JPH01156326A - Production of sulfur-containing polymer - Google Patents
Production of sulfur-containing polymerInfo
- Publication number
- JPH01156326A JPH01156326A JP62313159A JP31315987A JPH01156326A JP H01156326 A JPH01156326 A JP H01156326A JP 62313159 A JP62313159 A JP 62313159A JP 31315987 A JP31315987 A JP 31315987A JP H01156326 A JPH01156326 A JP H01156326A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- sulfur
- chloride
- solution
- monomer
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 53
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000011593 sulfur Substances 0.000 title claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 22
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 16
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229930192474 thiophene Natural products 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 6
- -1 hetero compound Chemical class 0.000 claims abstract description 6
- 230000000737 periodic effect Effects 0.000 claims abstract description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims abstract 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims abstract 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 13
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 229920001940 conductive polymer Polymers 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 3
- 239000004020 conductor Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000002216 antistatic agent Substances 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000000944 Soxhlet extraction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920000123 polythiophene Polymers 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ATRJNSFQBYKFSM-UHFFFAOYSA-N 2,3-dibromothiophene Chemical compound BrC=1C=CSC=1Br ATRJNSFQBYKFSM-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、イオウ含有導電性高分子の製造方法に関する
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a sulfur-containing conductive polymer.
［従来の技術］
骨格に硫黄を含む芳香族化合物およびヘテロ化合物の重
合体は導電性高分子となることが知られている。たとえ
ば、ポリチオフェン、ポリベンゾチオフェン等であり、
高いものでは１０２８／ｃｍ以上の導電性が得られてい
る。このような高い導電性を示す重合体は一般に電解重
合法を用いて電極上に薄膜として形成される（ Ｊ、
Ｐｈｙｓ、 Ｃｈｅｍ、 、 ８７゜２２８９、（１９
８３） ）。しかし、電解重合法は導電性の高い薄膜状
重合体を得るには適しているが、多量の重合体を製造す
る上では効率の好ましい方法ではない。[Prior Art] It is known that polymers of aromatic compounds and hetero compounds containing sulfur in their skeletons become conductive polymers. For example, polythiophene, polybenzothiophene, etc.
High conductivities of 1028/cm or higher have been obtained. Polymers exhibiting such high conductivity are generally formed as thin films on electrodes using electrolytic polymerization methods (J,
Phys, Chem, , 87°2289, (19
83) ). However, although the electrolytic polymerization method is suitable for obtaining a highly conductive thin film polymer, it is not an efficient method for producing a large amount of polymer.
一方、化学的に重合する方法も試みられており、この方
法では一般には多量の重合体を製造することが可能であ
る。たとえば、グリニヤー法により金属マグネシウムと
触媒の塩化ニッケルを用いて合成する方法が知られてい
る（Ｊ、ＰＯＩＶ…、ＳＣｉ、、ＰＯＩ３ 、 Ｌｅｔ
ｔ、Ｆｄ、 ＋’ １８．’９（１９８０） ） 。し
かし、この方法ではモノマーと、当モル程度のマグネシ
ウムを必要とするので安価な重合体を得る方法としては
好ましくない。また、一般に導電性高分子は剛直な構造
をしているため、溶媒に溶けにくく、重合の進行に伴っ
て沈澱しやすい。すなわち、溶液状態での重合が十分に
進行しない内に沈澱するため重合度が低くなりやすい。On the other hand, chemical polymerization methods have also been attempted, and it is generally possible to produce a large amount of polymer with this method. For example, a method of synthesis using metallic magnesium and nickel chloride as a catalyst by the Grignard method is known (J, POIV..., SCi,, POI3, Let
t, Fd, +' 18. '9 (1980)). However, this method requires a monomer and an equimolar amount of magnesium, so it is not preferred as a method for obtaining an inexpensive polymer. Furthermore, since conductive polymers generally have a rigid structure, they are difficult to dissolve in solvents and tend to precipitate as polymerization progresses. That is, since the polymer precipitates before the polymerization in the solution state progresses sufficiently, the degree of polymerization tends to decrease.
［発明が解決しようとする問題点］
上述したように、化学重合による含硫黄芳香族導電性高
分、子の製造方法では高重合度の“重合体を得ることが
難しく、そのため電解重合法による重合体と□比べて電
解′□度が低くなるという欠点がある。 ゛したがって
、形成された重合体が溶解できる溶媒中で重合反応が進
行するような重合方ｉ可能になればより導電性の高い導
電性重合体が得られるものと期待される。本発明は溶解
状態で導電性高分子の重合を行うことにより、より高導
電性の重合体をより安価に合成することを目的としてい
る。[Problems to be Solved by the Invention] As mentioned above, it is difficult to obtain a polymer with a high degree of polymerization by the method for producing sulfur-containing aromatic conductive polymers and molecules by chemical polymerization. It has the disadvantage that the degree of electrolysis is lower than that of polymers. Therefore, if a polymerization method in which the polymerization reaction proceeds in a solvent that can dissolve the formed polymer becomes possible, it will be possible to make it more conductive. It is expected that a highly conductive polymer will be obtained.The purpose of the present invention is to synthesize a highly conductive polymer at a lower cost by polymerizing a conductive polymer in a dissolved state.
［問題点を解決するための手段］
上記目的を達成するために本発明は下記の構成１を！す
る。[Means for Solving the Problems] In order to achieve the above object, the present invention has the following configuration 1! do.
「イオウを含む、ヘテロ化合物または芳香族化合物をモ
ノマーとして、周期律表第３族金属塩化物の塩化チオニ
ル溶液中で溶液重合することを特徴とするイオウ含有高
分子の製造方法。」本発明で言う硫黄を含む、ヘテロ化
合物または芳香族化合物とは、５員環内に硫黄を含む構
造を構成要素とする化合物、または芳香族スルフィド化
合物であり、使用される七ツマ−の例としては、チオフ
ェン、ベンゾチオフェン、ジベンゾチオフェン、チオフ
ェノール等が挙げられる。"A method for producing a sulfur-containing polymer, which comprises solution polymerizing a sulfur-containing hetero compound or an aromatic compound as a monomer in a thionyl chloride solution of a chloride of a Group 3 metal in the periodic table." The sulfur-containing hetero compounds or aromatic compounds are compounds having a structure containing sulfur in a five-membered ring, or aromatic sulfide compounds. , benzothiophene, dibenzothiophene, thiophenol and the like.
また、周期律表第３族金属塩化物としては三塩化鉄、三
塩化アルミニウム、三塩化リンが用いられるが好ましく
は三塩化アルミニウムが用いられる。塩化チオニルに対
する金属塩化物の濃度はＱ。Further, as the metal chloride of Group 3 of the periodic table, iron trichloride, aluminum trichloride, and phosphorus trichloride are used, and aluminum trichloride is preferably used. The concentration of metal chloride relative to thionyl chloride is Q.
１モル／αから２モル／Ｑの範囲で使用されるが、重合
反応、溶解性の観点から１モル１０付近が好ましい。反
応温度は溶媒の融点から沸点までが可能であり、−２０
℃から６０℃の範囲で実施されるが、より好ましくは２
０℃から４０℃で行う。It is used in a range of 1 mol/α to 2 mol/Q, but from the viewpoint of polymerization reaction and solubility, it is preferably around 1 mol/Q. The reaction temperature can range from the melting point to the boiling point of the solvent, and -20
It is carried out in the range of ℃ to 60℃, more preferably 2
The temperature is 0°C to 40°C.
反応が進むに伴って反応液は濃い黒色溶液に変化する。As the reaction progresses, the reaction solution turns into a dark black solution.
以上のようにして得られた溶液から該重合体を抽出する
には、重合体抽出方法としての一般的な方法が用いられ
る。すなわち、該重合体の貧溶媒であるトルエン、メタ
ノール、エーテル、ベンゼン、ジメチルスルホキシド、
ニトロメタン等の溶媒中で重合体を沈澱させることによ
って抽出することができる。ただし、これらの沈澱物中
には金属塩化物が含まれるため、沈澱物からさらに金属
塩化物の除去が必要となる。ニトロメタン、エーテル等
の金属塩化物を溶解する溶媒では、金属塩化物が抽出の
隙に除去されるので、特に好ましく使用される。In order to extract the polymer from the solution obtained as described above, a general method for extracting a polymer is used. That is, toluene, methanol, ether, benzene, dimethyl sulfoxide, which are poor solvents for the polymer,
Extraction can be achieved by precipitating the polymer in a solvent such as nitromethane. However, since these precipitates contain metal chlorides, it is necessary to further remove the metal chlorides from the precipitates. Solvents that dissolve metal chlorides, such as nitromethane and ether, are particularly preferably used because the metal chlorides are removed during the extraction process.
本発明に使用される金属塩化物は、重合反応の触媒とな
っている以外に、重合溶媒中に重合体を溶解させる効果
をも果たしている。さらに該金属塩化物は導電性重合体
に対するドーパントとしての作用をも兼ねているので、
溶解した重合体は導電性を発現している。そのため、こ
の溶液状態で導電性液体として利用することも可能であ
る。The metal chloride used in the present invention not only serves as a catalyst for the polymerization reaction, but also has the effect of dissolving the polymer in the polymerization solvent. Furthermore, since the metal chloride also acts as a dopant for the conductive polymer,
The dissolved polymer exhibits electrical conductivity. Therefore, it is also possible to use this solution state as a conductive liquid.
［実施例］ 以下、実施例によって本発明を更に詳細に説明する。[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
塩化アルミ１．３ｇと塩化チオニル１０ＣＣを三ツロフ
ラスコに入れてＮ２下で攪拌し、チオフェン’ｌｃｃを
加えて重合を行った。６時間の反応後に、塩化チオニル
／塩化アルミ溶液に溶解した状態でのチオフェン重合体
を得た。チオフェン重合体の溶解した該溶液をニトロメ
タンに滴下することによって、粉末状のチオフェン重合
体を沈澱物として得た。該重合体をメタノール、水で洗
浄した後、トルエン、エーテルを用いてソックスレー抽
出洗浄を行った。その後、真空乾燥を行い、５００＃Ｉ
ｆｆのチオフェン重合体を得た。該重合体を錠剤成形器
で厚さ１５０μｍのペレットに成形し、２端子法を用い
て導電度の測定を行った。該重合体の電導度は７．３ｘ
１０ ”Ｓ／Ｃｍであったが、ヨウ素ドーピングを施
ずことによって１．２Ｘ１０−３Ｓ／Ｃｍまで向上した
。Example 1 1.3 g of aluminum chloride and 10 cc of thionyl chloride were placed in a three-tube flask, stirred under N2, and thiophene'lcc was added to perform polymerization. After 6 hours of reaction, a thiophene polymer dissolved in the thionyl chloride/aluminum chloride solution was obtained. A powdered thiophene polymer was obtained as a precipitate by dropping the solution in which the thiophene polymer was dissolved into nitromethane. After washing the polymer with methanol and water, Soxhlet extraction washing was performed using toluene and ether. After that, perform vacuum drying and use 500#I
A thiophene polymer of ff was obtained. The polymer was molded into pellets with a thickness of 150 μm using a tablet molding machine, and the conductivity was measured using a two-terminal method. The conductivity of the polymer is 7.3x
10''S/Cm, but it was improved to 1.2X10-3S/Cm by not doping with iodine.
ざらに該重合体のＩＲ吸収スペクトルをＫＢｒ法により
測定した。図面にそのスペクトルを示す。In general, the IR absorption spectrum of the polymer was measured by the KBr method. The spectrum is shown in the drawing.
該スペクトルは、電解重合で得られたチオフェン重合体
のＩＲ吸収スペク１〜ルＵ、八ＫＩ１４０ＴＯ，ｅｔ
ａｌ。The spectra are IR absorption spectra of thiophene polymers obtained by electropolymerization.
al.
５ｙｎｅｈｔｉｃ Ｍｅｔａｌｓ、１５ （１９８６）
３５３−３６０ ）と一致している。７８０Ｃｍ−１
に２，５置換のＣＨ面外変角による吸収、及び１４９０
．１４．３０ｃｍ’にチオフェン環のＣ２＝Ｃ３とＣ４
＝Ｃ５の非対称伸縮と対称伸縮による吸収があり、チオ
フェン環が２゜５位で結合している構造であることが判
る。5ynehtic Metals, 15 (1986)
353-360). 780cm-1
Absorption due to CH out-of-plane bending of 2,5 substitution, and 1490
．． C2=C3 and C4 of the thiophene ring at 14.30cm'
It can be seen that there is absorption due to asymmetric stretching and symmetric stretching of =C5, and the structure is such that the thiophene ring is bonded at the 2°5 position.
比較例１
Ｊｏｕｒｎａｌ ｏｆ Ｐｏｌｙｍｅｒ ５ｃｉｅｎｃ
ｅ：Ｐｏｌｙｍ、Ｌｅｔｔ、Ｅｄ、。Comparative Example 1 Journal of Polymer 5cienc
e: Polym, Lett, Ed.
１８９−１２（１９８０）に記載の方法に従い、２，５
ジブロモチオフェン２．５０をテトラヒドロフラン中で
マグネシウム０．２６ＣＩと反応させ、その反応液に触
媒（Ｎ ！ ＣＱ ２ （２，２’−ｂｉｐｙｒｉｄｉ
ｎｅ） ） １０ｍｇを加えることにより、すなわちグ
リニヤール法を用いて重合体の合成を行い、本発明との
比較を行った。１時間の反応の後にざらに２時間リフラ
ックスを行い、粉末状のポリチオフェンを得た。該重合
体を塩酸を含むメタノール溶液で洗浄した後、熱クロロ
ホルムでソックスレー抽出を行い、熱クロロホルムに可
溶な重合体（２０％）と不溶な重合体（８０％〉に分け
た。熱クロロホルムに不溶な該重合体をペレツ１〜状に
成型し、二端子法を用いて電導度の測定を行った。該重
合体の電導度は１０”’ Ｓ／ｃｍであり、ヨウ素ドー
ピングによって１０’Ｓ／ｃｍに向上した。すなわち、
グリニヤール法で得られたチオフェン重合体よりも、本
発明によるチオフェン重合体のほうが導電度が一桁以上
高いことが判る。189-12 (1980), 2,5
2.50 dibromothiophene was reacted with 0.26 CI of magnesium in tetrahydrofuran, and the reaction solution was treated with a catalyst (N! CQ 2 (2,2'-bipyridi
A polymer was synthesized by adding 10 mg of ne)), that is, using the Grignard method, and compared with the present invention. After 1 hour of reaction, reflux was roughly performed for 2 hours to obtain powdered polythiophene. After washing the polymer with a methanol solution containing hydrochloric acid, Soxhlet extraction was performed with hot chloroform to separate the polymer soluble in hot chloroform (20%) and the polymer insoluble in hot chloroform (80%). The insoluble polymer was molded into pellets and the electrical conductivity was measured using the two-terminal method.The electrical conductivity of the polymer was 10''S/cm, and by iodine doping /cm. In other words,
It can be seen that the electrical conductivity of the thiophene polymer according to the present invention is one order of magnitude higher than that of the thiophene polymer obtained by the Grignard method.
実施例２
塩化アルミ１．３ｇと塩化チオニル’１Ｑｃｃを三ツロ
フラスコに入れてＮ２下で攪拌し、ベンゾ（ｂ）チオフ
ェン１ｇを加えて重合を行った。６時間の反応の後に、
溶解した状態のベンゾチオフェン重合体を得た。ベンゾ
チオフェン重合体が溶解した状態の該溶液を多量のニト
ロメタン中に滴下することによって、ベンゾチオフェン
重合体の粉末を５４０ｍｇ得た。該重合体粉末を、水、
及びエタノールで洗浄した後に、トルエン、エーテルを
用いてソックスレー抽出洗浄を行った。該重合体をペレ
ット状に成型して二端子法を用いて電導度の測定を行っ
た。該重合体の電導度は１０’Ｓ／ｃｍであるが、８０
３ドーピングを施すことによって３．７Ｘ １０−４Ｓ
／ｃｍまで向上した。Example 2 1.3 g of aluminum chloride and 1 Qcc of thionyl chloride were placed in a three-meter flask, stirred under N2, and 1 g of benzo(b)thiophene was added to carry out polymerization. After 6 hours of reaction,
A benzothiophene polymer in a dissolved state was obtained. The solution in which the benzothiophene polymer was dissolved was dropped into a large amount of nitromethane to obtain 540 mg of benzothiophene polymer powder. The polymer powder is mixed with water,
After washing with ethanol and ethanol, Soxhlet extraction washing was performed using toluene and ether. The polymer was molded into a pellet and its electrical conductivity was measured using a two-terminal method. The conductivity of the polymer is 10'S/cm, but 80
3.7X 10-4S by applying 3 doping
/cm.
実施例３
塩化アルミ１．３０と塩化チオニル１００Ｃを三ツロフ
ラスコに入れてＮ２下で゛攪拌し、チオフェン１ｃｃを
加えて一１０℃で７時間重合を行った。Example 3 1.30 C of aluminum chloride and 100 C of thionyl chloride were placed in a three-meter flask, stirred under N2, 1 cc of thiophene was added, and polymerization was carried out at -10° C. for 7 hours.
溶液に溶解した状態のチオフェン重合体が得られた。該
溶液を多量のニトロメタン中に投することによって、緑
色のポリチオフェン重合体粉末を６２０ｍｇ得た。A thiophene polymer dissolved in solution was obtained. By pouring the solution into a large amount of nitromethane, 620 mg of green polythiophene polymer powder was obtained.
実施例４
塩化アルミ３．３０と塩化チオニル２５Ｃ’（：を三ツ
ロフラスコに入れて、Ｎ２下で室温で攪拌し、チオフェ
ノール２ＣＣを加えて２時間重合させた。Example 4 3.30% of aluminum chloride and 25C' of thionyl chloride (: were placed in a three-meter flask, stirred at room temperature under N2, and 2CC of thiophenol was added to polymerize for 2 hours.
溶液に溶解した状態でのポリフェニレンスルフィド（Ｐ
ＰＳ）を得た。該溶液をニトロメタン中に滴下すること
によって、ＰＰＳの粉末を９８０ｍｇ得た。Polyphenylene sulfide (P) dissolved in solution
PS) was obtained. By dropping the solution into nitromethane, 980 mg of PPS powder was obtained.
［発明の効果］
本発明の特徴は導電性を有する重合体を製造する方法に
おいて、□重合体の可溶な溶媒である塩化チオニルと金
属塩化物からなる溶液中で重合体を製造するところにあ
り、従来の方法と比べてより高い導電性をもつ重合体が
得られる。これらの重合体は半導体として、光センサ−
、ガスセンサー材料、蓄電池電極材料、また導電体とし
て制電材料、軽量導電材料として利用される。[Effects of the Invention] The feature of the present invention is that in the method for producing a conductive polymer, the polymer is produced in a solution consisting of thionyl chloride, which is a solvent in which the polymer is soluble, and a metal chloride. This method yields polymers with higher electrical conductivity than conventional methods. These polymers can be used as semiconductors in optical sensors.
It is used as a gas sensor material, a storage battery electrode material, an antistatic material, and a lightweight conductive material.
また、本発明において使用される金属塩化物は、導電性
重合体に作用して導電性を発現させるドーパントとして
の役割をも同時に果しているので、該金属塩化物を含む
重合体溶液は導電性を示す溶液となる。このため導電性
液体としての利用も可能である。Furthermore, the metal chloride used in the present invention simultaneously acts as a dopant that acts on the conductive polymer to develop conductivity, so the polymer solution containing the metal chloride exhibits conductivity. The solution will be as shown. Therefore, it can also be used as a conductive liquid.
図面は、本発明実施例１の化合物について、赤外吸収ス
ペクトルを測定した結果を示す。The drawing shows the results of infrared absorption spectrum measurement for the compound of Example 1 of the present invention.
Claims (4)
をモノマーとして、周期律表第３族金属塩化物の塩化チ
オニル溶液中で溶液重合することを特徴とするイオウ含
有高分子の製造方法。(1) A method for producing a sulfur-containing polymer, which comprises solution polymerizing a sulfur-containing hetero compound or an aromatic compound as a monomer in a thionyl chloride solution of a metal chloride of Group 3 of the periodic table.
びチオフェノールから選ばれる少なくとも一種であるこ
とを特徴とする特許請求の範囲第（１）項記載のイオウ
含有高分子の製造方法。(2) The method for producing a sulfur-containing polymer according to claim (1), wherein the monomer is at least one selected from thiophene, benzothiophene, and thiophenol.
塩化鉄から選ばれる少なくとも一種であることを特徴と
する特許請求の範囲第（１）項記載のイオウ含有高分子
の製造方法。(3) The method for producing a sulfur-containing polymer according to claim (1), wherein the metal chloride of Group 3 of the periodic table is at least one selected from aluminum chloride and iron chloride.
で行なわれることを特徴とする特許請求の範囲第（１）
項記載のイオウ含有高分子の製造方法。(4) Claim No. 1, characterized in that the solution polymerization is carried out at a temperature range of -20°C or higher and 60°C or lower.
A method for producing a sulfur-containing polymer as described in Section 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62313159A JPH0653798B2 (en) | 1987-12-12 | 1987-12-12 | Method for producing sulfur-containing polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62313159A JPH0653798B2 (en) | 1987-12-12 | 1987-12-12 | Method for producing sulfur-containing polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01156326A true JPH01156326A (en) | 1989-06-19 |
| JPH0653798B2 JPH0653798B2 (en) | 1994-07-20 |
Family
ID=18037817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62313159A Expired - Lifetime JPH0653798B2 (en) | 1987-12-12 | 1987-12-12 | Method for producing sulfur-containing polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0653798B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2360776A (en) * | 2000-03-28 | 2001-10-03 | Sharp Kk | Oligomers or polymers of benzofuran, benzothiophene or indole |
| CN114082449A (en) * | 2021-12-01 | 2022-02-25 | 万华化学集团股份有限公司 | Preparation method and application of aluminum ligand catalyst |
-
1987
- 1987-12-12 JP JP62313159A patent/JPH0653798B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2360776A (en) * | 2000-03-28 | 2001-10-03 | Sharp Kk | Oligomers or polymers of benzofuran, benzothiophene or indole |
| CN114082449A (en) * | 2021-12-01 | 2022-02-25 | 万华化学集团股份有限公司 | Preparation method and application of aluminum ligand catalyst |
| CN114082449B (en) * | 2021-12-01 | 2023-10-17 | 万华化学集团股份有限公司 | Preparation method and application of aluminum ligand catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0653798B2 (en) | 1994-07-20 |
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