinyl sulfonic acid multipolymer, polyisoprene sulfonic acid copolymer, polyacrylic ester acrylic copolymer, polymethacryl methyl acrylic copolymer, polyacrylamide acrylic copolymer, PMAm Sipacril 2739OF, alkyl sulfo succinate, alkyl sulfuric ester salt, alkyl ether sulphate salts, the sulfuric acid of alkyl propenyl phenol polyethylene oxide affixture, the sulfuric acid of allyl group alkylphenol polyethylene oxide affixture, alkyl phosphate salt, polyoxyethylene alkyl ether phosphate ester salt, the sulfonate of higher fatty acid amides, the sulfuric acids of higher fatty acid hydroxyalkyl amide etc., as nonionic emulsifier, can list for example polyoxyalkylene alkylamine, alkyl alkylolamide, amine oxide is nonionic emulsifying agent, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyalkylene polycycle phenyl ether, alkyl propenyl phenol polyethylene oxide affixture, allyl group alkylphenol polyethylene oxide affixture, polyoxygenated ethylidene fatty acid ester, polyoxygenated ethylidene sorbitan-fatty acid ester, sorbitan-fatty acid ester, glycerol fatty acid ester, alkyl poly glucoside, sucrose fatty ester, polyoxygenated ethylidene polyoxy propylene glycol, polyvinyl alcohol, carboxymethyl cellulose, polyvinylpyrrolidone, Natvosol, polyacrylamide, PMAm, polymethyl acrylic acid dimethylaminoethyl, polyacrylic acid dimethylaminoethyl, polymethyl acrylic acid lignocaine ethyl ester, polyacrylic acid lignocaine ethyl ester, polymethyl acrylic acid tertiary butyl ethylamino ethyl ester, polyacrylic acid tertiary butyl amino ethyl ester, polymethyl acrylic acid dimethylaminoethyl/methylmethacrylate copolymer, polyacrylic acid dimethylaminoethyl/methylmethacrylate copolymer, polymethyl acrylic acid dimethylaminoethyl/butyl acrylate copolymer, polyacrylic acid dimethylaminoethyl/ethyl acrylate copolymers etc., as cationic emulsifier, can list for example alkylamine salt, alkyl type quaternary ammonium salt, fatty acid amide amine salt, alkylaminoacid salts etc., as amphoteric emulsifier, can list for example alkyl-dimethyl oxyneurine, the amino sultaine of alkyl-dimethyl, alkyl sulfo betaines etc.
PSS of the present invention (salt) is through the novel PSS of structure control (salt), industrially, in the manufacture of the aqueous dispersion of the nano-carbon material such as useful CNT, Graphene, soccerballene, becomes extremely useful dispersion agent.In addition, the aqueous dispersion of the nano-carbon material such as CNT of the present invention also can optionally contain pH adjusting agent, defoamer, sanitas, viscosity modifier, sequestrant etc.
Herein, in the aqueous dispersion of nano-carbon material of the present invention, the ratio of the aqueous mediums such as the carbon nanomaterials such as CNT, Graphene, soccerballene and water is that the concentration of nano-carbon material in aqueous medium is 0.05～10 % by weight, is preferably 0.1～5 % by weight.While being less than 0.05 % by weight, the carbon nanomaterial network of aqueous dispersion in filming forms and becomes insufficient, has the situation that cannot fully obtain electroconductibility.On the other hand, while surpassing 10 % by weight, have the situation that the nano-carbon materials such as CNT fully do not disperse, in addition, have the situation that cannot obtain with the corresponding electroconductibility of amount of used nano-carbon material.
In addition, in the aqueous dispersion of nano-carbon material of the present invention, with regard to the ratio of the nano-carbon materials such as CNT and PSS of the present invention (salt), the weight ratio of nano-carbon material/PSS (salt) is 1/10～10/1 times, is preferably 3/10～10/3 times.While being less than 1/10 times, it is many that PSS (salt) amount becomes relatively, has the situation that cannot obtain with the corresponding effect of amount of added PSS (salt).On the other hand, surpass at 10/1 o'clock, because PSS (salt) is insufficient with respect to the amount of nano-carbon material, therefore have nano-carbon material cannot be well-dispersed in the situation in the aqueous mediums such as water.
In addition, PSS of the present invention (salt) also can be expected to as carbon pigment, C.I. Pigment Yellow 73 74, C.I. Pigment Yellow 73 109, C.I. pigment Yellow 12 8, C.I. Pigment Yellow 73 151, C.I. pigment Yellow 14, C.I. Pigment Yellow 73 16, C.I. the azo pigment such as pigment yellow 17, copper phthalocyanine blue or derivatives thereof (C.I. pigment Blue 15: 3, C.I. Pigment blue: 15:4), the phthualocyanine pigments such as aluminium phthalocyanine, C.I. pigment violet 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. pigment violet 207, C.I. pigment violet 209, C.I. pigment violet 19, C.I. pigment violet 42 quinacridone pigments such as grade, and isoindolinone pigment, two the purposes of the dispersion agent of piperazine pigment, perylene dye, purple cyclic ketones pigment, thioindigo color, anthraquinone pigment, quinophthalone (quinophthalone), indanthrene series pigments, diketopyrrolo-pyrrole series pigments, nigrosine pigment, the yellow series pigments of hetero ring type etc.
Then, the manufacture method for the aqueous dispersion of the electric conductive polymers such as the sub-vinyl of polythiophene class, polypyrrole class, polyaniline compound, polyphenylene, polyphenylene class is illustrated.There is no particular restriction for this manufacture method, can application of known method (for example Japanese kokai publication hei 7-90060 communique, TOHKEMY 2004-59666 communique, TOHKEMY 2010-40770 communique, TOHKEMY 2011-102376 communique).
For example, the monomer of supplying with electric conductive polymer is scattered in the aqueous solvent containing PSS (salt), adds oxygenant and carry out oxypolymerization, can manufacture thus the aqueous dispersion of electric conductive polymer.Now, in order to generate finer dispersed particle, also can irradiate ultrasonic wave in limit, oxypolymerization is carried out on limit.Subsequently, also can remove by ion exchange method, dialysis method, ultrafiltrationmembrane process and redeposition purifying etc. the impurity of oxygenant etc.Or, also can make the monomer of supplying with electric conductive polymer be scattered in the aqueous solvent that contains PSS (salt) above-mentioned doping agent in addition, adding oxygenant carries out after oxypolymerization, add the poor solvents such as ethanol, methyl alcohol, electric conductive polymer is separated out, not make water or alcohol cleaning that electric conductive polymer dissolves remove after impurity, subsequently, add PSS (salt) aqueous solution, with emulsifier units such as clarifixators, make it redispersion.
Herein, as oxygenant, can list the over cure acids such as persulfuric acid, Potassium Persulphate, ammonium persulphate, Sodium Persulfate, mineral acid iron (III), the oxygen etc. such as the organic acid iron (III) such as Phenylsulfonic acid iron (III), tosic acid iron (III), Witco 1298 Soft Acid iron, iron(ic) chloride (III), iron nitrate (III), ferric sulfate (III), ferric ammonium sulfate (III), Iron triperchlorate (III), Tetrafluoroboric acid iron (III).
In the aqueous dispersion of electric conductive polymer of the present invention, the ratio of the aqueous mediums such as the electric conductive polymers such as PEDOT and water is that the concentration of the conductive polymer material in aqueous medium is 0.1～20 % by weight, is preferably 1～10 % by weight.While being less than 0.1 % by weight, from aqueous dispersion, obtain film the network of electric conductive polymer form and become insufficient, have the situation that cannot obtain fully electroconductibility.On the other hand, while surpassing 10 % by weight, have the situation that cannot the electric conductive polymers such as PEDOT fully be disperseed, in addition, have the situation that cannot obtain with the corresponding electroconductibility of amount of used electric conductive polymer.
In addition, in the aqueous dispersion of electric conductive polymer of the present invention, the ratio of the electric conductive polymers such as PEDOT and PSS of the present invention (salt) is that the weight ratio of electric conductive polymer/PSS (salt) is 1/10～10/1 times, is preferably 3/10～10/3 times.Be less than at 1/10 o'clock, PSS (salt) amount is relatively many, has the situation that cannot obtain the electric conductivity of filming obtaining from dispersion because of remaining PSS (salt).On the other hand, surpass at 10/1 o'clock, because PSS (salt) is insufficient with respect to the amount of electric conductive polymer, therefore having electric conductive polymer is not well-dispersed in the situation in the aqueous mediums such as water.
As above aqueous solvent (aqueous medium), preferably water, but also can be the mixed stocker of water and water-soluble solvent.As water-soluble solvent, can list acetone, methyl alcohol, ethanol, propyl alcohol, butanols, ethoxy ethanol, methyl cellosolve, glycerine, propylene glycol, ethylene glycol, butyleneglycol, acetic acid, propionic acid, DMF, dimethyl sulfoxide (DMSO), acetonitrile etc.
In addition, in order to improve the dispersiveness of electric conductive polymer, also can auxiliarily add a small amount of tensio-active agent.Though restriction especially, can not used the tensio-active agent of enumerating in the Production Example of nano-carbon material aqueous dispersion.
In addition, as the oxygen compound that becomes doping agent, preferred PSS of the present invention (salt), but also can and use methanesulfonic, Phenylsulfonic acid, tosic acid, naphthene sulfonic acid, 2-naphthene sulfonic acid, 10-camphorsulfonic acid, 4-hydroxy benzenesulfonic acid, nitrobenzene-sulfonic acid, camphorsulfonic acid, 2-anthraquinone sulfonic acid, 1, 5-anthraquinone disulfonic acid, 2, 6-anthraquinone disulfonic acid, poly-(2-acrylamide-2-propane sulfonic acid), lignosulfonic acid, phenol sulfonic acid novolac resin, sulfonated polyester, polyvinyl sulfonic acid, polyisoprene sulfonic acid, polymethyl oxygen base Phenylsulfonic acid, the acid of two (trifluoromethane sulfonyl group) imide, two (perfluor alkane alkylsulfonyl) imide, the sulfoacid compounds such as polyacrylic acid methanesulfonic, polyacrylic acid, polymethyl acrylic acid, poly aspartic acid, polymaleic acid, polyvinyl phenylformic acid, acetic acid, toxilic acid, carboxyl phenol, phthalic acid aldehyde, carboxyl phenol, carboxyl cresols, carboxyl naphthalene, the carboxylic acid cpds such as dicarboxyl naphthalene, Tripyrophosphoric acid etc.
In addition, in order to promote the arrangement again of electric conductive polymer chain, improve electric conductivity, also can in the aqueous dispersion of the electric conductive polymer of above-mentioned manufacture, add the sugar alcohols such as dimethyl sulfoxide (DMSO), ethylene glycol, Diethylene Glycol, glycerine, gamma-butyrolactone, tetramethylene sulfone, N-Methyl pyrrolidone, dimethyl sulfone and erythritol as secondary doping agent, tetramethylolmethane, Sorbitol Powder.
In addition, for improving the object of filming to the adaptation of various base materials or mechanics physical property formed by electric conductive polymer, the aqueous solution or the dispersion that also can in the aqueous dispersion of the electric conductive polymer of above-mentioned manufacture, add other polymkeric substance.Can list such as vibrin, acrylic resin, polyurethane resin, celluosic resin, butyral resin, polyamide resin, polyimide resin, polystyrene resin, polyether resin, gelatin, casein, starch, gum arabic, poly-(vinyl alcohol), PVP, cellulose family, polyalkylene glycol etc.
In addition, the burn into of considering coating machine etc. is during to the detrimentally affect of base material, also can in the aqueous dispersion of the electric conductive polymer of above-mentioned manufacture, add the pH adjusting agents such as ammonia, amine, sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, lithium hydroxide, sodium phosphate.
The PSS through structure control manufacturing in the present invention (salt) is except utilizing as in order to manufacture the dispersion agent of the carbon nanomaterial of above-mentioned explanation or electric conductive polymer aqueous dispersion etc., also can expect the interlayer adaptation rising agent towards solid electrolytic capacitor, the electrode protective membrane of lithium secondary battery or sodium rechargeable battery or distance piece, solid electrolyte, photoresistance acid producing agent, ion exchange resin, anaphylactogen trapping agent, water conditioner, the clean-out system that semi-conductor or hard disk manufacturing are used, the modification agent of emulsion coatings, the dispersion agent that letex polymerization or suspension polymerization are used, the purposes of static inhibitor etc.Embodiment
By following examples, the present invention is more specifically described, but the present invention is not subject to any restriction of these embodiment.
Should illustrate, in following examples, the analysis of p styrene sulfonic acid salt, PSS salt, CNT and PEDOT aqueous dispersion, preparation and evaluation are implemented with following condition.
< utilizes the mensuration > of the impurity in the p styrene sulfonic acid salt that HPLC carries out
With following elutriant A, dissolve p styrene sulfonic acid salt sample, the solution that preparation concentration is 0.5mg/ml, carries out HPLC analysis.Condition is as following.
The LC-8020 that type=TOSOH manufactures
(de-aerator: SD-8022, pump: CCPM-II, thermocolumn case: CO-8020, ultraviolet visible light detector: UV-8020)
Post=TSKgel ODS-80TsQA (4.6mm * 25cm)
Elutriant=A liquid) water/acetonitrile=95/5+0.1% trifluoroacetic acid
B liquid) water/acetonitrile=80/20+0.1% trifluoroacetic acid
Gradient condition=to till 55 minutes being A liquid 100%, 55 minute～95 minutes be B liquid 100%
Flow=0.8ml/min, UV testing conditions=230nm, column temperature=normal temperature, injection rate=20 μl
In addition, each peak detecting with HPLC is identified with following method in advance.
Divide and get each composition detecting with HPLC, with ion exchange resin treatment, p styrene sulfonic acid salt is converted to after sulfonic acid type, with diazomethane, make sulfonic group carry out esterification, carry out gas chromatography mass analysis (M-80B that Hitachi manufactures), fourier transform infrared analysis (System2000 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 structure.
The mensuration > of the polymerisation conversion of < p styrene sulfonic acid salt
In following GPC measures, from the absorption peak strength of residual monomer, calculate.
The mensuration > of the polymerisation conversion of < hydrophobic monomer
After methyl alcohol dilution polymeric solution, use gas chromatograph (G-17A, Shimadzu Seisakusho Ltd.'s manufacture) measure the hydrophobic monomer (post=NEUTRA BOND-5 in supernatant liquor, heating schedule=50～200 ℃ * after within 10 minutes, keeping, be warming up to 300 ℃ with 5 ℃/min, the typical curve=1-methylnaphthalene of usining is used and forms as interior mark).
The mensuration > of < GPC molecular weight
The molecular weight of PSS salt and molecular weight distribution are measured with following condition.
The LC-8020 that type=TOSOH manufactures
(de-aerator: SD-8022, pump: DP-8020, thermocolumn case: CO-8020, ultraviolet visible light detector: UV-8020)
Post=TSK guard column α+tsk gel α-6000+TSK gel α-3000
The solution that the volume ratio of elutriant=phosphoric acid buffer (pH=7) and acetonitrile is 9:1
(above-mentioned phosphoric acid buffer is by the KH of 0.08 mole 2pO 4na with 0.12 mole 2hPO 4being dissolved in pure water and being modulated into total amount is that 1L obtains)
40 ℃ of column temperatures, flow=0.6ml/min
Detector=UV detector (wavelength 230nm), injection rate=100 μ l
The polystyrene standard sodium sulfonate of typical curve=wound and science
The molecular weight of PSS salt-polystyrene block copolymer is in above-mentioned condition, eluent components is changed to following composition and measure.
The solution that the volume ratio of elutriant=aqueous sodium persulfate solution (0.05mol/L) and acetonitrile is 65:35
The ultimate analysis > of < (being total to) polymkeric substance
About carbon, hydrogen, nitrogen, to make dry sample [make (being total to) polymers soln 100 ℃ of vacuum-dryings after 3 hours, dry polymkeric substance is dropped in the acetone of 100 times of amounts of its weight, stirring at normal temperature 24 hours, filtered and recycled is solute not, 50 ℃ of vacuum-dryings, within 1 hour, form, removed unreacted hydrophobic monomer] after crushed, the 2400II ultimate analysis instrumentation of manufacturing with Perkin Elmer is fixed.
In ultimate analysis, about sulphur, be the sample precision of above-mentioned drying, pulverizing is taken and burn after absorption, with ion-chromatographic determination with oxygen flask combustion method.
Condition determination with ion chromatography is as follows.
Post=tsk gel Super IC-AP, elutriant=2.7mM sodium bicarbonate+1.8mM sodium carbonate, column temperature=40 ℃, flow=0.8ml/min, detector=conductance
The FT-IR of < (being total to) polymkeric substance analyzes >
With KBr pressed disc method, make sample, use Perkin Elmer system 2000 to measure.Total range of wavelength is 4000～400cm -1, measuring number of times is 16 times.
The particle size determination > of < CNT and PEDOT aqueous dispersion
By the visual observation of aqueous dispersion and the particle size determination of carrying out in dynamic light scattering formula size-grade distribution Nanotrac UPA-UT151 (Nikkiso Company Limited's manufacture), evaluate dispersiveness and stability.Use D50% particle diameter (median particle diameter) as median size, be made as the standard of dispersity.
< precipitates >
The upper separating centrifuge NT-8 of table that uses MICROTEC NITION Co., Ltd. to manufacture, by aqueous dispersion with 3500rpm centrifugal treating 30 minutes, visual observation has or not precipitation, respectively the complete aqueous dispersion without precipitation is evaluated as to zero, the aqueous dispersion of a little precipitation is only evaluated as to △, the aqueous dispersion that precipitation is many is evaluated as *.
The electric conductivity measuring > of < electric conductive polymer
On sheet glass, drip the aqueous dispersion of the electric conductive polymer of 100 μ l, after the coating of No.8 rod spreader, in thermostatic bath, at 80 ℃, be dried 10 minutes, and then be dried 30 minutes at 150 ℃, make electric conductive polymer film.Subsequently, in numeral micron (MDC-25NJ that MITUTOYO manufactures), measure thickness, use resistrivity meter [LORESTA-GP (MCP-T600) that Mitsubishi Chemical manufactures], in room temperature, according to JIS-K7194, measure surface resistivity (Ω/) and electric conductivity.
The estimation of stability > of < electric conductive polymer aqueous dispersion
Aqueous dispersion is preserved in the thermostatic bath of 50 ℃ after 7 days, with aforesaid method, measured particle diameter and electric conductivity, and evaluate stability.
Synthesizing of Production Example 1[radical polymerization initiator (radical polymerization control agent)]
Under nitrogen atmosphere, methyl alcohol 24ml, dithiocarbonic anhydride 4.21g (55.31mmol), azo initiator V-50 (manufacture of He Guangchun medicine industrial) 1.00g (3.69mmol) and tri-n-butyl phosphine 3.73g (18.44mmol) are dropped in the reaction vessel of withstand voltage glass system, under nitrogen atmosphere, stir with magnetite agitator on limit, and limit was 50 ℃ of reactions 72 hours.After reaction, decompression is heated up in a steamer except methyl alcohol and unreacted dithiocarbonic anhydride, obtains active free radical polymerization control agent.
Embodiment 1 (Production Example of high purity PSSNa and CNT dispersion)
(manufacture of high purity PSSNa)
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 are dropped in the removable flask of 2L, 60 ℃ of heating 1 hour, dissolve completely while stirring.Subsequently, with the 1 hour speed of 10 ℃, be cooled to 10 ℃, crystallization, reclaims sodium p styrene sulfonate by centrifuging.Precision takes a small amount of sample, by 50 ℃ of vacuum-dryings the weight after 6 hours calculate after moisture, be 9.2 % by weight.The Sodium Bromide that the ion chromatograph of take is measured is 0.19 % by weight, and sodium sulfate is 0.04 % by weight.That is the monomer component that, is added with β-bromo ethyl phenenyl sodium sulfonate is 90.57 % by weight.
With HPLC, analyze the organic impuritys such as isomer contained in above-mentioned sodium p styrene sulfonate, result is (a) 0.16%, (b) 0.43%, (c) 2.65%, (d) 0.04% (collection of illustrative plates of HPLC shown in Fig. 1).
Then, in the 1L glass flask that reflux cooling pipe, nitrogen ingress pipe, paddle stirrer have been installed, drop into pure water 100.00g, under nitrogen atmosphere with the oil bath heating of 85 ℃.Within 104 minutes, to drip the sodium p styrene sulfonate aqueous solution [being that the moisture high purity sodium p styrene sulfonate 223.00g grading of above-mentioned acquisition is dissolved in pure water 884.00g and is formed] of preparation separately, to drip initiator solution (ammonium persulphate 2.77g is dissolved in pure water 121.00g and is formed) with 113 minutes, carry out polymerization therein.Start, after polyase 13 hour, to make oil bath temperature be warming up to 90 ℃, then to continue polyase 13 hour, obtain the sodium polystyrene sulfonate aqueous solution.
The number-average molecular weight Mn of the sodium polystyrene sulfonate that the GPC of take tries to achieve is 57000, and weight-average molecular weight Mw is 160000 (Mw/Mn=2.81).This polymkeric substance is made as 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 solvent of pure water 8ml and acetone 2ml (0.1 % by weight solution).(Tokyo changes into industrial and manufactures to add therein the multi-layer C NT of 0.1g, diameter 20～40nm, length 1～2 μ m) after, with ultrasonic emulsator (Japan essence mechanism US-600T) dispersion treatment 1 hour, obtain CNT aqueous dispersion (CNT concentration 1 % by weight, CNT/ poly styrene sulfonate weight ratio=1).Now, liquid temperature remains on below 40 ℃.
The composition of CNT aqueous dispersion and evaluation result (median size and pH after just having manufactured and after preserving for 50 ℃ * 14 days) are shown in to table 1.With comparative example described later 1 relatively, known all have an excellent storage stability.
Embodiment 2 (Production Example of high purity PSSLi and CNT dispersion)
(manufacture of high purity PSSLi)
In embodiment 1, use p styrene sulfonic acid lithium (LiSS that TOSOH organic chemistry company manufactures) to replace sodium p styrene sulfonate and sodium hydroxid with lithium hydroxide, repeat the recrystallize purifying identical with embodiment 1 twice, obtain the high purity p styrene sulfonic acid lithium of foreign matter content (a) 0.14%, (b) 0.04%, (c) 0.01%, (d) 0.09%.The HPLC collection of illustrative plates of this product shown in Fig. 2.
Then,, except using this p styrene sulfonic acid lithium 205.00g, to carry out polymerization with the identical condition of embodiment 1, obtain the polystyrolsulfon acid lithium aqueous solution.
The number-average molecular weight Mn of the polystyrolsulfon acid lithium that the GPC of take tries to achieve is 59000, and weight-average molecular weight Mw is 156000 (Mw/Mn=2.64).This polymkeric substance is made as to PSS-2.
(manufacture of CNT aqueous dispersion)
Except using the vacuum-drying thing of poly styrene sulfonate of above-mentioned acquisition, to obtain CNT aqueous dispersion with the identical condition of embodiment 1.
The composition of CNT aqueous dispersion and evaluation result (median size and pH after just having manufactured and after preserving for 50 ℃ * 14 days) are shown in to table 1.With comparative example described later 1 relatively, known all have an excellent storage stability.
Embodiment 3 (Production Example of the PSSLi of high purity and narrow molecular weight distribution and CNT aqueous dispersion)
(manufacture of the PSSLi of high purity and narrow molecular weight distribution)
The high purity p styrene sulfonic acid lithium [foreign matter content (a) 0.14%, (b) 0.04%, (c) 0.01%, (d) 0.09%] 205.00g, the pure water 800.00g that drop into embodiment 2 in the 1L glass flask that reflux cooling pipe, nitrogen ingress pipe, paddle stirrer have been installed in, obtain, under nitrogen atmosphere, with 40 ℃ of heating, stirring 5 minutes, make it to dissolve.Add therein the active free radical polymerization initiator 3.02g obtaining in Production Example 1,65 ℃ of polymerizations of oil bath temperature 12 hours, obtain the polystyrolsulfon acid lithium aqueous solution.
The number-average molecular weight of the polystyrolsulfon acid lithium that the GPC of take tries to achieve is 127000, and weight-average molecular weight is 165000 (Mw/Mn=1.30).This polymkeric substance is made as to PSS-3.
(manufacture of CNT aqueous dispersion)
Except using the vacuum-drying thing of poly styrene sulfonate of above-mentioned acquisition, to obtain CNT aqueous dispersion with the identical condition of embodiment 1.
The composition of CNT aqueous dispersion and evaluation result (median size and pH after just having manufactured and after preserving for 50 ℃ * 14 days) are shown in to table 1.With comparative example described later 1 relatively, known all have an excellent storage stability.Therefore in addition, because dispersiveness is than embodiment 1,2 excellences, think to make that the molecular weight distribution of PSS is narrow brings impact.
Embodiment 4 (manufacture of high purity and narrow molecular weight distribution PSSLi (lower molecular weight of PSS-3) and CNT aqueous dispersion)
(manufacture of high purity and narrow molecular weight distribution PSSLi)
In embodiment 3, except the addition of the active free radical polymerization initiator obtaining in Production Example 1 being changed to 5.00g, all the other obtain the polystyrolsulfon acid lithium aqueous solution to carry out polymerization with the identical condition of embodiment 3.
The number-average molecular weight Mn of the polystyrolsulfon acid lithium that the GPC of take tries to achieve is 73000, and weight-average molecular weight Mw is 94000 (Mw/Mn=1.29).This polymkeric substance is made as to PSS-4.
(manufacture of CNT aqueous dispersion)
Except using the vacuum-drying thing of poly styrene sulfonate of above-mentioned acquisition, to obtain CNT aqueous dispersion with the identical condition of embodiment 1.
The composition of CNT aqueous dispersion and evaluation result (median size and pH after just having manufactured and after preserving for 50 ℃ * 14 days) are shown in to table 1.With comparative example 1 relatively, known all have an excellent storage stability.Therefore in addition, because dispersiveness is more excellent than embodiment 1,2, think to make that the molecular weight distribution of PSS is narrow brings impact.
Embodiment 5 (Production Example of the manufacture of N-phenylmaleimide random copolymers and narrow molecular weight distribution and CNT aqueous dispersion)
(manufacture of random copolymers)
The high purity sodium p styrene sulfonate [foreign matter content (a) 0.16%, (b) 0.43%, (c) 2.65%, (d) 0.04%] 35.00g, the pure water 282.00g that drop into embodiment 1 in the 1L glass flask that reflux cooling pipe, nitrogen ingress pipe, paddle stirrer have been installed in, obtain, under nitrogen atmosphere, with oil bath heating, stirring 5 minutes the dissolving of 40 ℃.Add therein the acetone soln (dissolving N-phenylmaleimide 7.00g in acetone 254.00g) of N-phenylmaleimide, and after heating up with the oil baths of 65 ℃, add the active free radical polymerization initiator 4.00g obtaining in Production Example 1, when the temperature of 65 ℃, polymerization is 12 hours.
Polymeric solution is transparent, the residual monomer concentration in analytical solution, and result sodium p styrene sulfonate, N-phenylmaleimide are <0.1 % by weight.
Ultimate analysis value through vacuum drying polymkeric substance is carbon 45.8 % by weight, hydrogen 3.20 % by weight, nitrogen 1.3 % by weight, sulphur 10.7 % by weight, almost consistent with the monomer composition dropping into, although and the N-phenylmaleimide composition of the water fast of containing 17 % by weight, but multipolymer is still water-soluble, in FT-IR spectrum, see the absorption peak that is derived from N-phenylmaleimide and sodium p styrene sulfonate and (be respectively 1707cm -1and 1040cm -1), therefore this polymkeric substance is judged as and has sodium p styrene sulfonate residue: the multipolymer of the composition of N-phenylmaleimide residue=80:20 % by mole.The number-average molecular weight Mn of the multipolymer that the GPC of take tries to achieve is 19000, and weight-average molecular weight Mw is 26000 (Mw/Mn=1.37).This polymkeric substance is made as to PSS-5.
(manufacture of CNT aqueous dispersion)
Except using the vacuum-drying thing of poly styrene sulfonate of above-mentioned acquisition, to obtain CNT aqueous dispersion with the identical condition of embodiment 1.
The composition of CNT aqueous dispersion and evaluation result (median size and pH after just having manufactured and after preserving for 50 ℃ * 14 days) are shown in to table 1.With comparative example 1 relatively, known all have an excellent storage stability.In addition, because dispersiveness is more excellent than embodiment 1～4, therefore think and import and can bring impact to the strong N-phenylmaleimide of the adsorptivity of CNT in PSS skeleton.
Embodiment 6 (Production Example of methacrylic acid segmented copolymer and CNT aqueous dispersion)
(manufacture of methacrylic acid segmented copolymer)
In the 1L glass flask of reflux cooling pipe, nitrogen ingress pipe, paddle stirrer has been installed, under nitrogen atmosphere, drop into the high purity Sodium styrene sulfonate [foreign matter content (a) 0.16%, (b) 0.43%, (c) 2.65%, (d) 0.04%] 120.00g, the pure water 546.00g that in embodiment 1, obtain, with the oil bath heated and stirred of 40 ℃, sodium p styrene sulfonate is dissolved.Oil bath is warming up to after 65 ℃, adds rapidly the active free radical polymerization initiator 2.00g obtaining in Production Example 1, heated polymerizable 10 hours.
With syringe, extract the polymeric solution of 0.5ml out, through GPC, measure, result p styrene sulfonic acid concentration <0.1 % by weight, number-average molecular weight Mn is 109000, weight-average molecular weight Mw is 136000 (Mw/Mn=1.25).
Make to bathe temperature and remain on 65 ℃, add methacrylic acid sodium water solution 69.04g (solution being formed by methacrylic acid 13.00g, sodium hydroxide 6.04g and pure water 50.00g), continue polymerization 12 hours.
The number-average molecular weight Mn of the multipolymer that the GPC of take tries to achieve is 121000, and weight-average molecular weight Mw is 164000 (Mw/Mn=1.36), and the peak of the sodium polystyrene sulfonate of initial polymerization is towards the displacement of high molecular side.Methacrylic acid concentration <0.1 % by weight in polymeric solution.
Ultimate analysis value through vacuum drying polymkeric substance is carbon 48.1 % by weight, hydrogen 3.4 % by weight, sulphur 13.2 % by weight, due to almost consistent with the monomer composition dropping into, therefore this polymkeric substance be judged as and have sodium polystyrene sulfonate: the segmented copolymer of the composition of polymethyl acrylic acid=79:21 % by mole.This polymkeric substance is made as to PSS-6.
(manufacture of CNT aqueous dispersion)
Except using the vacuum-drying thing of poly styrene sulfonate of above-mentioned acquisition, to obtain CNT aqueous dispersion with the identical condition of embodiment 1.
The composition of CNT aqueous dispersion and evaluation result (median size and pH after just having manufactured and after within 50 ℃ * 14 days, preserving) are shown in table 1.With comparative example 1 relatively, known all have an excellent storage stability.In addition, because dispersiveness is more excellent than embodiment 1～4, therefore think that on PSS, linking the one-tenth branch that wetting ability is lower than p styrene sulfonic acid brings impact.
Embodiment 7 (Production Example of styrene block copolymer and CNT aqueous dispersion)
(manufacture of styrene block copolymer)
The high purity Sodium styrene sulfonate [foreign matter content (a) 0.16%, (b) 0.43%, (c) 2.65%, (d) 0.04%] 35.00g and the pure water 280g that drop into embodiment 1 in the 1L glass flask that reflux cooling pipe, nitrogen ingress pipe, paddle stirrer have been installed in, obtain, with the oil bath heated and stirred of 40 ℃, sodium p styrene sulfonate is dissolved.Oil bath is warming up to after 65 ℃, adds rapidly the active free radical polymerization initiator 0.88g obtaining in Production Example 1, heated polymerizable 12 hours.
With syringe, extract the polymeric solution of 0.5ml out, through GPC, measure, result, the concentration <0.1 % by weight of p styrene sulfonic acid, number-average molecular weight Mn is 73000, weight-average molecular weight Mw is 91000 (Mw/Mn=1.25).
Make to bathe temperature and remain on 65 ℃, add styrene solution 232g (solution being formed by vinylbenzene 2.00g and acetone 230g), continue polymerization 24 hours.
Polymeric solution is transparent, the concentration of styrene <0.1 % by weight in solution.
Ultimate analysis value through vacuum drying polymkeric substance is carbon 44.3 % by weight, hydrogen 3.4 % by weight, sulphur 13.8 % by weight, due to almost consistent with the monomer composition dropping into, although the vinylbenzene composition of the water fast of therefore containing 5 % by weight, but multipolymer is still water-soluble, and this polymkeric substance is judged as and has sodium polystyrene sulfonate residue: the multipolymer of the composition of vinylbenzene residue=90:10 % by mole.The number-average molecular weight Mn of the multipolymer that the GPC of take tries to achieve is 77000, and weight-average molecular weight Mw is 116000 (Mw/Mn=1.51).This polymkeric substance is made as to PSS-7.
(manufacture of CNT aqueous dispersion)
Except using the vacuum-drying thing of poly styrene sulfonate of above-mentioned acquisition, to obtain CNT aqueous dispersion with the identical condition of embodiment 1.
The composition of CNT aqueous dispersion and evaluation result (median size and pH after just having manufactured and after preserving for 50 ℃ * 14 days) are shown in to table 1.With comparative example described later 1 relatively, known all have an excellent storage stability.In addition, because dispersiveness is more excellent than embodiment 1～4, therefore think that on PSS, linking the polystyrene that hydrophobicity is higher can bring impact.
Comparative example 1 (using the example of low-purity Sodium styrene sulfonate)
(manufacture of low-purity PSSNa)
Except using the low-purity sodium p styrene sulfonate 223.00g of commercially available foreign matter content (a) 0.38%, (b) 3.87%, (c) 7.77%, (d) 0.06%, to carry out polymerization with the identical condition of embodiment 1, obtain the sodium polystyrene sulfonate aqueous solution.
The number-average molecular weight Mn of the sodium polystyrene sulfonate that the GPC of take tries to achieve is 52000, and weight-average molecular weight Mw is 161000 (Mw/Mn=3.10).This polymkeric substance is made as to PSS-8.In addition, the HPLC collection of illustrative plates of above-mentioned low-purity sodium p styrene sulfonate shown in Fig. 3.
(manufacture of CNT aqueous dispersion)
Except using the vacuum-drying thing of poly styrene sulfonate of above-mentioned acquisition, to obtain CNT aqueous dispersion with the identical condition of embodiment 1.
The composition of CNT aqueous dispersion and evaluation result (median size and pH after just having manufactured and after within 50 ℃ * 14 days, preserving) are shown in table 1.With embodiment comparison, though the particle diameter after just preparation is not seen significant difference, clearly see through time dispersion stabilization decline or pH declines.
Embodiment 8～13 (manufacture of electric conductive polymer dispersion and evaluation)
First, according to the method for Japanese kokai publication sho 60-15408 communique, remove contained unwanted ion in the polystyrene acid salt solution obtaining in embodiment 1～4,6,7.; by processing poly styrene sulfonate solution to be filled with the post of anionite-exchange resin [Amberlite IRA-410 (with the resin of sodium hydroxide regeneration)]; remove after the negatively charged ion of bromine, sulfate ion etc., by being filled with the post of Zeo-karb [the Amberlite RB-120 (with the resin of regeneration of hydrochloric acid) that Organo company manufactures], remove the positively charged ions such as sodium, lithium.Subsequently, solids component (measuring after 3 hours 100 ℃ of vacuum-dryings) is adjusted to 10.00 % by weight.
At normal temperature, above-mentioned PSS salt brine solution 20.00g and 3,4-Ethylenedioxy Thiophene (Tokyo changes into the reagent that industrial manufactures) 1.00g is dropped in pure water 100ml, with agitating vane vigorous stirring 30 minutes.Then, under the condition of normal temperature, stirring, add the 20 % by weight ammonium persulfate aqueous solutions of 1ml as oxygenant, start oxypolymerization.Subsequently, the 20 % by weight ammonium persulfate aqueous solution 7 times (adding up to 8ml) at interval of adding 1ml for 10 minutes, stirs limit polymerization in 60 hours on normal temperature limit.
Subsequently, at normal temperatures through 10 minutes ultrasonic irradiations (US-600T that Japanese smart machine is manufactured), so that the PEDOT dispersion particle of above-mentioned acquisition diminishes.
Subsequently, add the Zeo-karb [the Amberlite RB-120 (with the resin of regeneration of hydrochloric acid) that Organo company manufactures] of 5ml, the anionite-exchange resin of 7ml [Amberlite IRA-410 (with the resin of sodium hydroxide regeneration)], at normal temperature, slowly stir 2 hours.Subsequently, by filtering Zeo-karb and anionite-exchange resin, obtain the PEDOT of solids component 1.9 % by weight.And then adding is the dimethyl sulfoxide (DMSO) of 5 % by weight with respect to the PEDOT composition in PEDOT aqueous dispersion, evaluate the physical property of dispersion.The kind of PSS salt of using as dispersion agent and the proterties of dispersion (median size and electric conductivity after just having manufactured and after preserving for 50 ℃ * 7 days) are shown in to table 2.
Compare with comparative example 2 described later, known electric conductivity and storage stability are all excellent.In addition, known in styrene sulfonate homopolymer, molecular weight distribution narrower (having used PSS-3,4 embodiment 10,11), electric conductivity is more excellent.
Comparative example 2
In embodiment 8～13, except the poly styrene sulfonate solution that the poly styrene sulfonate solution with obtaining in comparative example 1 replaces obtaining in embodiment 1～4,6,7, to obtain PEDOT aqueous dispersion with the identical condition of embodiment 8～13.
The kind of PSS salt of using as dispersion agent and the proterties of dispersion (median size and electric conductivity after just having manufactured and after preserving for 50 ℃ * 7 days) are shown in to table 2.Though just the particle diameter after preparation is not seen notable difference, clearly see through time electric conductivity and the decline of stability.
In industry, utilize possibility
Utilize nano-carbon material that the polystyrolsulfon acid through structure control of the present invention or its salt forms and the aqueous dispersion of electric conductive polymer to can be used for, in the purposes of conductive coating paint, LSI distribution, electromagnetic shielding material, electrochemical appliance (fuel cell, secondary cell, electrical condenser, Field Emission Display, transistor, solar cell, various electrode), antistatic coating, organic EL, contact panel, can bringing contribution to the industrialization of nano-carbon material or electric conductive polymer.
Nomenclature
(a): the absorption intensity of adjacent styrene sulfonate
(b): the absorption intensity of β-bromo ethyl phenenyl sulfonate
(c): the absorption intensity of a styrene sulfonate
(d): the absorption intensity of bromstyrol sulfonate

Claims (12)

1. a high purity p styrene sulfonic acid (salt), as (a) the adjacent styrene sulfonic acid (salt) that is derived from the cinnamic major impurity of raw material sometimes containing in p styrene sulfonic acid (salt), (b) β-bromo ethyl phenenyl sulfonic acid (salt), (c) styrene sulfonic acid between (salt), (d) ratio that contains of the peak area benchmark of trying to achieve with high performance liquid chromatography of bromstyrol sulfonic acid (salt) is respectively (a)≤0.20%, (b)≤0.50%, (c)≤3.00%, and (d)≤0.10%, wherein, p styrene sulfonic acid (salt) with (a)～(d) summation of peak area is 100.
2. a polystyrolsulfon acid (salt), is that right to use requires the high purity p styrene sulfonic acid (salt) described in 1 to manufacture, there is following repeated structural unit A, or there is following repeated structural unit A and following repeated structural unit B,
In repeated structural unit A, B, M represents sodium cation, lithium cation, potassium cationic, ammonium cation, quaternary ammonium cation or proton, and Q represents other free radical polymerization monomer residue, and n represents more than 1 integer, and m represents more than 0 integer.
3. polystyrolsulfon acid as claimed in claim 2 (salt), wherein, described polystyrolsulfon acid (salt) has at least arbitrary structure in following formula (I)～(III),
In formula (I)～(III), M represents 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 ' represent more than 1 integer, and m and m ' represent more than 0 integer.
4. polystyrolsulfon acid as claimed in claim 2 (salt), wherein, the weight-average molecular weight that the gel permeation chromatography of take is tried to achieve is 2,000～1,000,000, weight-average molecular weight is less than 2.0 with the ratio (weight-average molecular weight/number-average molecular weight) of number-average molecular weight.
5. polystyrolsulfon acid as claimed in claim 2 (salt), wherein, Q is for being selected from more than one the free radical polymerization monomer residue in vinylbenzene residue, styrene derivatives residue, methacrylic acid residue, 2-hydroxyethyl methacrylate residue, glycidyl methacrylate residue, (methyl) acrylamide residue, NVP residue, N-phenylmaleimide residue and maleic anhydride residue.
6. a dispersion agent, usings in claim 2～5 polystyrolsulfon acid (salt) described in any one as effective constituent.
7. an electric conductive polymer doping agent, usings in claim 2～5 polystyrolsulfon acid (salt) described in any one as effective constituent.
8. a nano-carbon material aqueous dispersion, usings in claim 2～5 polystyrolsulfon acid (salt) described in any one as dispersion agent.
9. an electric conductive polymer aqueous dispersion, right to use requires the polystyrolsulfon acid (salt) described in any one in 2～5 to manufacture as doping agent.
10. a manufacture method for the polystyrolsulfon acid described in any one (salt) in claim 2～5 wherein, is carried out radical polymerization or active free radical polymerization by high purity p styrene sulfonic acid claimed in claim 1 (salt) in aqueous solvent.
The manufacture method of the polystyrolsulfon acid (salt) in 11. 1 kinds of claims 2～5 described in any one, wherein, in aqueous solvent, free radical polymerization monomer is carried out after active free radical polymerization, add p styrene sulfonic acid claimed in claim 1 (salt), continue again active free radical polymerization, or
In aqueous solvent, this p styrene sulfonic acid (salt) is carried out after active free radical polymerization, add free radical polymerization monomer, then continue active free radical polymerization.
The manufacture method of 12. polystyrolsulfon acids (salt) as described in claim 10 or 11, wherein, active free radical polymerization initiator represents with following formula (IV),
In formula (IV), R 3, R 4, R 5representing independently of one another can substituted straight chain shape or the alkyl or phenyl of branch-like, R 1and R 2expression, can be mutually the same corresponding to the univalent perssad of the free radical being produced by free-radical generating agent, also can be different.
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