JPWO2018097085A1 - Conductive polymer dopant, conductive polymer using the same, and method for producing conductive polymer - Google Patents
Conductive polymer dopant, conductive polymer using the same, and method for producing conductive polymer Download PDFInfo
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- JPWO2018097085A1 JPWO2018097085A1 JP2018552562A JP2018552562A JPWO2018097085A1 JP WO2018097085 A1 JPWO2018097085 A1 JP WO2018097085A1 JP 2018552562 A JP2018552562 A JP 2018552562A JP 2018552562 A JP2018552562 A JP 2018552562A JP WO2018097085 A1 JPWO2018097085 A1 JP WO2018097085A1
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- Prior art keywords
- conductive polymer
- dopant
- polymer
- group
- conductive
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- 125000001424 substituent group Chemical group 0.000 claims abstract description 20
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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Abstract
本発明は、有機溶剤への分散性に優れた導電性高分子を得ることを可能にする、導電性高分子用ドーパントを提供するものである。本発明によれば、重量平均分子量500以上であり、シリコーン骨格を有し、かつ、置換基を少なくとも1つ以上有する化合物であり、前記置換基がスルホン酸基又はリン酸基若しくはそれらの塩のいずれかである導電性高分子用ドーパント、が提供される。The present invention provides a dopant for a conductive polymer that makes it possible to obtain a conductive polymer excellent in dispersibility in an organic solvent. According to the present invention, the compound has a weight average molecular weight of 500 or more, a silicone skeleton, and at least one substituent. The substituent is a sulfonic acid group, a phosphate group, or a salt thereof. Any of the dopants for conductive polymers is provided.
Description
本発明は、導電性高分子用ドーパント及びそれを用いた導電性高分子の製造方法、並びに導電性高分子に関するものである。 The present invention relates to a dopant for a conductive polymer, a method for producing a conductive polymer using the same, and a conductive polymer.
従来の導電性高分子として、ポリエチレンジオキシチオフェン(PEDOT)にポリスチレンスルホン酸(PSS)をドープしたPEDOT−PSSが代表として挙げられ、工業的に利用されている。(例えば、特許文献1)しかし、このPEDOT−PSSはPSSのドープとして用いられないスルホン酸基によって、水中における分散安定を特徴としているため、高い酸性度による金属腐食性を有する、といった課題や、有機溶剤には安定的に分散しない、といった課題があった。また、各種材料を混合し、塗料として配合する際には、バインダー及び各種添加剤は水系に限定される、といった課題があった。 As a conventional conductive polymer, PEDOT-PSS in which polystyrene sulfonic acid (PSS) is doped into polyethylene dioxythiophene (PEDOT) is cited as a representative, and is used industrially. However, since this PEDOT-PSS is characterized by dispersion stability in water due to a sulfonic acid group that is not used as a PSS dope, it has a problem of having metal corrosivity due to high acidity, There was a problem that the organic solvent was not stably dispersed. Moreover, when mixing various materials and mix | blending as a coating material, there existed a subject that a binder and various additives were limited to an aqueous system.
これらの課題に対して、本質的に溶剤に可溶しないポリアニリンを、ナノサイズレベルまで粉砕微粉化しポリアニリンおよび溶剤に親和性の高いパラトルエンスルホン酸や(特許文献2)、ドデシルベンゼンスルホン酸(特許文献3)等のスルホン酸アニオン乳化剤を分散剤として用いながら溶剤に共分散させ、ナノレベルでの微分散体溶液の提供に関する検討や、更に立体障害性の高い分岐型アルキルを用いた、ジ(2−エチルヘキシル)スルホコハク酸を用いた検討(特許文献4)がなされている。また、溶剤への溶解性を目的として、スルホン酸基含有ポリ(メタ)アクリル酸エステルをドープした導電性高分子に関する検討もなされている(特許文献5)。 In response to these problems, polyaniline, which is essentially insoluble in solvents, is pulverized and pulverized to a nano-size level. Reference 3) and other sulfonic acid anion emulsifiers are used as dispersants and co-dispersed in a solvent to investigate the provision of fine dispersion solutions at the nano level. Studies using 2-ethylhexyl) sulfosuccinic acid have been made (Patent Document 4). In addition, for the purpose of solubility in a solvent, studies have been made on a conductive polymer doped with a sulfonic acid group-containing poly (meth) acrylic ester (Patent Document 5).
しかし、特許文献2、3における検討では、分子サイズの小さいドーパントである事や各種有機溶剤との親和性に制限があるためπ共役系部分間のスタック抑制効果が小さく、溶剤分散性を十分に付与できないという課題がある。 However, in the studies in Patent Documents 2 and 3, since the dopant is small in molecular size and the affinity with various organic solvents is limited, the effect of suppressing the stacking between the π-conjugated parts is small, and the solvent dispersibility is sufficient. There is a problem that it cannot be granted.
特許文献4における検討では、分散性がまだ十分ではなく、幅広い極性の溶剤に分散させることは困難であった。 According to the study in Patent Document 4, the dispersibility is not yet sufficient, and it has been difficult to disperse in a wide range of polar solvents.
また、特許文献5における検討では、ある程度の溶剤分散性を得ることができるものの、高分子ドーパント上に不均一にπ共役が生成されるため、不溶部位であるπ共役部分が分子内及び分子間で凝集状態を取りやすい構造となり、導電性高分子の粒子径が大きくなることが多く、分散安定状態を確保することが難しい、という課題がある。 Further, in the study in Patent Document 5, although a certain degree of solvent dispersibility can be obtained, π conjugate is generated non-uniformly on the polymer dopant. Therefore, there is a problem that the structure is easy to take an agglomerated state, the particle diameter of the conductive polymer is often increased, and it is difficult to ensure a stable dispersion state.
本発明はこのような事情に鑑みてなされたもので、有機溶剤への分散性に優れた導電性高分子を得ることを可能にする、導電性高分子用ドーパントを提供するものである。 This invention is made | formed in view of such a situation, and provides the dopant for conductive polymers which makes it possible to obtain the conductive polymer excellent in the dispersibility to an organic solvent.
本発明によれば、重量平均分子量500以上であり、シリコーン骨格を有し、かつ、置換基を少なくとも1つ以上有する化合物であり、前記置換基がスルホン酸基又はリン酸基若しくはそれらの塩のいずれかである導電性高分子用ドーパント、が提供される。 According to the present invention, the compound has a weight average molecular weight of 500 or more, a silicone skeleton, and at least one substituent. The substituent is a sulfonic acid group, a phosphate group, or a salt thereof. A conductive polymer dopant is provided.
本発明者らは、導電性高分子の溶剤分散性を向上させるべく鋭意検討を行った結果、導電性高分子用ドーパントが重量平均分子量500以上であり、シリコーン骨格を有しており、スルホン酸又はリン酸若しくはそれらの塩を1つ以上有する化合物である場合に、導電性高分子の溶剤分散性が優れることを見出し、本発明の完成に到った。 As a result of intensive studies to improve the solvent dispersibility of the conductive polymer, the present inventors have found that the conductive polymer dopant has a weight average molecular weight of 500 or more, has a silicone skeleton, and has a sulfonic acid. Alternatively, in the case of a compound having at least one phosphoric acid or a salt thereof, it has been found that the solvent dispersibility of the conductive polymer is excellent, and the present invention has been completed.
以下、本発明の種々の実施形態を例示する。以下に示す実施形態は、互いに組み合わせ可能である。 Hereinafter, various embodiments of the present invention will be exemplified. The embodiments described below can be combined with each other.
好ましくは、前記置換基が、シリコーン骨格における片末端又は両末端に結合されている、導電性高分子用ドーパントである。 Preferably, the substituent is a conductive polymer dopant in which the substituent is bonded to one end or both ends of the silicone skeleton.
好ましくは、前記シリコーン骨格が、下記の一般式(1)で表される構造単位を有する化合物である、導電性高分子用ドーパントである。
好ましくは、前記重量平均分子量が、500〜20000である、導電性高分子用ドーパントである。 Preferably, it is a dopant for conductive polymers whose weight average molecular weight is 500-20000.
本発明によれば、前記導電性高分子用ドーパントと、π共役系高分子を含む導電性高分子、が提供される。 According to the present invention, the conductive polymer dopant and a conductive polymer containing a π-conjugated polymer are provided.
好ましくは、前記π共役系高分子が、チオフェン、アニリン、ピロール及びこれらの誘導体からなる群から選択される少なくとも1つのモノマーを重合してなる、導電性高分子である。 Preferably, the π-conjugated polymer is a conductive polymer obtained by polymerizing at least one monomer selected from the group consisting of thiophene, aniline, pyrrole and derivatives thereof.
本発明によれば、前記導電性高分子を有機溶剤に分散させた導電性高分子の分散液、が提供される。 According to the present invention, there is provided a conductive polymer dispersion in which the conductive polymer is dispersed in an organic solvent.
本発明によれば、前記導電性高分子用ドーパントを準備する工程と、前記導電性高分子用ドーパント及びπ共役系高分子のモノマーを含む混合物を準備する工程と、前記混合物において重合を行う工程とを有する導電性高分子の製造方法、が提供される。 According to the present invention, a step of preparing the conductive polymer dopant, a step of preparing a mixture containing the conductive polymer dopant and a π-conjugated polymer monomer, and a step of performing polymerization in the mixture The manufacturing method of the conductive polymer which has these is provided.
以下、本発明の実施形態について説明する。以下に示す実施形態中で示した各種特徴事項は、互いに組み合わせ可能である。また、各特徴事項について独立して発明が成立する。 Hereinafter, embodiments of the present invention will be described. Various characteristic items shown in the following embodiments can be combined with each other. In addition, the invention is independently established for each feature.
<1.導電性高分子用ドーパントA>
本発明の導電性高分子用ドーパントは、重量平均分子量500以上であり、シリコーン骨格を有し、スルホン酸基又はリン酸基若しくはそれらの塩である置換基を少なくとも1つ以上有する化合物である(以下、導電性高分子用ドーパントAと称する)。すなわち、上記構成とすることで有機溶剤への溶解性を得ることができる。また、導電性高分子用ドーパントAは、化合物中に親水性基の部位と疎水性基の部位とを有しているが、上記構成であることで極性溶媒、非極性溶媒にかかわらず広範な種類の溶剤への溶解性を得ることができる。 <1. Conductive polymer dopant A>
The dopant for a conductive polymer of the present invention is a compound having a weight average molecular weight of 500 or more, a silicone skeleton, and at least one substituent which is a sulfonic acid group, a phosphoric acid group or a salt thereof ( Hereinafter, it is referred to as a conductive polymer dopant A). That is, the solubility to an organic solvent can be obtained by setting it as the said structure. In addition, the conductive polymer dopant A has a hydrophilic group portion and a hydrophobic group portion in the compound, but it has a wide range regardless of whether it is a polar solvent or a nonpolar solvent. Solubility in various types of solvents can be obtained.
<1.1 重量平均分子量>
本発明の導電性高分子用ドーパントAの重量平均分子量は、500以上であり、好ましくは1000以上であり、より好ましくは2000以上である。この場合、ドーパントA自体の溶剤溶解性が良好になり、且つこのドーパントAを用いて作製した導電性高分子の有機溶剤への分散性が向上する。ドーパントAの重量平均分子量は、好ましくは20000以下であり、より好ましくは15000以下であり、より好ましくは10000以下である。この場合、導電性高分子の合成時の重合場(水溶性)への溶解性及び導電性高分子の溶剤分散性を得ることができる。ドーパントAの重量平均分子量は、具体的には例えば、500、1000、1500、2000、2500、3000、3500、4000、4500、5000、5500、6000、7000、8000、9000、10000、12000、14000、16000、18000、20000であり、ここで例示した数値の何れか2つの間の範囲内であってもよい。 <1.1 Weight average molecular weight>
The weight average molecular weight of the conductive polymer dopant A of the present invention is 500 or more, preferably 1000 or more, more preferably 2000 or more. In this case, the solvent solubility of the dopant A itself is improved, and the dispersibility of the conductive polymer produced using the dopant A in the organic solvent is improved. The weight average molecular weight of the dopant A is preferably 20000 or less, more preferably 15000 or less, and more preferably 10,000 or less. In this case, it is possible to obtain the solubility in the polymerization field (water-soluble) during the synthesis of the conductive polymer and the solvent dispersibility of the conductive polymer. Specifically, the weight average molecular weight of the dopant A is, for example, 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 7000, 8000, 9000, 10,000, 12000, 14000, 16000, 18000, 20000, and may be within a range between any two of the numerical values exemplified here.
導電性高分子用ドーパントの重量平均分子量は、例えば、GPC(ゲルパーミエーションクロマトグラフィー)を用いて測定することができる。 The weight average molecular weight of the dopant for conductive polymers can be measured using, for example, GPC (gel permeation chromatography).
<1.2 シリコーン骨格>
導電性高分子用ドーパントAは、主鎖にシリコーン骨格を有しているものであれば特に限定されないが、例えば、下記の一般式(1)で表される構造単位を有する化合物等があげられる。 <1.2 Silicone skeleton>
The conductive polymer dopant A is not particularly limited as long as it has a silicone skeleton in the main chain, and examples thereof include compounds having a structural unit represented by the following general formula (1). .
ここで、アルキル基は、好ましくはメチル基であり、より好ましくは各Rが共にメチル基であることで、導電性高分子の凝集を抑制してさらに優れた溶剤分散性を確保できる点で好ましい。nの値は、2〜200であり、好ましくは2〜120であり、より好ましくは2〜60である。 Here, the alkyl group is preferably a methyl group, and more preferably each R is a methyl group, which is preferable in that it can suppress aggregation of the conductive polymer and ensure excellent solvent dispersibility. . The value of n is 2 to 200, preferably 2 to 120, and more preferably 2 to 60.
<1.3 置換基>
導電性高分子用ドーパントAは、置換基としてスルホン酸基又はリン酸基若しくはそれらの塩を少なくとも1つ以上有しているものであれば特に限定されない。すなわち、導電性高分子用ドーパントが上記置換基を有していることで水溶性を得ることができ、水中下での導電性高分子の重合を進行させ、且つ同時にドープすることができるようになる。ここで、より好ましくは置換基がスルホン酸基である。 <1.3 Substituent>
The conductive polymer dopant A is not particularly limited as long as it has at least one sulfonic acid group, phosphoric acid group or salt thereof as a substituent. That is, the conductive polymer dopant has the above substituents so that water solubility can be obtained, the polymerization of the conductive polymer in water can proceed, and doping can be performed simultaneously. Become. Here, more preferably, the substituent is a sulfonic acid group.
上記スルホン酸塩あるいはリン酸塩としては、例えば、スルホン酸ナトリウム、スルホン酸カリウム等のスルホン酸金属塩やスルホン酸アンモニウム塩、スルホン酸ピリジウム塩等あるいはリン酸ナトリウム、リン酸カリウム等のリン酸金属塩やリン酸アンモニウム塩等があげられる。 Examples of the sulfonate or phosphate include sulfonate metal salts such as sodium sulfonate and potassium sulfonate, ammonium sulfonate salts, pyridium sulfonate salts and the like, and metal phosphates such as sodium phosphate and potassium phosphate. Examples thereof include salts and ammonium phosphates.
導電性高分子用ドーパントAは、好ましくは置換基数が1つまたは2つである。より好ましくは前記置換基がシリコーン骨格の片末端又は両末端に結合されているものである。すなわち、そのような化合物であれば導電性高分子用ドーパントとしてドープした際に得られた導電性高分子の凝集を抑制し、導電性高分子の粒径が大きくなることを抑制することができ、有機溶剤に対して高い分散性を得ることができる。より優れた溶剤分散性を得るためには、前記置換基がシリコーン骨格の片末端に結合されているものであることが好ましい。 The conductive polymer dopant A preferably has one or two substituents. More preferably, the substituent is bonded to one or both ends of the silicone skeleton. That is, with such a compound, aggregation of the conductive polymer obtained when doped as a dopant for the conductive polymer can be suppressed, and an increase in the particle size of the conductive polymer can be suppressed. High dispersibility can be obtained with respect to organic solvents. In order to obtain better solvent dispersibility, the substituent is preferably bonded to one end of the silicone skeleton.
<1.4 導電性高分子用ドーパントAの合成>
導電性高分子用ドーパントAの合成経路については特に限定されず、導電性高分子用ドーパント中の一部が有機基で変性された化合物に対してスルホン酸基あるいはその塩、又はリン酸基あるいはその塩を導入できるものであればよい。例えば、シリコーン化合物の一部がエポキシ基、カルビノール基、ジオール基、メタクリル基、カルボキシル基、ポリエーテル基、アミノ基、メルカプト基、フェノール、シラノール基、アクリル基等によって変性されたもの対してスルホン酸基又はリン酸基若しくはそれらの塩を導入したもの等があげられる。 <1.4 Synthesis of dopant A for conductive polymer>
The synthesis route of the conductive polymer dopant A is not particularly limited, and a sulfonic acid group or a salt thereof, a phosphate group or a compound in which a part of the conductive polymer dopant is modified with an organic group is used. Any salt capable of introducing the salt may be used. For example, a part of the silicone compound is sulfone for those modified with epoxy group, carbinol group, diol group, methacryl group, carboxyl group, polyether group, amino group, mercapto group, phenol, silanol group, acrylic group, etc. Examples thereof include an acid group, a phosphate group, or a salt thereof introduced.
導電性高分子用ドーパントAは、例えば、次のようにして合成することができる。すなわち、重量平均分子量500以上であり、シリコーン骨格を有する化合物(例えば、片末端エポキシオルガノシロキサン(信越化学工業製 X−22−173BX))と、2−メルカプトエタンスルホン酸ナトリウムと、イソプロピルアルコールと、トリエチルアミンとを混合し、加熱還流下所定時間(例えば、15時間)反応させた後、反応物に水を加え減圧留去によりイソプロピルアルコールを除去してスルホン酸化合物の乳化液により導電性高分子用ドーパントAを得ることができる。ここで、有機置換基の結合位置は片末端に限られず両末端に結合しているものであってもよい。 The conductive polymer dopant A can be synthesized, for example, as follows. That is, a compound having a weight average molecular weight of 500 or more and having a silicone skeleton (for example, one-end epoxyorganosiloxane (X-22-173BX manufactured by Shin-Etsu Chemical Co., Ltd.)), sodium 2-mercaptoethanesulfonate, isopropyl alcohol, After mixing with triethylamine and reacting with heating under reflux for a predetermined time (for example, 15 hours), water is added to the reaction product, isopropyl alcohol is removed by distillation under reduced pressure, and the sulfonic acid compound emulsion is used for the conductive polymer. The dopant A can be obtained. Here, the bonding position of the organic substituent is not limited to one end and may be bonded to both ends.
<2.導電性高分子>
本発明の導電性高分子は、導電性高分子用ドーパントAと、π共役系高分子を含む。この導電性高分子は、溶剤分散性を有している。ここで、導電性高分子用ドーパントについては本発明のドーパントAの構成の範囲内であれば適宜変更することが可能である。 <2. Conductive polymer>
The conductive polymer of the present invention includes a conductive polymer dopant A and a π-conjugated polymer. This conductive polymer has solvent dispersibility. Here, about the dopant for conductive polymers, if it is in the range of the structure of the dopant A of this invention, it can change suitably.
また、前記高分子用ドーパントA以外に、導電性高分子の分野で一般的に使用されるドーパントを併用することも可能である。 In addition to the polymer dopant A, a dopant generally used in the field of conductive polymers can be used in combination.
導電性高分子の分野で一般的に使用されるドーパントは、一般には電子受容性の物質であり、例えばハロゲン、ルイス酸、プロトン酸、遷移金属ハロゲン化物などが用いられる。前記導電性高分子用ドーパントAに加えて、前述の一般的なドーパントを導電性高分子用ドーパントBとして併用する場合は、ドーパントA及びドーパントBは、任意の割合で併用することができ、目的に合わせて適宜選択することが可能である。 The dopant generally used in the field of the conductive polymer is generally an electron-accepting substance, and for example, halogen, Lewis acid, proton acid, transition metal halide and the like are used. In addition to the conductive polymer dopant A, when the above-mentioned general dopant is used in combination as the conductive polymer dopant B, the dopant A and the dopant B can be used in an arbitrary ratio. It is possible to select appropriately according to.
前記π共役系高分子とは、π共役系高分子のモノマーの重合により得られる高分子をいい、具体的には、ポリチオフェン、ポリアニリン、ポリピロール、ポリ3,4−エチレンジオキシチオフェン、ポリ3−メトキシチオフェン、ポリ3,4−ジメトキシチオフェン、ポリ3−ヘキシルチオフェン、ポリ3−メチルピロール、ポリ3−メチルチオフェン、ポリo−トルイジン、ポリo−アニシジン、ポリo−エチルアニリン、ポリsec−ブチルアニリン等があげられる。 The π-conjugated polymer refers to a polymer obtained by polymerization of a monomer of a π-conjugated polymer. Specifically, polythiophene, polyaniline, polypyrrole, poly3,4-ethylenedioxythiophene, poly-3- Methoxythiophene, poly3,4-dimethoxythiophene, poly-3-hexylthiophene, poly-3-methylpyrrole, poly-3-methylthiophene, poly-o-toluidine, poly-o-anisidine, poly-o-ethylaniline, poly-sec-butylaniline Etc.
また、π共役系高分子の数平均分子量は、通常1000〜300000である。この範囲内であれば導電性高分子として用途を限定せず利用することができるという点で好ましい。この数平均分子量は、ドープ成分を脱離させた後にπ共役系高分子骨格が可溶となる溶剤を用いてGPCで測定した値であり、ドープ脱離行程(アルカリ処理や電気的分解等)の時点でのπ共役系高分子の分解等も包括された参考値である。 The number average molecular weight of the π-conjugated polymer is usually 1000 to 300,000. If it exists in this range, it is preferable at the point that it can utilize, without limiting a use as a conductive polymer. This number average molecular weight is a value measured by GPC using a solvent in which the π-conjugated polymer skeleton becomes soluble after the dope component is desorbed, and the dope desorption process (alkali treatment, electrolysis, etc.) This is a comprehensive reference value including the decomposition of the π-conjugated polymer at the point of time.
本発明の導電性高分子は、ポリチオフェン、ポリアニリン、ポリピロール等のπ共役系高分子にドープして得られる導電性高分子が有する導電率(10−6[S/cm]以上)と同等以上の導電率を有しており、導電性が要求される部分に適用することが可能であり、用途については特に限定されない。導電性高分子の導電率は、具体的には例えば、10−6〜10−1[S/cm]、の範囲内の導電率を示すものであればよく、この範囲の導電率よりも高い導電率を示してもよい。また、導電性高分子の導電率は、10−6、10−5、10−4、10−3、10−2、10−1[S/cm]で示される数値から選択される何れか2つの間の範囲内であってもよい。その中でも、実用上、安定した性能を発現する観点から10−3[S/cm]以上の導電率を示すことが好ましい。The conductive polymer of the present invention has an electrical conductivity (10 −6 [S / cm] or higher) equal to or higher than that of a conductive polymer obtained by doping a π-conjugated polymer such as polythiophene, polyaniline, or polypyrrole. It has electrical conductivity and can be applied to a portion requiring electrical conductivity, and the use is not particularly limited. Specifically, the conductivity of the conductive polymer is not particularly limited as long as it exhibits conductivity within a range of 10 −6 to 10 −1 [S / cm], and is higher than the conductivity within this range. Conductivity may be indicated. The conductivity of the conductive polymer is any one selected from the values represented by 10 −6 , 10 −5 , 10 −4 , 10 −3 , 10 −2 , and 10 −1 [S / cm]. It may be within a range between the two. Among them, it is preferable that a conductivity of 10 −3 [S / cm] or more is practically exhibited from the viewpoint of expressing stable performance.
また、本発明の導電性高分子は、本発明の導電性高分子以外の高分子と併用して用いてもよい。ここで高分子としては特に限定されるものではなく、公知のものを適用でき、例えば、アクリル樹脂、メタクリル樹脂、ポリウレタン樹脂、ポリエステル樹脂、エポキシ樹脂等の各種樹脂が挙げられる。 The conductive polymer of the present invention may be used in combination with a polymer other than the conductive polymer of the present invention. Here, the polymer is not particularly limited, and a known polymer can be applied, and examples thereof include various resins such as acrylic resin, methacrylic resin, polyurethane resin, polyester resin, and epoxy resin.
<3.導電性高分子の分散液>
本発明の導電性高分子は、メチルエチルケトン、メチルイソブチルケトン、アセトン等のケトン系溶剤、酢酸エチル、酢酸ブチル等のエステル系溶剤、トルエン等の芳香族系溶剤、テトラヒドロフラン等のエーテル系溶剤等に安定的に分散可能である。ここで、本発明の導電性高分子をより安定的に分散でき、かつ種々の溶剤系樹脂の汎用溶剤として用いられるという点でメチルエチルケトン、酢酸エチルに分散させることが好ましい。 <3. Conductive polymer dispersion>
The conductive polymer of the present invention is stable in ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and acetone, ester solvents such as ethyl acetate and butyl acetate, aromatic solvents such as toluene, ether solvents such as tetrahydrofuran and the like. Dispersible. Here, it is preferable to disperse the conductive polymer of the present invention in methyl ethyl ketone or ethyl acetate because it can be more stably dispersed and used as a general-purpose solvent for various solvent-based resins.
導電性高分子の分散液は、例えば、次のようにして準備することができる。前述の溶剤等を投入した容器に、分散機を用いてせん断をかけながら本発明の導電性高分子を投入して分散液を調製する。ここで、導電性高分子の投入は、一度に行ってもよいし、その一部を分割して複数回に亘って投入してもよい。一度に投入することが分散時間を短縮できるため好ましい。また、溶剤及び導電性高分子を同時に投入することで分散液を調製しても何ら問題はない。分散機としては、ホモミキサー、高圧ホモジナイザー、超音波ホモジナイザー等を使用できる。 The dispersion liquid of the conductive polymer can be prepared as follows, for example. The conductive polymer of the present invention is charged into a container charged with the above-described solvent or the like while shearing using a disperser to prepare a dispersion. Here, the conducting polymer may be charged at a time, or a part thereof may be divided and charged a plurality of times. It is preferable to input all at once because the dispersion time can be shortened. Moreover, there is no problem even if a dispersion is prepared by simultaneously adding a solvent and a conductive polymer. As the disperser, a homomixer, a high-pressure homogenizer, an ultrasonic homogenizer, or the like can be used.
以上のようにして得られる導電性高分子の分散液には、高導電化を促進する助剤や、分散安定性を底上げするための分散剤、その他にはレベリング剤、可塑剤、濡れ剤、増粘剤、酸化防止剤、紫外線吸収剤、充填剤、防錆剤、顔料などの各種汎用添加剤を用いても良い。 In the dispersion of the conductive polymer obtained as described above, an auxiliary agent that promotes high conductivity, a dispersant for raising the dispersion stability, other leveling agents, plasticizers, wetting agents, Various general-purpose additives such as thickeners, antioxidants, ultraviolet absorbers, fillers, rust inhibitors and pigments may be used.
<4.導電性高分子の製造方法>
本発明の導電性高分子の製造方法は、前記導電性高分子用ドーパントAを準備する工程と、前記導電性高分子用ドーパントA及びπ共役系高分子のモノマーを含む混合物を準備する工程と、前記混合物において重合する工程とを有するものである。すなわち、本発明の導電性高分子は、π共役系高分子のモノマーの重合時に前記導電性高分子用ドーパントAをドープして得ることができる。その結果、導電性高分子の凝集を抑制することができ、有機溶剤(例えば、極性、非極性を問わず、酢酸エチル、メチルエチルケトン、トルエン等)への安定的な分散性を得ることができる。 <4. Method for producing conductive polymer>
The method for producing a conductive polymer of the present invention includes a step of preparing the conductive polymer dopant A, and a step of preparing a mixture containing the conductive polymer dopant A and a π-conjugated polymer monomer. And a step of polymerizing in the mixture. That is, the conductive polymer of the present invention can be obtained by doping the conductive polymer dopant A when the monomer of the π-conjugated polymer is polymerized. As a result, aggregation of the conductive polymer can be suppressed, and stable dispersibility in an organic solvent (for example, ethyl acetate, methyl ethyl ketone, toluene, etc., regardless of polarity or nonpolarity) can be obtained.
本発明の導電性高分子は、例えば、つぎのようにして合成することができる。すなわち、前記π共役系高分子のモノマー(例えば、チオフェン)と、導電性高分子用ドーパントAと、濃塩酸、硫酸鉄を混合し、所定温度(例えば、30℃)を保持するように制御しながら所定時間撹拌した後、過硫酸アンモニウム等の酸化剤を所定時間(例えば、1時間)かけて滴下し、数時間(例えば、5時間)酸化重合させて、重合物を得る。その後、反応液を所定の方法により固液分離を行い導電性高分子の湿体品を得る。その後、導電性高分子の湿体品を所定時間、所定温度の条件で凍結乾燥し、導電性高分子を得ることができる。 The conductive polymer of the present invention can be synthesized, for example, as follows. That is, the π-conjugated polymer monomer (for example, thiophene), the conductive polymer dopant A, concentrated hydrochloric acid, and iron sulfate are mixed and controlled to maintain a predetermined temperature (for example, 30 ° C.). Then, after stirring for a predetermined time, an oxidizing agent such as ammonium persulfate is dropped over a predetermined time (for example, 1 hour) and subjected to oxidative polymerization for several hours (for example, 5 hours) to obtain a polymer. Thereafter, the reaction solution is subjected to solid-liquid separation by a predetermined method to obtain a wet product of conductive polymer. Thereafter, the wet product of the conductive polymer can be freeze-dried for a predetermined time at a predetermined temperature to obtain the conductive polymer.
本発明の導電性高分子の製造方法において、導電性高分子用ドーパントAについては前述の方法により準備することができる。 In the method for producing a conductive polymer of the present invention, the conductive polymer dopant A can be prepared by the above-described method.
つぎに、前記導電性高分子用ドーパントAにπ共役系高分子のモノマーを含むことで導電性高分子を重合するための混合物を得ることができる。また、前記高分子用ドーパントA以外のドーパントを併用しても良い。 Next, a mixture for polymerizing a conductive polymer can be obtained by including a π-conjugated polymer monomer in the conductive polymer dopant A. Moreover, you may use together dopants other than the said dopant A for polymers.
前記π共役系高分子のモノマーとは、重合して得られた高分子が、π電子が共役できる構造、または単結合と多重結合とが交互に連なった構造をとることが可能な高分子を得られるモノマーのことをいい、例えば、チオフェン、アニリン、ピロール、およびこれらの誘導体等のモノマーがあげられる。また、上記モノマーは、炭素数1〜4のアルキル置換基(例えば、メチル基、エチル基、プロピル基、ブチル基)およびアルコキシ置換基(例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基)の少なくとも一方の置換基を有しているものが、溶剤溶解性の点から、好ましい。 The monomer of the π-conjugated polymer is a polymer in which a polymer obtained by polymerization can take a structure in which π electrons can be conjugated, or a structure in which single bonds and multiple bonds are alternately linked. This refers to the monomer obtained, and examples thereof include monomers such as thiophene, aniline, pyrrole, and derivatives thereof. In addition, the monomer includes an alkyl substituent having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group) and an alkoxy substituent (for example, methoxy group, ethoxy group, propoxy group, butoxy group). Those having at least one substituent are preferred from the viewpoint of solvent solubility.
なお、前記π共役系高分子のモノマーの重合開始剤としては、例えば、過硫酸アンモニウム、過酸化水素水や過酸化ベンゾイル等の過酸化物、クロラニル等のベンゾキノン、塩化第二鉄等の化学酸化剤を用いることが可能である。 Examples of the polymerization initiator of the monomer of the π-conjugated polymer include, for example, ammonium persulfate, peroxides such as hydrogen peroxide and benzoyl peroxide, benzoquinones such as chloranil, and chemical oxidants such as ferric chloride. Can be used.
本発明の導電性高分子は、先に述べた前記導電性高分子用ドーパントA及びπ共役系高分子のモノマーの混合物に対して所定の酸化剤等の添加剤を含み、重合反応させることで得ることができる。 The conductive polymer of the present invention contains an additive such as a predetermined oxidizer with respect to the mixture of the above-described dopant A for conductive polymer and the monomer of the π-conjugated polymer, and is subjected to a polymerization reaction. Obtainable.
ここで、前記π共役系高分子のモノマーと前記導電性高分子用ドーパントAとのモル混合比は、π共役系高分子のモノマー/導電性高分子用ドーパントA=100/1〜100/70の範囲内であることが好ましく、より好ましくは、π共役系高分子のモノマー/導電性高分子用ドーパントA=100/5〜100/50の範囲内である。すなわち、π共役系高分子のモノマー/導電性高分子用ドーパントA=100/5〜100/50の範囲内であることでドーパントの立体障害によりπ共役高分子骨格同士のスタッキングが抑制され溶剤への安定分散が可能になると同時に、加熱乾燥により溶剤を揮発させた場合にはπ共役高分子骨格同士がスタッキングすることにより高い導電性を発現できるという理由で好ましい。 Here, the molar mixing ratio of the monomer of the π-conjugated polymer and the dopant A for the conductive polymer is: π-conjugated polymer monomer / conductive polymer dopant A = 100/1 to 100/70. It is preferable to be within the range of π-conjugated polymer monomer / conductive polymer dopant A = 100/5 to 100/50. That is, the stacking of π-conjugated polymer skeletons is suppressed by the steric hindrance of the dopant by being in the range of π-conjugated polymer monomer / conductive polymer dopant A = 100/5 to 100/50, and thus into the solvent. When the solvent is volatilized by heat drying, high conductivity can be expressed by stacking the π-conjugated polymer skeletons with each other.
本発明の導電性高分子は、その重合の際に非π共役系高分子のモノマーやこれらから誘導される高分子、導電剤等を必要に応じて適宜に配合しても差し支えない。 The conductive polymer of the present invention may contain a non-π conjugated polymer monomer, a polymer derived therefrom, a conductive agent, and the like as needed during the polymerization.
本発明において、非π共役系高分子とは、前記π共役系高分子のように、単結合と多重結合とが交互に連なった高分子以外の高分子を意味する。 In the present invention, the non-π conjugated polymer means a polymer other than a polymer in which single bonds and multiple bonds are alternately connected, such as the π conjugated polymer.
前記非π共役系高分子としては、例えば、アクリル系高分子、メタクリル系高分子、ウレタン系高分子、ゴム系高分子などの熱可塑性樹脂、フェノール系高分子などの熱硬化性樹脂、熱可塑性エラストマー等があげられる。これらは単独でもしくは2種以上併せて用いてもよい。 Examples of the non-π conjugated polymer include thermoplastic resins such as acrylic polymers, methacrylic polymers, urethane polymers, and rubber polymers, thermosetting resins such as phenolic polymers, and thermoplastics. Examples thereof include elastomers. These may be used alone or in combination of two or more.
つぎに、実施例について、比較例と併せて以下に説明する。 Next, examples will be described below together with comparative examples.
<シリコーン化合物の合成>
合成例1:シリコーン化合物1の合成
片末端エポキシオルガノシロキサン(信越化学工業製 X−22−173BX)を30g、2−メルカプトエタンスルホン酸ナトリウムを1.98g、イソプロピルアルコールを23g、トリエチルアミンを0.3g混合し加熱還流下15時間反応させた。反応物に水を加え減圧留去によりイソプロピルアルコールを除去することでシリコーン化合物1の乳化液(不揮発分12.6%)を得た。化合物1の重量平均分子量をGPCによって測定したところ、3500であった。 <Synthesis of silicone compounds>
Synthesis Example 1: Synthesis of Silicone Compound 1 One -terminal epoxyorganosiloxane (X-22-173BX manufactured by Shin-Etsu Chemical Co., Ltd.), 1.98 g of sodium 2-mercaptoethanesulfonate, 23 g of isopropyl alcohol, and 0.3 g of triethylamine The mixture was mixed and reacted for 15 hours under reflux. Water was added to the reaction product, and isopropyl alcohol was removed by distillation under reduced pressure to obtain an emulsion of silicone compound 1 (nonvolatile content 12.6%). It was 3500 when the weight average molecular weight of the compound 1 was measured by GPC.
合成例2:シリコーン化合物2の合成
片末端エポキシオルガノシロキサン(信越化学工業製 X−22−173DX)と2−メルカプトエタンスルホン酸ナトリウムを合成例1と同様の手順で反応させシリコーン化合物2の乳化液を得た。化合物2の重量平均分子量をGPCによって測定したところ、5400であった。 Synthesis Example 2: Synthesis of Silicone Compound 2 Single-end epoxy organosiloxane (X-22-173DX, manufactured by Shin-Etsu Chemical Co., Ltd.) and sodium 2-mercaptoethanesulfonate were reacted in the same procedure as in Synthesis Example 1, and an emulsion of silicone compound 2 Got. It was 5400 when the weight average molecular weight of the compound 2 was measured by GPC.
合成例3:シリコーン化合物3の合成
片末端メタクリロイルオルガノシロキサン(信越化学工業製 X−22−2426)を15g、2−メルカプトエタンスルホン酸ナトリウムを2.08g、イソプロピルアルコールを48g混合し窒素雰囲気下、加熱還流下で30分攪拌した。その後、ベンゾイルペルオキシド1.55gを加え15時間反応させた。反応物に水を加え減圧留去によりイソプロピルアルコールを除去することでシリコーン化合物3の乳化液を得た。化合物3の重量平均分子量をGPCによって測定したところ、16300であった。 Synthesis Example 3 Synthesis of Silicone Compound 3 Single-terminal methacryloylorganosiloxane (X-22-2426 manufactured by Shin-Etsu Chemical Co., Ltd.), 2.08 g of sodium 2-mercaptoethanesulfonate, and 48 g of isopropyl alcohol were mixed in a nitrogen atmosphere. The mixture was stirred for 30 minutes under heating to reflux. Thereafter, 1.55 g of benzoyl peroxide was added and allowed to react for 15 hours. Water was added to the reaction product, and isopropyl alcohol was removed by distillation under reduced pressure to obtain an emulsion of silicone compound 3. It was 16300 when the weight average molecular weight of the compound 3 was measured by GPC.
合成例4:シリコーン化合物4の合成
片末端メタクリロイルオルガノシロキサン(信越化学工業製 X−22−2404)を15g、2−メルカプトエタンスルホン酸ナトリウムを5.93g、イソプロピルアルコールを66g混合し窒素雰囲気下、加熱還流下で30分攪拌した。その後、ベンゾイルペルオキシド4.12gを加え7時間反応させた。反応物に水を加え減圧留去によりイソプロピルアルコールを除去することでシリコーン化合物4の乳化液を得た。化合物4の重量平均分子量をGPCによって測定したところ、750であった。 Synthesis Example 4: Synthesis of silicone compound 4 15 g of terminal methacryloylorganosiloxane (X-22-2404 manufactured by Shin-Etsu Chemical Co., Ltd.), 5.93 g of sodium 2-mercaptoethanesulfonate, and 66 g of isopropyl alcohol were mixed in a nitrogen atmosphere. The mixture was stirred for 30 minutes under heating to reflux. Then, 4.12 g of benzoyl peroxide was added and reacted for 7 hours. Water was added to the reaction product, and isopropyl alcohol was removed by distillation under reduced pressure to obtain an emulsion of silicone compound 4. It was 750 when the weight average molecular weight of the compound 4 was measured by GPC.
合成例5:シリコーン化合物5の合成
両末端カルボキシオルガノシロキサン(信越化学工業製 X−22−162C)を30g、塩化チオニルを20g窒素雰囲気下、室温で5時間反応させ、その後減圧留去により未反応の塩化チオニルを除去することで、カルボン酸クロリドに官能基変換した。得られたカルボン酸クロリド体にイセチオン酸ナトリウム3.68gを60℃、5時間反応することによりシリコーン化合物5の乳化液を得た。化合物5の重量平均分子量をGPCによって測定したところ、5600であった。 Synthesis Example 5: Synthesis of silicone compound 5 30 g of both-terminal carboxyorganosiloxane (X-22-162C, manufactured by Shin-Etsu Chemical Co., Ltd.) and 20 g of thionyl chloride were reacted in a nitrogen atmosphere at room temperature for 5 hours, and then unreacted by distillation under reduced pressure. By removing thionyl chloride, the functional group was converted to carboxylic acid chloride. The obtained carboxylic acid chloride was reacted with 3.68 g of sodium isethionate at 60 ° C. for 5 hours to obtain an emulsion of silicone compound 5. It was 5600 when the weight average molecular weight of the compound 5 was measured by GPC.
合成例6:シリコーン化合物6の合成
両末端チオールオルガノシロキサン(信越化学工業製 X−22−167B)を30gとリン酸2−(メタクリロイルオキシ)エチルを3.70g、イソプロピルアルコールを66g混合し窒素雰囲気下、加熱還流下で30分攪拌した。その後、ベンゾイルペルオキシド4.27gを加え7時間反応させた。反応物に水を加え減圧留去によりイソプロピルアルコールを除去し、さらに炭酸水素ナトリウムを用いて中和することによりシリコーン化合物6の乳化液を得た。化合物6の重量平均分子量をGPCによって測定したところ、4100であった。 Synthesis Example 6: Synthesis of Silicone Compound 6 30 g of both-end thiol organosiloxane (X-22-167B manufactured by Shin-Etsu Chemical Co., Ltd.), 3.70 g of 2- (methacryloyloxy) ethyl phosphate, and 66 g of isopropyl alcohol were mixed in a nitrogen atmosphere. The mixture was stirred for 30 minutes under heating and reflux. Then, 4.27 g of benzoyl peroxide was added and reacted for 7 hours. Water was added to the reaction product, isopropyl alcohol was removed by distillation under reduced pressure, and further neutralized with sodium bicarbonate to obtain an emulsion of silicone compound 6. It was 4100 when the weight average molecular weight of the compound 6 was measured by GPC.
合成例7:シリコーン化合物7の合成
アクリル酸トリイソプロピルシリルを15g、3−スルホプロピルメタクリレートカリウムを16.2g、イソプロピルアルコールを66g混合し窒素雰囲気下、加熱還流下で30分攪拌した。その後、ベンゾイルペルオキシド16.2gを加え7時間反応させた。反応物に水を加え減圧留去によりイソプロピルアルコールを除去することでシリコーン化合物7の乳化液を得た。化合物7の重量平均分子量をGPCによって測定したところ、340であった。 Synthesis Example 7: Synthesis of Silicone Compound 7 15 g of triisopropylsilyl acrylate, 16.2 g of potassium 3-sulfopropyl methacrylate, and 66 g of isopropyl alcohol were mixed and stirred for 30 minutes under heating and refluxing in a nitrogen atmosphere. Thereafter, 16.2 g of benzoyl peroxide was added and reacted for 7 hours. Water was added to the reaction product, and isopropyl alcohol was removed by distillation under reduced pressure to obtain an emulsion of silicone compound 7. It was 340 when the weight average molecular weight of the compound 7 was measured by GPC.
上記合成例1〜7で得られたシリコーン化合物1〜7及び比較対象として用いたその他の化合物A〜C並びにそれらの構造(分子量、主鎖の構造、置換基等)を一覧にしたものを表1として以下に示す。 Table showing the list of silicone compounds 1 to 7 obtained in Synthesis Examples 1 to 7 and other compounds A to C used as comparison targets and their structures (molecular weight, main chain structure, substituents, etc.) 1 is shown below.
化合物A:多環フェニルエーテルのポリエチレンオキサイド末端スルホン酸系乳化剤(日本乳化剤製ニューコール723−SF 分子量1100)
化合物B:ドデシルベンゼンスルホン酸ナトリウム(分子量348)
化合物C:両末端カルボキシオルガノシロキサン(信越化学工業製 X−22−162C、分子量4600)
Compound A: Polyethylene Phenyl Ether Polyethylene Oxide Terminal Sulfonic Acid Emulsifier (Nippon Emulsifier Newcor 723-SF Molecular Weight 1100)
Compound B: Sodium dodecylbenzenesulfonate (molecular weight 348)
Compound C: Carboxyorganosiloxane at both ends (Shin-Etsu Chemical X-22-162C, molecular weight 4600)
導電性高分子用ドーパントの重量平均分子量は、GPC(HLC-8120GPC:東ソー製)を用いて、以下の条件により測定を行った。尚、測定の際に、イオン交換を行いテトラヒドロフランに溶解させた上で、下記の条件で、標準ポリエチレンオキサイド換算により求めた。
<測定条件>
GPCカラム構成:以下の5連カラム
(i)TSK−GEL HXL−H(ガードカラム、東ソー製)
(ii)TSK−GEL 7000HXL(東ソー製)
(iii)TSK−GEL GMHXL(東ソー製)
(iv)TSK−GEL GMHXL(東ソー製)
(v)TSK−GEL G2500HXL(東ソー製)
サンプル濃度:1.0mg/cm3となるようにテトラヒドロフランで希釈
移動相溶媒:テトラヒドロフラン
流速:1.0cm3/min.
カラム温度:40℃The weight average molecular weight of the conductive polymer dopant was measured using GPC (HLC-8120GPC: manufactured by Tosoh Corporation) under the following conditions. In the measurement, after ion exchange and dissolution in tetrahydrofuran, the measurement was performed in terms of standard polyethylene oxide under the following conditions.
<Measurement conditions>
GPC column configuration: the following five columns (i) TSK-GEL HXL-H (guard column, manufactured by Tosoh Corporation)
(Ii) TSK-GEL 7000HXL (manufactured by Tosoh Corporation)
(Iii) TSK-GEL GMHXL (manufactured by Tosoh)
(Iv) TSK-GEL GMHXL (manufactured by Tosoh Corporation)
(V) TSK-GEL G2500HXL (manufactured by Tosoh Corporation)
Sample concentration: diluted with tetrahydrofuran to 1.0 mg / cm 3 Mobile phase solvent: tetrahydrofuran Flow rate: 1.0 cm 3 / min.
Column temperature: 40 ° C
<導電性高分子の合成>
表1に示したシリコーン化合物及びその他の化合物A〜Cをドーパントとして用いて、導電性高分子の合成を行った。 <Synthesis of conductive polymer>
Conductive polymers were synthesized using the silicone compounds shown in Table 1 and other compounds A to C as dopants.
合成例8:導電性高分子の合成
合成例1で得た酸変性シリコーン化合物1の乳化液142.5g、濃塩酸1.6g、π共役系高分子のモノマーとしてエチレンジオキシチオフェン(EDOT)3.2g、硫酸鉄0.09gをそれぞれ混合し、30℃で30分攪拌した。その後、上記混合物に、過硫酸アンモニウム5.9gをイオン交換水50gに溶かした水溶液を1時間かけて滴下した。その後、30℃の状態を保ち5時間反応させた。得られた反応液を固液分離することで導電性高分子1の湿体品を得た。該湿体品を24時間、0℃で凍結乾燥し、導電性高分子1の乾燥粉末を得た。 Synthesis Example 8: Synthesis of conductive polymer 142.5 g of acid-modified silicone compound 1 emulsion obtained in Synthesis Example 1, 1.6 g of concentrated hydrochloric acid, ethylenedioxythiophene (EDOT) 3 as a monomer of π-conjugated polymer .2 g and iron sulfate 0.09 g were mixed and stirred at 30 ° C. for 30 minutes. Thereafter, an aqueous solution prepared by dissolving 5.9 g of ammonium persulfate in 50 g of ion-exchanged water was dropped into the above mixture over 1 hour. Then, it was made to react for 5 hours, keeping the state of 30 degreeC. A wet product of the conductive polymer 1 was obtained by solid-liquid separation of the obtained reaction solution. The wet product was freeze-dried at 0 ° C. for 24 hours to obtain a dry powder of the conductive polymer 1.
合成例9〜19:導電性高分子の合成
表2に示すドーパント及びπ共役系高分子のモノマーを用いて、合成例8と同様の手順によって導電性高分子2〜12を合成し、各導電性高分子の乾燥粉末を得た。(導電性高分子12については重合が進行せず、得ることができなかった)ここで、何れの合成例においても、π共役系高分子のモノマー/ドーパントのモル比率は100/23であり、同じである。それらについて以下表2に示す。 Synthesis Examples 9 to 19: Synthesis of Conductive Polymers Using the dopants shown in Table 2 and monomers of π-conjugated polymers, the conductive polymers 2 to 12 were synthesized by the same procedure as in Synthesis Example 8, A dry powder of a functional polymer was obtained. (Polymerization did not proceed for conductive polymer 12 and could not be obtained) Here, in any synthesis example, the monomer / dopant molar ratio of the π-conjugated polymer was 100/23, The same. These are shown in Table 2 below.
実施例1〜8、比較例1〜4
上記の手順で合成した各導電性高分子1〜11を用いて、以下の通り溶剤分散性及び導電性について評価した。その結果を表3として以下に示す。 Examples 1-8, Comparative Examples 1-4
Using each of the conductive polymers 1 to 11 synthesized by the above procedure, solvent dispersibility and conductivity were evaluated as follows. The results are shown in Table 3 below.
<溶剤分散性の評価>
各導電性高分子1〜11を、酢酸エチル、メチルエチルケトン、トルエンに対して不揮発分が1.5%になる比率で混合し、プローブ型超音波ホモジナイザーで処理を行い、各導電性高分子1〜11の有機溶剤分散液を調製した。それぞれの有機溶剤分散液において超音波処理から1時間経過後の沈殿物を目視にて確認する方法により評価した。ここで、分散処理から1時間後に定性ろ紙(No.2)でろ過したときに凝集物が確認されないものを○、凝集物が確認されるものを△、超音波処理直後に凝集物が発生して不均質液になるものを×とした。<Evaluation of solvent dispersibility>
Each of the conductive polymers 1 to 11 is mixed with ethyl acetate, methyl ethyl ketone, and toluene at a ratio of the non-volatile content of 1.5%, and processed with a probe type ultrasonic homogenizer. 11 organic solvent dispersions were prepared. Each organic solvent dispersion was evaluated by a method of visually confirming a precipitate after 1 hour from ultrasonic treatment. Here, one hour after the dispersion treatment, when no flocculation is confirmed when filtered through qualitative filter paper (No. 2), ◯ when the flocculation is confirmed, △, and flocculation occurs immediately after the ultrasonic treatment. The sample that became a heterogeneous liquid was marked with x.
<導電性の評価>
溶剤分散性の評価において作製した各導電性高分子1〜11の酢酸エチル分散液を洗浄したガラス基板上に乾燥膜厚が2μmとなるように滴下した後、90℃で5分間加熱乾燥し、導電率測定サンプルを作製した。作製したサンプルについて抵抗率計(三菱化学アナリテック製、ロレスタGP)を用いて導電率(S/cm)を測定した。<Evaluation of conductivity>
After dropping the ethyl acetate dispersion of each conductive polymer 1-11 produced in the evaluation of solvent dispersibility onto a washed glass substrate so as to have a dry film thickness of 2 μm, it is heated and dried at 90 ° C. for 5 minutes, A conductivity measurement sample was prepared. About the produced sample, electrical conductivity (S / cm) was measured using the resistivity meter (the Mitsubishi Chemical Analytech make, Loresta GP).
実施例1〜8に示す通り、導電性高分子1〜8は、極性溶媒から非極性溶媒まで幅広い一定以上の有機溶剤への分散性と、導電性を示していることが分かった。中でも、実施例1、2においては、好ましい溶剤種である酢酸エチル、メチルエチルケトンに対して優れた分散性を示すと同時に、高い導電率を示した。また、ドーパントAの重量平均分子量が大きい実施例3は、導電率が低下する一方で、より優れた溶剤分散性を示し、重量平均分子量の小さい実施例4は溶剤分散性が低下する一方でより高い導電率を示した。実施例5,6については、両末端に官能基を有することから、実施例1、2に対して溶剤分散性が劣るものの、比較例に対しては十分高い溶剤分散性と導電率を示した。実施例7、8については、π共役系高分子のモノマーを変更しても、高い溶剤分散性を有することが示された。
一方、比較例1は、ドーパントAの重量平均分子量が500より小さく、比較例2においては、シリコーン骨格を有さないことから、溶剤への分散性が非常に悪く、そのため膜質も悪く、導電率は低いか、あるいは導電率の測定が不可能であった。比較例3については、分子量は500より小さく、シリコーン骨格を有さないことから、溶剤分散性が無く、そのため、製膜して導電率の評価を行うことができなかった。比較例4においては、ドーパントAに水溶性が無いため、導電性高分子の重合が適切に進行しなかったため評価を行うことができなかった。
As shown in Examples 1 to 8, it was found that the conductive polymers 1 to 8 exhibited dispersibility in a wide range of organic solvents from polar solvents to nonpolar solvents and conductivity. Among them, Examples 1 and 2 showed excellent dispersibility with respect to preferable solvent species such as ethyl acetate and methyl ethyl ketone, and at the same time, showed high conductivity. Moreover, Example 3 with a large weight average molecular weight of the dopant A shows better solvent dispersibility while the electrical conductivity is lowered, while Example 4 with a small weight average molecular weight has a lower solvent dispersibility. High conductivity was shown. Examples 5 and 6 have functional groups at both ends, so that the solvent dispersibility is inferior to those of Examples 1 and 2, but sufficiently high solvent dispersibility and conductivity are shown for the comparative examples. . About Example 7, 8, even if it changed the monomer of (pi) conjugated polymer, it was shown that it has high solvent dispersibility.
On the other hand, in Comparative Example 1, the weight average molecular weight of the dopant A is smaller than 500, and in Comparative Example 2, since it does not have a silicone skeleton, the dispersibility in the solvent is very poor, so the film quality is also poor, and the conductivity is low. Was low or conductivity could not be measured. In Comparative Example 3, since the molecular weight was smaller than 500 and it did not have a silicone skeleton, there was no solvent dispersibility. Therefore, the film could not be formed and the conductivity could not be evaluated. In Comparative Example 4, since the dopant A was not water-soluble, the polymerization of the conductive polymer did not proceed properly, so that the evaluation could not be performed.
Claims (8)
A step of preparing the conductive polymer dopant according to any one of claims 1 to 4, and a step of preparing a mixture containing the conductive polymer dopant and a π-conjugated polymer monomer. And a method for producing a conductive polymer comprising polymerizing the mixture.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06125519A (en) * | 1992-04-28 | 1994-05-06 | Internatl Business Mach Corp <Ibm> | Wear-resistant and scratch-resistant conductive polymer composition |
JP2001247582A (en) * | 2000-03-08 | 2001-09-11 | Nippon Unicar Co Ltd | Polyogranosiloxane phosphate, composition comprising the same, and method of producing the same |
JP2003171467A (en) * | 2001-12-05 | 2003-06-20 | Nippon Unicar Co Ltd | Phosphorylated polyorganosiloxane, method for producing the same, flame-retardant and resin composition |
JP2006249160A (en) * | 2005-03-09 | 2006-09-21 | Konishi Kagaku Ind Co Ltd | Sulfonated polyorganosilsesquioxane and its preparation method |
KR20110116879A (en) * | 2010-04-20 | 2011-10-26 | 아주대학교산학협력단 | Polyaniline doped by sulfonated polyphenylsilsesquioxane with high stability of electrical conductivity and menufacturing method of the same |
WO2015129515A1 (en) * | 2014-02-27 | 2015-09-03 | テイカ株式会社 | Oxidant/dopant for conductive polymer production, solution of said oxidant/dopant, conductive particles produced using either of these, and electrolytic capacitor using said conductive particles as electrolyte |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3870043A (en) | 1974-03-28 | 1975-03-11 | Allan R Dunn | U-shaped intravenous needle structure |
DE59010247D1 (en) | 1990-02-08 | 1996-05-02 | Bayer Ag | New polythiophene dispersions, their preparation and their use |
FR2830535B1 (en) | 2001-10-10 | 2003-12-19 | Commissariat Energie Atomique | USE OF SULFONIC, PHOSPHONIC ACIDS AS DOPANTS OF POLYANILINE AND CONDUCTIVE COMPOSITE MATERIALS BASED ON POLYANILINE |
DE102004003784B4 (en) | 2004-01-23 | 2011-01-13 | Ormecon Gmbh | Dispersion of intrinsically conductive polyaniline and their use |
KR101595928B1 (en) * | 2011-11-10 | 2016-02-26 | 난징 유니버시티 | Conducting polymer materials based on carbonyl-functionalized polysilicones and methods for their preparation |
KR101444927B1 (en) | 2012-12-11 | 2014-09-26 | 주식회사 펨스 | Slot coater and gap controlling method of slot die nozzle of the same |
-
2017
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06125519A (en) * | 1992-04-28 | 1994-05-06 | Internatl Business Mach Corp <Ibm> | Wear-resistant and scratch-resistant conductive polymer composition |
JP2001247582A (en) * | 2000-03-08 | 2001-09-11 | Nippon Unicar Co Ltd | Polyogranosiloxane phosphate, composition comprising the same, and method of producing the same |
JP2003171467A (en) * | 2001-12-05 | 2003-06-20 | Nippon Unicar Co Ltd | Phosphorylated polyorganosiloxane, method for producing the same, flame-retardant and resin composition |
JP2006249160A (en) * | 2005-03-09 | 2006-09-21 | Konishi Kagaku Ind Co Ltd | Sulfonated polyorganosilsesquioxane and its preparation method |
KR20110116879A (en) * | 2010-04-20 | 2011-10-26 | 아주대학교산학협력단 | Polyaniline doped by sulfonated polyphenylsilsesquioxane with high stability of electrical conductivity and menufacturing method of the same |
WO2015129515A1 (en) * | 2014-02-27 | 2015-09-03 | テイカ株式会社 | Oxidant/dopant for conductive polymer production, solution of said oxidant/dopant, conductive particles produced using either of these, and electrolytic capacitor using said conductive particles as electrolyte |
Non-Patent Citations (1)
Title |
---|
LIU, JUN-KANG ET AL.: "Reactions of Silyl Ketene Acetal-Functionalized Polysiloxanes. Synthesis of Sulfonated Polysiloxanes", MACROMOLECULES, vol. 27, JPN6018005506, 1994, pages 4080 - 4083, XP000456649, ISSN: 0004482306, DOI: 10.1021/ma00093a008 * |
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