JPH0345707A - Polyaniline fiber - Google Patents
Polyaniline fiberInfo
- Publication number
- JPH0345707A JPH0345707A JP18192289A JP18192289A JPH0345707A JP H0345707 A JPH0345707 A JP H0345707A JP 18192289 A JP18192289 A JP 18192289A JP 18192289 A JP18192289 A JP 18192289A JP H0345707 A JPH0345707 A JP H0345707A
- Authority
- JP
- Japan
- Prior art keywords
- polyaniline
- state
- mol
- quinoid
- diimine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 54
- 239000000835 fiber Substances 0.000 title claims abstract description 15
- 229910000071 diazene Inorganic materials 0.000 claims abstract description 20
- 239000002861 polymer material Substances 0.000 claims description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 abstract description 19
- 238000009987 spinning Methods 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 9
- XLHUBROMZOAQMV-UHFFFAOYSA-N 1,4-benzosemiquinone Chemical group [O]C1=CC=C(O)C=C1 XLHUBROMZOAQMV-UHFFFAOYSA-N 0.000 abstract description 7
- 150000003863 ammonium salts Chemical class 0.000 abstract description 6
- 150000001412 amines Chemical class 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 5
- 239000002216 antistatic agent Substances 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 4
- 239000012779 reinforcing material Substances 0.000 abstract description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003063 flame retardant Substances 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 19
- 238000000034 method Methods 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000003302 ferromagnetic material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- -1 etc. Polymers 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Artificial Filaments (AREA)
Abstract
Description
【発明の詳細な説明】 産遺１引韮公身− 本発明は、導電性、配向性に優れ、補強材料。[Detailed description of the invention] Legacy 1 Hikikoshin- The present invention is a reinforcing material with excellent conductivity and orientation.
導電性材料、帯電防止材料、電極材料、静電及び電磁シ
ールド材料９ｗ１燃材料９強磁性材料等として好適に使
用し得るポリアニリン繊維に関する。The present invention relates to polyaniline fibers that can be suitably used as conductive materials, antistatic materials, electrode materials, electrostatic and electromagnetic shielding materials, and ferromagnetic materials.
来の び が しよ゛と る
近年、有機導電材料としてポリアニリンが注目されてお
り、電池、センサ、エレクトロミックデイスプレィ等Ｃ
各種分野への応用が提案されている。In recent years, polyaniline has been attracting attention as an organic conductive material and is being used in batteries, sensors, electromic displays, etc.
Applications to various fields have been proposed.
ポリアニリンは、通常アニリンを酸化重合することによ
り得られるが、これを電子材料等として用いる場合、ア
ニリンの酸性水溶液を用いて電解又は触媒により酸化重
合したポリアニリンが好適である。この場合、アニリン
を酸化重合する方法としては、アニリンの塩酸、ホウフ
ッ化水素酸。Polyaniline is usually obtained by oxidative polymerization of aniline, but when using it as an electronic material, polyaniline is preferably oxidatively polymerized by electrolysis or catalyst using an acidic aqueous solution of aniline. In this case, methods for oxidative polymerization of aniline include hydrochloric acid and fluoroboric acid.
硫酸、過塩素酸等による酸性水溶液より電解酸化してポ
リアニリンを得る方法、及び上記酸性水溶液より過硫酸
アンモニウム、塩化第二鉄２重クロム酸カリウム、過マ
ンガン酸カリウム等の酸化剤にてポリアニリンを得る方
法が知られている。Polyaniline is obtained by electrolytic oxidation from an acidic aqueous solution using sulfuric acid, perchloric acid, etc., and polyaniline is obtained from the above acidic aqueous solution using an oxidizing agent such as ammonium persulfate, potassium ferric chloride dichromate, potassium permanganate, etc. method is known.
このような重合法により得られるポリアニリンは、重合
条件により繊維性構造をとり得ることが知られている（
特開昭６２−１７７０２５号公報。It is known that polyaniline obtained by such a polymerization method can have a fibrous structure depending on the polymerization conditions (
JP-A-62-177025.
特開昭６３−２２８３０号公報）。しかしながら。(Japanese Unexamined Patent Publication No. 63-22830). however.
このようなポリアニリン繊維を巨視的なスケールにまで
紡積するにはいたっていない。It has not yet been possible to spin such polyaniline fibers on a macroscopic scale.
本発明者らの研究によれば、ポリアニリンはその重合、
精製条件を種々！ｌ整することにより、ある程度の結晶
化が可能であることが見い出されており（特開昭６３−
４６２２３号公報）、ポリアニリンの紡糸が可能である
ことが予想される。このようにポリアニリンを紡糸して
繊維化することにより高い結晶配向性が実現化されれば
、より高い導電性、破断強度１強磁性を示すことが予想
され、その用途の拡張が期待できる。According to the research of the present inventors, polyaniline is
Various purification conditions! It has been discovered that a certain degree of crystallization is possible by adjusting the
46223), it is expected that polyaniline can be spun. If high crystal orientation is realized by spinning polyaniline into fibers in this way, it is expected to exhibit higher electrical conductivity and ferromagnetism at break strength, and an expansion of its uses can be expected.
この場合、濃硫酸よりポリアニリンを水中に再沈殿する
事により結晶性を付与できるとの報告もあり、紡糸も可
能とされている（Ａ、アンドレツタ等：シンセチック
メタルス、２６ （１９８８）３８３）が、その広角Ｘ
線回折写真によれば、ここで得られたポリアニリン繊維
は配向性が低く、上記期待に沿うものではない。In this case, it has been reported that crystallinity can be imparted by reprecipitating polyaniline in water from concentrated sulfuric acid, and spinning is also possible (A, Andretsuta, etc.: Synthetic
Metals, 26 (1988) 383), the wide-angle
According to the line diffraction photograph, the polyaniline fiber obtained here has low orientation and does not meet the above expectations.
本発明は、上記事情に鑑みなされたもので、導電性、配
向性に優れ、補強材料、導電性材料、帯電防止材料、電
極材料、静電及び電磁シールド材料１強磁性材料等とし
て好適に使用し得るポリアニリン繊維を提供することを
目的とする。The present invention was made in view of the above circumstances, and has excellent conductivity and orientation, and is suitable for use as reinforcing materials, conductive materials, antistatic materials, electrode materials, electrostatic and electromagnetic shielding materials 1 ferromagnetic materials, etc. The purpose of the present invention is to provide a polyaniline fiber that can be used as a polyaniline fiber.
を するための び
本発明者は、上記目的を達成するため、種々検討を行な
った結果、キノイドニジイミン状態になっている部分が
２５モル％以下であるポリアニリン又はその誘導体を主
成分とする高分子化合物を紡糸することにより、高い導
電性、結晶配向性を有するポリアニリン繊維が得られる
ことを見い出した。In order to achieve the above object, the inventors of the present invention have conducted various studies, and as a result, they have found that a polymer whose main component is polyaniline or a derivative thereof, in which the portion in the quinoid diimine state is 25 mol% or less. We have discovered that polyaniline fibers with high electrical conductivity and crystal orientation can be obtained by spinning molecular compounds.
即ち、本発明者の研究によれば、ポリアニリンは通常下
記式（Ａ）〜（Ｄ）（なお、式（Ｂ）。That is, according to the research of the present inventor, polyaniline usually has the following formulas (A) to (D) (formula (B)).
（Ｃ）は負イオン種がＢＦ４の例である）に示す如く、
ベンゾノイド＝アミン状態
（式Ａ）
ベンゾノイ
ド＝アンモニウム塩状態（式Ｂ）、ドープ＝セミキノン
ラジカル状態（弐〇）及びキノイドニジイミン状態（式
Ｄ）の混合状態よりなるもので、通常の酸性水溶液中で
電解重合又は触媒酸化重合により得られたポリアニリン
の各状態の割合は、重合液中でベンゾノイド＝アミン状
態２０〜６０モル％、ベンゾノイド＝アンモニウム塩状
態１２〜２５モル％、ドープ＝セミキノンラジカル状態
３０〜５５モル％、キノイドニジイミン状態Ｏ〜５モル
％であるが、このポリアニリンは、ベンゾキノン、ヒド
ロキノン、ジフェニルアミンなどの低分子量物質及びア
ニリンモノマーと重合に用いた酸の塩化物とを大量を含
んでいる。そこで、ポリアニリン以外の物質を除去し、
ベンゾノイド＝アンモニウム塩状態部分を減少させるた
めに水洗を施すと１通常ベンゾノイド＝アミン状態４０
〜７０モル％、ベンゾノイド＝アンモニウム塩状態０〜
５モル％、ドープ＝セミキノンラジカル状態５〜１５モ
ル％、キノイドニジイミン状態２５〜４０モル％となる
。しかし、上記式（Ｄ）に示したようにキノイドニジイ
ミン状態のポリアニリンは、窒素原子に結合する水素原
子を持たないので分子間水素結合が生成せず、そのため
キノイドニジイミン状態の含有量が多いと高い配向性が
得られないこと、ポリアニリン中の上記キノイドニジイ
ミン状態部分を２５モル％以下とすることにより、この
ポリアニリンから良好な結晶配向性を有するポリアニリ
ン繊維が紡糸し得ることを見い出し１本発明を完成した
ものである。(C) is an example in which the negative ion species is BF4), benzonoid = amine state (Formula A), benzonoid = ammonium salt state (Formula B), dope = semiquinone radical state (2〇), and quinoid diimine The proportion of each state of polyaniline obtained by electrolytic polymerization or catalytic oxidation polymerization in a normal acidic aqueous solution is 20 to 60 mol% of the benzonoid=amine state in the polymerization solution. , benzonoid = ammonium salt state 12-25 mol%, dope = semiquinone radical state 30-55 mol%, quinoid diimine state O-5 mol%, but this polyaniline is a low molecular weight compound such as benzoquinone, hydroquinone, diphenylamine, etc. It contains large amounts of substances and aniline monomers and chlorides of the acids used in the polymerization. Therefore, we removed substances other than polyaniline,
When washed with water to reduce the benzonoid = ammonium salt state portion, 1 normal benzonoid = amine state 40
~70 mol%, benzonoid=ammonium salt state 0~
5 mol%, dope=semiquinone radical state 5 to 15 mol%, and quinoid diimine state 25 to 40 mol%. However, as shown in the above formula (D), polyaniline in the quinoid diimine state does not have a hydrogen atom bonded to a nitrogen atom, so no intermolecular hydrogen bonds are formed, and therefore the content of the quinoid diimine state is high. We found that polyaniline fibers with good crystal orientation could be spun from this polyaniline by reducing the amount of the quinoid-nidimine state portion in the polyaniline to 25 mol% or less. It is a completed invention.
実際、上述した文献において濃硫酸から紡糸されるポリ
アニリンは、そのキノイドニジイミン状態部分が可視吸
収スペクトルより判断すると２５％以上であり、このた
めに配向性が低いものと思われる。In fact, in the above-mentioned literature, the polyaniline spun from concentrated sulfuric acid has a quinoid diimine state portion of 25% or more, as judged from the visible absorption spectrum, and is therefore thought to have low orientation.
従って、本発明は、キノイドニジイミン状態になってい
る部分が２５モル％以下であるポリアニリン又はその誘
導体を主成分とする高分子物質を紡糸したことを特徴と
するポリアニリン繊維を提供するものである。Therefore, the present invention provides a polyaniline fiber characterized by being spun from a polymer material whose main component is polyaniline or a derivative thereof, in which the portion in the quinoid diimine state is 25 mol % or less. .
以下、本発明につき更に詳しく説明する。The present invention will be explained in more detail below.
本発明に用いるポリアニリン又はその誘導体としては、
キノイドニジイミン状態部分が２５モル％以下、好まし
くは１８モル％以下のものである。Polyaniline or its derivatives used in the present invention include:
The quinoid diimine state moiety is 25 mol% or less, preferably 18 mol% or less.
また、より好ましくはキノイドニジイミン状態部分が２
５モル％以下、特に１８モル％以下でベンゾノイド＝ア
ミン状態部分が１８〜１００モル％、特に２４〜９７モ
ル％、ベンゾノイド＝アンモニウム塩状態部分が０〜１
５モル％、特に０〜１０モル％、ドープ＝セミキノンラ
ジカル状態部分が０〜５０モル％、特に０〜４５モル％
のポリアニリン又はその誘導体を使用する。More preferably, the quinoid diimine state moiety is 2
5 mol% or less, especially 18 mol% or less, the benzonoid=amine state part is 18 to 100 mol%, especially 24 to 97 mol%, and the benzonoid=ammonium salt state part is 0 to 1
5 mol%, especially 0 to 10 mol%, dope=semiquinone radical state moiety 0 to 50 mol%, especially 0 to 45 mol%
polyaniline or its derivatives.
なお１本発明において、ポリアニリンの誘導体としては
、
（式中、Ｒ０〜Ｒ３は、それぞれ水素原子、アリール基
、アルキル基、Ｎ○ｚｔ ＮＨ，、ＣＦ、。In addition, in the present invention, the polyaniline derivatives include (wherein R0 to R3 are each a hydrogen atom, an aryl group, an alkyl group, N○zt NH,, CF, etc.).
リール基又はアルキル基）から選択される互に同−又は
異種の基を表わす。）
等が挙げられる。aryl group or alkyl group), which are the same or different from each other. ) etc.
上記ポリアニリン又はその誘導体としては、電解酸化重
合法により重合したものでも、触媒酸化重合性により重
合したものでもよい。更に、重合したポリアニリン又は
その誘導体に各種の酸処理。The polyaniline or its derivative may be one polymerized by electrolytic oxidative polymerization or one polymerized by catalytic oxidative polymerization. Furthermore, the polymerized polyaniline or its derivatives are treated with various acids.
アルカリ処理、還元処理、酸化処理等を施したものも好
適に使用し得るが、特に重合時に塩酸、硫酸、ホウフッ
化水素酸を用いて製造し、酸化状態でアルカリ洗浄や過
度の洗浄を施していないもの。Products that have been subjected to alkali treatment, reduction treatment, oxidation treatment, etc. can also be suitably used, but in particular those that have been produced using hydrochloric acid, sulfuric acid, or fluoroboric acid during polymerization and are subjected to alkali washing or excessive washing in an oxidized state. Something that isn't there.
還元状態で空気中に装置していないものが好適である。Those that are not placed in air under reduced conditions are preferred.
なお、上記キノイドニジイミン状態部分が２５モル％以
下のポリアニリン又はその誘導体を特定する方法として
は、Ｘ線光電子分光分析法と電気化学的方法とを併用す
る方法、更にはこれにラマン分光分析法やＮＭＲ法を組
み合わせる方法（特願昭６３−１４２４６０号公報参照
）が好適に用いられるが、便法としては可視吸収スペク
トルを用いることもできる。即ち、キノイドニジイミン
状態部分のポリアニリンは５００ｎｍ付近に吸収を示す
ので（Ｒ，Ｊ、キャッシュマン、Ｐ、Ｍ。In addition, methods for identifying polyaniline or its derivatives having 25 mol% or less of the above-mentioned quinoid diimine state moiety include a method using a combination of X-ray photoelectron spectroscopy and an electrochemical method, and furthermore, a method using Raman spectroscopy. Although a method combining NMR and NMR methods (see Japanese Patent Application No. 63-142460) is preferably used, a visible absorption spectrum can also be used as a convenient method. That is, polyaniline in the quinoid diimine state exhibits absorption near 500 nm (R, J, Cashman, P, M).
マクナマン、Ｓ、Ｃ，ヤング：ジャーナルオブエレクト
ロアナルケミストリー２９１ （１９８６）３３５）、
これを利用することができる。この場合、簡易な判定法
としては、５００ｎｍ付近における吸収よりも４００ｎ
ｍ付近における吸収が大きいことを確認すればよい。McNaman, S., C. Young: Journal of Electroanal Chemistry 291 (1986) 335),
You can take advantage of this. In this case, a simple judgment method is that absorption at 400 nm is higher than absorption near 500 nm.
It is sufficient to confirm that the absorption near m is large.
上記ポリアニリン又はその誘導体を主成分とする高分子
物質を紡糸する場合、上記高分子物質中のポリアニリン
又はその誘導体以外の成分としては、各種ポリアミドや
ポリエステル等が挙げられ、ポリアニリン又はその誘導
体とこれらとの混合物又はこれらの七ツマ−との共重合
物やブロック重合物とすることができる。この場合、副
成分モノマーに制限はないが、ε−カプロラクタム、ア
ジピン酸、ヘキサメチレンジアミン、テレフタル酸等が
好ましい。なお、ポリアニリン又はその誘導体を単独で
用いることは熱論差支えなく、高分子物質中のポリアニ
リン又はその誘導体の含有量は５０〜１００モル％とす
ることが好ましい。When spinning a polymer substance containing the above-mentioned polyaniline or its derivative as a main component, components other than polyaniline or its derivative in the above-mentioned polymer substance include various polyamides, polyesters, etc., and polyaniline or its derivative and these or a copolymer or block polymer with these seven polymers. In this case, the subcomponent monomer is not limited, but ε-caprolactam, adipic acid, hexamethylene diamine, terephthalic acid, etc. are preferable. Note that there is no problem with the thermal theory of using polyaniline or its derivative alone, and it is preferable that the content of polyaniline or its derivative in the polymer substance is 50 to 100 mol%.
上記高分子物質を紡糸する方法としては、通常良溶剤中
に溶解した高分子物質を貧溶剤中に加圧射出する紡糸法
が好適に採用される。As a method for spinning the above-mentioned polymeric substance, a spinning method in which a polymeric substance dissolved in a good solvent is injected under pressure into a poor solvent is usually suitably employed.
ここで゛、ポリアニリン又はその誘導体の溶剤としては
、ジメチルフォルムアミド、ジメチルスルフオキシド、
ピリジン、メチルピロリドンなどの有機溶剤及び硫酸、
硝酸、王水などの強酸を挙げることができるが、この場
合の良溶剤としては、２４Ｎ以上の硫酸、特に３２Ｎ以
上の硫酸が好ましい。この際、ポリアニリン又はその誘
導体のキノイドニジイミン状態部分は酸性溶液中で若干
量がドープ＝セミキノンラジカル状態に変化するが、２
５モル％以上のキノイドニジイミン状態を含むポリアニ
リン又はその誘導体を特徴とする特許を用い、溶液中で
キノイド＝ジイミン状態部分が２５モル％以下とするの
は得策ではなく、酸性溶液中でのキノイド＝ジイミン状
態からドープ＝セミキノンラジカル状態への変化は、そ
の効率がきわめて低いので、２４Ｎ以上の硫酸を良溶剤
として用いる場合でも当初よりキノイド＝ジイミン状態
部分が２５モル％以下のポリアニリン又はその誘導体を
主成分とする高分子物質を用いることが好ましい。なお
、該高分子物質を良溶剤に溶解させる濃度としては工〜
５０％（溶質重量／溶剤体積）、特に１０〜３０％とす
ることが好ましい。Here, examples of the solvent for polyaniline or its derivatives include dimethylformamide, dimethyl sulfoxide,
Organic solvents such as pyridine and methylpyrrolidone and sulfuric acid,
Strong acids such as nitric acid and aqua regia can be used, but as a good solvent in this case, 24N or higher sulfuric acid, particularly 32N or higher sulfuric acid is preferred. At this time, a small amount of the quinoid diimine state portion of polyaniline or its derivatives changes to the dope=semiquinone radical state in the acidic solution, but 2
Using a patent that features polyaniline or its derivatives containing 5 mol% or more of the quinoid diimine state, it is not a good idea to have 25 mol% or less of the quinoid = diimine state moiety in solution; Since the efficiency of changing from the =diimine state to the doped = semiquinone radical state is extremely low, even when 24N or higher sulfuric acid is used as a good solvent, polyaniline or its derivatives with a quinoid = diimine state portion of 25 mol% or less are used from the beginning. It is preferable to use a polymeric substance containing as a main component. In addition, the concentration at which the polymer substance is dissolved in a good solvent is
It is preferably 50% (solute weight/solvent volume), particularly 10 to 30%.
また、貧溶剤としては、特に制限されないが、濃硫酸を
良溶剤とする場合であれば、イオン交換水、蒸留水、２
Ｎ以下の硫酸、塩酸、アンモニア水、水酸化ナトリウム
水溶液、水酸化カリウム水Ｉ容液、アセトン、アセトニ
トリル、メタノール、エタノール等を挙げることができ
る。The poor solvent is not particularly limited, but if concentrated sulfuric acid is used as a good solvent, ion-exchanged water, distilled water,
Examples include sulfuric acid of N or less, hydrochloric acid, aqueous ammonia, aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, acetone, acetonitrile, methanol, and ethanol.
上記方法により紡糸する場合、６０℃〜貧溶剤の凝固点
の間の温度、特に１０〜−１０℃の温度で紡糸すること
が好ましい。なお、その他の条件は通常の合成繊維の場
合と同様の紡糸条件とすることができる。When spinning by the above method, it is preferable to perform the spinning at a temperature between 60°C and the freezing point of the poor solvent, particularly at a temperature of 10°C to -10°C. Note that the other spinning conditions can be the same as those for ordinary synthetic fibers.
遣」■だか果
以上説明したように、本発明のポリアニリン繊維は、導
電性、結晶配向性に優れ、補強材料、導電性材料、帯電
防止材料２電極材料、静電及び電磁シールド材料、難燃
材料２強磁性材料等として好適に使用し得るものでる。As explained above, the polyaniline fiber of the present invention has excellent conductivity and crystal orientation, and can be used as reinforcing materials, conductive materials, antistatic materials, two-electrode materials, electrostatic and electromagnetic shielding materials, and flame retardant materials. Material 2 This material can be suitably used as a ferromagnetic material.
以下、実施例を示し５本発明を具体的に説明するが、本
発明は下記実施例に制限されるものではない。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the following Examples.
アニリン３０ｃｃ、３６Ｎ硫酸１７ｃｃを含む水溶液５
００ｃ５と過硫酸アンモニウム１１４．５ｇを含む水溶
液５００ｃｃとを０℃にて混合、撹拌し、その後静置し
てポリアニリンを合成した（キノイド＝ジイミン状態約
Ｏモル％）。このポリアニリンをイオン交換水で洗浄し
た後、アセトニトリルにて洗浄し、真空乾燥してこれを
ガラス乳ばちにて微粉化した。Aqueous solution 5 containing 30 cc of aniline and 17 cc of 36N sulfuric acid
00c5 and 500 cc of an aqueous solution containing 114.5 g of ammonium persulfate were mixed at 0° C., stirred, and then allowed to stand to synthesize polyaniline (quinoid=diimine state approximately 0 mol %). This polyaniline was washed with ion-exchanged water, washed with acetonitrile, dried in vacuum, and pulverized using a glass mortar.
上記微粉状のポリアニリン３ｇを３６ＮｉＪｔ酸１０ｃ
ｃに溶解したものから、シリンジを用いてイオン交換水
中に加圧射出することにより、高配向性のポリアニリン
繊維を得た。3g of the above fine powder polyaniline was added to 10c of 36NiJt acid.
A highly oriented polyaniline fiber was obtained by injecting the solution dissolved in c into ion-exchanged water under pressure using a syringe.
Claims (1)
ル％以下であるポリアニリン又はその誘導体を主成分と
する高分子物質を紡糸したことを特徴とするポリアニリ
ン繊維。1. A polyaniline fiber characterized by being spun from a polymer material whose main component is polyaniline or a derivative thereof, in which the portion in the quinoid-diimine state is 25 mol% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18192289A JPH0345707A (en) | 1989-07-14 | 1989-07-14 | Polyaniline fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18192289A JPH0345707A (en) | 1989-07-14 | 1989-07-14 | Polyaniline fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0345707A true JPH0345707A (en) | 1991-02-27 |
Family
ID=16109252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18192289A Pending JPH0345707A (en) | 1989-07-14 | 1989-07-14 | Polyaniline fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0345707A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007521405A (en) * | 2003-11-03 | 2007-08-02 | アルバニー インターナショナル コーポレイション | Durable highly conductive synthetic fabric structure |
-
1989
- 1989-07-14 JP JP18192289A patent/JPH0345707A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007521405A (en) * | 2003-11-03 | 2007-08-02 | アルバニー インターナショナル コーポレイション | Durable highly conductive synthetic fabric structure |
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