JPH0317120A - Polyphenylene-based polymer and production thereof - Google Patents
Polyphenylene-based polymer and production thereofInfo
- Publication number
- JPH0317120A JPH0317120A JP15055889A JP15055889A JPH0317120A JP H0317120 A JPH0317120 A JP H0317120A JP 15055889 A JP15055889 A JP 15055889A JP 15055889 A JP15055889 A JP 15055889A JP H0317120 A JPH0317120 A JP H0317120A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- general formula
- oxidative polymerization
- fluorene
- polyphenylene
- 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
- 229920000265 Polyparaphenylene Polymers 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920000642 polymer Polymers 0.000 title abstract description 51
- -1 Polyphenylene Polymers 0.000 title description 4
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 5
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- 239000012300 argon atmosphere Substances 0.000 abstract description 4
- 239000012769 display material Substances 0.000 abstract description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 3
- 239000008151 electrolyte solution Substances 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 38
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 23
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 150000002220 fluorenes Chemical class 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000000944 Soxhlet extraction Methods 0.000 description 4
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- MIHYKOZJQMWHCQ-UHFFFAOYSA-N 9-hexadecyl-9h-fluorene Chemical compound C1=CC=C2C(CCCCCCCCCCCCCCCC)C3=CC=CC=C3C2=C1 MIHYKOZJQMWHCQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000219112 Cucumis Species 0.000 description 2
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 229950005228 bromoform Drugs 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HFVIYAZBVIGNAN-UHFFFAOYSA-N 1,1-dibromodecane Chemical compound CCCCCCCCCC(Br)Br HFVIYAZBVIGNAN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 101000685083 Centruroides infamatus Beta-toxin Cii1 Proteins 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910019785 NBF4 Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- CURUTKGFNZGFSE-UHFFFAOYSA-N dicyclomine Chemical group C1CCCCC1C1(C(=O)OCCN(CC)CC)CCCCC1 CURUTKGFNZGFSE-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【発明の詳細な説明】
［ａ業上の利用分野］
本発明は導電性を有するとともに戊形加工性のよい新規
なポリフェニレン系重合体およびその製造法に関するも
のである。本発明により得られる新規なボリフェニレン
系重合体は電気的信号等により色，電導度を変化させる
ことができるため、？気・電子機器分野等における表示
材料としで用いることができる。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel polyphenylene polymer that is electrically conductive and has good moldability, and a method for producing the same. The novel polyphenylene polymer obtained by the present invention can change its color and conductivity by electrical signals, etc. It can be used as a display material in the fields of air and electronic equipment, etc.
［従来の技術及び発明が解決しようとする課題ゴ主鎮に
芳香環が連なったボリフエニレン系重合体はポリアセチ
レン，ポリチオフエンと並び、導電性高分子として知ら
れており、５フッ化ヒ素ドープにより導電率１０”〜Ｉ
Ｑ’ｓ／ｃｍを示す。[Problems to be solved by the prior art and the invention Polyphenylene polymers in which aromatic rings are linked to the main chain are known as conductive polymers, along with polyacetylene and polythiophene, and doping with arsenic pentafluoride increases conductivity. 10”~I
Indicates Q's/cm.
このポリフェニレン系瓜合体については、フリーデルタ
ラフト触媒（ Ａｉ’Ｃｉ’ａ−ＣｕＣＪｌ■なと）に
よりベンゼンを直接酸化重合することにより、不溶不融
な赤褐色粉末として得られることが報告されている（Ｋ
ｏｖａｃｉｃら． Ｊ． Ａｍ． Ｃｈｅｗ． Ｓｃｉ
．， ８５， ４５４（１９５：］））。It has been reported that this polyphenylene-based melon agglomerate can be obtained as an insoluble, infusible reddish-brown powder by direct oxidation polymerization of benzene using a Friedelta raft catalyst (Ai'Ci'a-CuCJl) ( K
Ovacic et al. J. Am. Chew. Sci
．． , 85, 454 (195:])).
また、ベンゼンを特定の電解質を用いて電解酸化重合す
ると陽極上にフィルムが生成し、高い導電率（１０’Ｓ
／Ｃｍ程度）を示すことも知られている（佐藤ら， Ｊ
． Ｃｈｅｍ． Ｓｏｃ． Ｃｈｅｍ． Ｃｏｍｍｕｎ
．． １６２９（１９８５））。Furthermore, when benzene is electrolytically oxidized and polymerized using a specific electrolyte, a film is formed on the anode and has a high electrical conductivity (10'S
/Cm) (Sato et al., J
．． Chem. Soc. Chem. Commun
．． ．． 1629 (1985)).
しかしながら、この方法で得られるボリフエニレン系重
合体も溶剤に不溶であり、しかも熱的に不融であるとい
う欠点がある。これら従来の方法によって得られる重合
体は、いずれも溶剤への可溶性，熱可塑性を有していな
いため、その成形加工が困難であり、導電性高分子材料
の応用開発の大きな障害となっていた。However, the polyphenylene polymer obtained by this method also has the disadvantage of being insoluble in solvents and thermally infusible. None of the polymers obtained by these conventional methods have solubility in solvents or thermoplasticity, making it difficult to mold them, which has been a major obstacle in the development of applications for conductive polymer materials. .
［課題を解決するための手段］
本発明者らは上記従来の問題点を解消し、導電性を有す
るとともに威形加工性のよい重合体を得るため鋭意研究
を瓜ねた。その結果、特定の構造を有するフルオレン誘
導体を化学的酸化重合または電気化学的酸化重合するこ
とにより、導電性を有し、かつ成形加工性のよい新規な
ポリフェニレン系重合体を見出すに至った。[Means for Solving the Problems] The present inventors have conducted extensive research in order to solve the above-mentioned conventional problems and to obtain a polymer that has electrical conductivity and good formability. As a result, by chemically oxidatively polymerizing or electrochemically oxidizing a fluorene derivative having a specific structure, we have discovered a novel polyphenylene polymer that is electrically conductive and has good moldability.
すなわち本発明は、
一般式
［式中、Ｒｌ， Ｒ２は水素原子または炭素数１〜３０
のアルキル基，シクロアルキル基を示し、Ｒｌ， Ｒ２
は同じものであっても異なったものでもよい。また、ｎ
は１以上の実数である。］
で表わされる繰り返し単位を有し、かつ、重量平均分子
量が３，０００以上であるポリフエニレン系重合体を提
供するとともに、
一般式
［式中、Ｒ’， Ｒ２． ｎは前記と同じ］で表わされ
るフルオレン誘導体を化学的酸化重合または電気化学的
酸化重合することを特徴とする、上記の新規なボリフエ
ニレン系重合体の製造冫去を提イ共するものである。That is, the present invention is based on the general formula [wherein Rl, R2 are hydrogen atoms or have 1 to 30 carbon atoms]
represents an alkyl group, a cycloalkyl group, Rl, R2
may be the same or different. Also, n
is a real number greater than or equal to 1. ] It provides a polyphenylene polymer having a repeating unit represented by the following and a weight average molecular weight of 3,000 or more, and having the general formula [wherein R', R2. The present invention also proposes the production of the above-mentioned novel polyphenylene polymer, which is characterized by subjecting a fluorene derivative represented by the above formula to chemical oxidative polymerization or electrochemical oxidative polymerization.
本発明の新規ポリフェニレン系重合体は、上記一般式ク
！）で表わされる繰り返し単位を有するものであるが、
この繰り返し単位の配列に関しては、重合条件によって
異なり、三次元的に架橋した網目構造を有する重合体を
形成することもできる。上記一般式（１）において、ｎ
１、 Ｒ２は水素原子または炭素数１〜３０のアルキル
基，シクロアルキル基を示しており、アルキル基として
具体的にはメチル基，エチル基．プロビル基，ブチル基
，ベンチル基．ヘキシル基，ヘブチル基．オクチル基．
ノニル基．デシル基．ウンデシル基．ドデシル基，ヘキ
サデシル基．ドコシル基．シクロヘキシル基などが挙げ
られ、とりわけ炭素数５以上のアルキル基が好ましい。The novel polyphenylene polymer of the present invention has the above general formula K! ) has a repeating unit represented by
The arrangement of the repeating units varies depending on the polymerization conditions, and it is also possible to form a polymer having a three-dimensionally crosslinked network structure. In the general formula (1) above, n
1. R2 represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or a cycloalkyl group, and specific examples of the alkyl group include a methyl group and an ethyl group. Probyl group, butyl group, bentyl group. Hexyl group, hebutyl group. Octyl group.
Nonyl group. Decyl group. Undecyl group. Dodecyl group, hexadecyl group. docosyl group. Examples include a cyclohexyl group, and an alkyl group having 5 or more carbon atoms is particularly preferred.
なお、上記Ｒ’． Ｒ”ＩＣおいてアルキル基としては
、直鎖状．分岐状，′５Ｍ状いずれの構造のものであっ
てもよい．
また ３１． Ｒ２は同じものであっても、あるいは異
なったものであってもよい。さらに本発明のポリフェニ
レン系重合体は、ｉｎ平均分子量が３．０００以上であ
るものが有用性が高い．ｌｉ量平均分子量が３，０００
未満では熱的性買，＄！１械的性質がともに十分でない
。Note that the above R'. The alkyl group in R"IC may have a linear, branched, or '5M structure. Also, 31. R2 may be the same or different. Furthermore, the polyphenylene polymer of the present invention is highly useful if it has an in average molecular weight of 3,000 or more.
Hot sex purchase for less than $! Both mechanical properties are insufficient.
ざらにｎは１以上の実数、好ましくは１〜３０の実数で
ある。Generally, n is a real number of 1 or more, preferably a real number of 1 to 30.
以上の如き本発明の新規ポリフェニレン系重合体は、具
体的には例えば、
などの構成単位を有するものである。Specifically, the novel polyphenylene polymer of the present invention as described above has, for example, the following structural units.
本発明の新規ポリフェニレン系重合体は、例えば以下の
如くして製造することができる。The novel polyphenylene polymer of the present invention can be produced, for example, as follows.
すなわち、原料物質として前記一般式（ Ｉ１ ）で表
わされるフル才レン誘導体を用い、このものを化学的酸
化重合または電気化学的酸化重合することにより、前記
一般式（１）で表わされる繰り返し単位を有する新規な
ボソフエニレン系重合体を製造することができる。That is, the repeating unit represented by the general formula (1) can be obtained by chemically oxidatively polymerizing or electrochemically oxidizingly polymerizing the full polymer derivative represented by the general formula (I1) as a raw material. It is possible to produce a novel bosophenylene polymer having the following properties.
前記一般式（■！）において、Ｒ’， Ｒ２， ｎは
前記一般式（ｒ）における説明中で記穀した通りである
。In the general formula (■!), R', R2, and n are as described in the description of the general formula (r).
このような前記一般式（１１）で表わされるフルオレン
誘導体は、例えば次の如くして得ることができる。Such a fluorene derivative represented by the general formula (11) can be obtained, for example, as follows.
まずフルオレンを室温にてアルゴン雰囲気下、攪拌しな
がら次の式のような反応により下記一般式（ ＩＩＩ
）で表わされる化合物（フルオレンモノアルキル体）を
得る．
Ｌｉ
この場合フルオレンとＢｕＬｉ （ ｎ−ブチルリチウ
ム）との配合割合（モル比、以下同様）は前者／後者！
１．０〜０．５、好ましくは０．９〜０．７５であり、
１〜２時間攪拌（反応）を行なう。First, fluorene is reacted with the following formula while stirring under an argon atmosphere at room temperature to form the following general formula (III
) to obtain a compound (fluorene monoalkyl compound). Li In this case, the blending ratio (molar ratio, same below) of fluorene and BuLi (n-butyllithium) is former/latter!
1.0 to 0.5, preferably 0.9 to 0.75,
Stirring (reaction) is performed for 1 to 2 hours.
また、リチウムフルオレンに加えるＲ’Ｂｒ （ ｎ
−プロムアルキル）の配合割合は前者／後者＝ １．０
〜０．５、好ましくは０．９〜０，７５であり、３〜１
０時間攪拌（反応）を行なうことによりモノアルキル体
を得ることができる。なお、Ｒ′は前記と同様である．
次に、上記一般式（ ＩＩ１ ）で表わされる化合物（
フルオレンモノアルキル体）を次の式のような反応によ
り下記一般式（ ＩＶ ）で表わされる化合物（フル才
レンアルキルブロモ体）を得る。In addition, R'Br ( n
- promalkyl) blending ratio is former/latter = 1.0
~0.5, preferably 0.9-0.75, and 3-1
A monoalkyl compound can be obtained by stirring (reacting) for 0 hours. Note that R' is the same as above. Next, a compound represented by the above general formula (II1) (
A compound (fluorene monoalkyl bromo) represented by the following general formula (IV) is obtained by reacting the fluorene monoalkyl (fluorene monoalkyl) as shown in the following formula.
様である。It's like that.
一方、上記一般式（ ＩＩ！ ）で表わされる化合物（
フルオレンモノアルキル体）の合成と同様にして次の式
のような反応により下記一般式（Ｖ）で表わされる化合
物（フルオレンモノアルキル体）を得る。On the other hand, the compound represented by the above general formula (II!) (
A compound (fluorene monoalkyl compound) represented by the following general formula (V) is obtained by the reaction shown in the following formula in the same manner as in the synthesis of the fluorene monoalkyl compound (fluorene monoalkyl compound).
］ １
この場合、上記一般式（ ！ＩＴ ）で表わされる化合
物（フルオレンモノアルキル体）とＢｕＬｉの配合割合
は、前者／後者＝１．０〜０，５、好ましくは０．９〜
０．７５であり、中間生成物（リチウムモノアルキル体
）とＢｒ （ＣＨ２） ．Ｂｒの配合割合は１．０ 〜
０．５、好ましくは０．９〜０．７５であり、攪拌（反
応）時間は、上記一般式（ Ｕｔ ）で表わされる化合
物（フルオレンモノアルキル体）を得た場合と同次に上
記一般式（Ｖ）で表わされる化合物（フルオレンモノア
ルキル体）にＢｕＬｉを加え、攪拌（反応）して下記一
般式（Ｖｌ）で表わされる化合物（リチウムモノアルキ
ル体）を得る。] 1 In this case, the compounding ratio of the compound represented by the above general formula (!IT) (fluorene monoalkyl form) and BuLi is former/latter = 1.0 to 0.5, preferably 0.9 to 0.5.
0.75, and the intermediate product (lithium monoalkyl form) and Br (CH2) . The blending ratio of Br is 1.0 ~
0.5, preferably 0.9 to 0.75, and the stirring (reaction) time is the same as when the compound (fluorene monoalkyl compound) represented by the above general formula (Ut) is obtained. BuLi is added to the compound represented by (V) (fluorene monoalkyl form) and stirred (reacted) to obtain a compound (lithium monoalkyl form) represented by the following general formula (Vl).
（Ｖ）
この場合、上記一般式（Ｖ）で表わされる化合物（フル
オレンモノアルキル体）とＢｕＬｌの配合割合は前者／
後者＝１．０〜０．５、好ましくは０．９〜０．７５で
あり、攪拌（反応）時間は、上記一般式（川）で表わさ
れる化合物（フルオレンモノアルキル体）を得た場合と
同様である。(V) In this case, the compounding ratio of the compound represented by the above general formula (V) (fluorene monoalkyl form) and BuLl is the former/
The latter = 1.0 to 0.5, preferably 0.9 to 0.75, and the stirring (reaction) time is the same as when obtaining the compound (fluorene monoalkyl form) represented by the above general formula (Kawa). The same is true.
そして上記一般式（Ｖｌ）で表わされる化合物（リチウ
ムモノアルキル体）に、上記一般式（ ＩＶ ）で表わ
される化合物（フルオレンアルキルブロモ体）を次のよ
うに反応させて、目的とする、前記一般式（ Ｉ１ ）
で表わされるフルオレン誘導体を得ることができる。Then, the compound represented by the above general formula (Vl) (lithium monoalkyl form) is reacted with the compound represented by the above general formula (IV) (fluorene alkyl bromo form) as follows to obtain the desired general Formula (I1)
A fluorene derivative represented by can be obtained.
この場合、上記一般式（ Ｖｌ ）で表わされる化合物
（リチウムモノアルキル体）と、一般式（ＩＶ）で表わ
される化合物（フルオレンアルキルブロモ体）との配合
割合は、前者／後者−１，０〜０。５、好ましくは０．
９〜０．７５であり、攪拌（反応）時間は３〜１０時間
である。In this case, the compounding ratio of the compound represented by the above general formula (Vl) (lithium monoalkyl form) and the compound represented by general formula (IV) (fluorene alkyl bromo form) is from -1,0 to -1,0 for the former/latter. 0.5, preferably 0.5.
9 to 0.75, and the stirring (reaction) time is 3 to 10 hours.
式（！Ｉ）で表わされるフルオレン誘導体のＲｌと８２
が同一である場合には、下記のごとく、フルオレンのリ
チウム・モノアルキル体に０．５当量のジブロムアルカ
ンを加えて合成すればよい．（ Ｖｌ ）
この場合のフルオレンのリチウム・モノアルキル体とジ
ブロムアルカンの配合割合は、前者／後（ ＩＩ ）
者＝３．０〜２．０、好ましくは２．５〜２．１である
。Rl and 82 of the fluorene derivative represented by formula (!I)
If they are the same, they can be synthesized by adding 0.5 equivalent of dibromoalkane to the lithium monoalkyl form of fluorene as shown below. (Vl) In this case, the blending ratio of the lithium monoalkyl form of fluorene and dibromoalkane is former/latter (II) = 3.0 to 2.0, preferably 2.5 to 2.1.
本発明においては、例えば上記の如くして得られる一般
式（！Ｉ）で表わされるフルオレン誘導体を用い、この
ものについて化学的酸化重合または電気化学的酸化重合
を行なう。これにより最終的な目的生成物である前記一
般式（１）で表わされる繰り返し単位を有する新規なボ
リフェニレン系重合体を製造することができる。In the present invention, for example, a fluorene derivative represented by the general formula (!I) obtained as described above is used and subjected to chemical oxidative polymerization or electrochemical oxidative polymerization. As a result, a new polyphenylene polymer having a repeating unit represented by the general formula (1), which is the final target product, can be produced.
ここで化学的酸化重合は、酸化剤を重合触媒として用い
る方法である。このような酸化剤としてはＦｅＣｊ３，
ＭｏＣｉ！ｓ． ＷＣｊ！ａなど酸化剤単独であって
もよいが、＾ＲＣ１１３−ＣｕＣＲ２，＾ｉ’Ｃｉ３−
ＭｎＯｚなどルイス酸と組合せたものを用いてもよい。Here, chemical oxidative polymerization is a method using an oxidizing agent as a polymerization catalyst. Such oxidizing agents include FeCj3,
MoCi! s. WCj! An oxidizing agent such as a may be used alone, but ^RC113-CuCR2, ^i'Ci3-
A combination with a Lewis acid such as MnOz may also be used.
これらの酸化剤（触媒）をクロロホルム．塩化メチレン
などのハロゲン系溶媒に分敗させ、これに、上記一般式
（Ｉ＋）で表わされる化合物を加え、アルゴン雰囲気下
、温度０〜１００℃、好ましくは２０〜５０℃で、５〜
２００時間、好ましくはｌＯ〜１００時間攪拌して重合
反応を行なう。反応の進行にともなって、溶液の流動性
が低下し、弾性が現われるが、このような流動性が消失
する前に反応を停止し、反応液をメタノール中に注入し
て、重合体を冫戸別回収する。重合体はさらにクロロホ
ルムなどを用いて精製することが好ましい。These oxidizing agents (catalysts) are chloroform. A halogenated solvent such as methylene chloride is added thereto, and a compound represented by the above general formula (I+) is added thereto.
The polymerization reaction is carried out by stirring for 200 hours, preferably 10 to 100 hours. As the reaction progresses, the fluidity of the solution decreases and elasticity appears, but the reaction is stopped before such fluidity disappears, and the reaction solution is poured into methanol to separate the polymer. to recover. Preferably, the polymer is further purified using chloroform or the like.
一方、反応溶液が流動性を失い、弾性が現われるまで反
応を続けることにより、三次元的に架橋したゲル状の重
合体が得られる。On the other hand, by continuing the reaction until the reaction solution loses fluidity and exhibits elasticity, a three-dimensionally crosslinked gel-like polymer can be obtained.
このようにして得られたゲルを、メタノール，水などに
投入して重合物を洗浄，炉別する。さらに、この重合物
を再度クロロホルムなどで膨潤させた後、メタノールな
どに投入して洗浄．炉別し乾燥させることにより、精製
された架橋化重合体を得ることができる。The gel thus obtained is poured into methanol, water, etc., and the polymer is washed and separated in a furnace. Furthermore, after swelling this polymer again with chloroform etc., it is poured into methanol etc. and washed. A purified crosslinked polymer can be obtained by oven separation and drying.
なお、上記反応の中間段階では、クロロホルムなどの溶
媒に可溶な重合体と、ゲル状の重合体の両者の混合物が
得られるが、この場合には、クロロホルムなどの溶媒を
用いてソックスレー抽出することによって両者を分離す
ることができる。In addition, in the intermediate stage of the above reaction, a mixture of both a polymer soluble in a solvent such as chloroform and a gel-like polymer is obtained, but in this case, Soxhlet extraction is performed using a solvent such as chloroform. This allows the two to be separated.
一方、電気化学的酸化重合は、上記一般式（ＴＩ）で表
わされる化合物と電解質を溶媒に溶かした電解質液中に
、１対の電極（Ｎｉ， Ｐｔなど）を浸漬し、このｔ極
間に電圧（３〜２０Ｖ）を印加し、通電することにより
行なわれ、陽極表面に重合体が生戊する。On the other hand, in electrochemical oxidative polymerization, a pair of electrodes (Ni, Pt, etc.) is immersed in an electrolyte solution in which the compound represented by the above general formula (TI) and an electrolyte are dissolved in a solvent, and a This is carried out by applying a voltage (3 to 20 V) and energizing, and a polymer is formed on the surface of the anode.
ここで用いる電解貿としては種々のものが用いられるが
例えばＬＩＢＦ４， ＬＩＡＳＦ８， ＬＩＣｉ’０４
，（ｎ−Ｂｕ）４”ＮＢＦ４． （Ｅｔ）ＪＣ１０４な
どが挙げられ、特にＬｉＢＦ４，ＬｉＣｊＯ．が好まし
い。また、溶媒としてはアセトニトリル，ペンゾニトリ
ル，プロピレンカーボネート．ジメチルスルホキシド，
ニトロメタンなどを用いることができる。Various types of electrolytic trade are used here, such as LIBF4, LIASF8, and LICi'04.
, (n-Bu)4''NBF4. (Et)JC104, etc., and LiBF4, LiCjO. are particularly preferred. Also, as a solvent, acetonitrile, penzonitrile, propylene carbonate, dimethyl sulfoxide,
Nitromethane and the like can be used.
叙上のようにして陽極表面に連続的に生戒する重合体は
電解槽に沈殿する。この沈殿物を枦別．洗浄して本発明
のボリフェニレン系重合体を得ることができる。As described above, the polymer continuously deposited on the anode surface is precipitated in the electrolytic cell. Separate this precipitate. The polyphenylene polymer of the present invention can be obtained by washing.
このようにして得られる重合体は、フルオレン環の酸化
反応に対する活性が高いとされている２．７位［ Ｒ．
Ｊ．Ｗａｌｔｍａｎら， Ｊ．Ｅ１ｅｃｔｒｏａｎａ１
、ＣｈｅｏＩ．， １９４． ４９（１９８５）］での
結合が主成分をなしていると考えられるが、酸化反応の
進行にともなって、２．７位以外の部位での架橋反応が
進行し、三次元的な網目構造を有する架橋重合体が得ら
れると考えられる。The polymer obtained in this manner has the fluorene ring at the 2.7-position [R.
J. Waltman et al., J. E1 electroana1
, CheoI. , 194. 49 (1985)] is considered to be the main component, but as the oxidation reaction progresses, crosslinking reactions at sites other than the 2.7-position progress, forming a three-dimensional network structure. It is considered that a crosslinked polymer having the following properties can be obtained.
［実施例］ 次に、本発明を実施例により詳しく説明する。[Example] Next, the present invention will be explained in detail with reference to examples.
実施例１
（１） １．１０−ビス（９′−ヘキサデシルフルオレ
ニル）デカンの合成
フルオレン８．３ｇをエーテルに溶かし、ｎ−プチルリ
チウム（１５％へキチン溶液） ３０＋ｍ２を加え、ア
ルゴン雰囲気下、１時間攪拌した。その後、ｎ−プロモ
ヘキサデカン１８ｇを滴下し、さらに４時間攪拌した。Example 1 (1) Synthesis of 1.10-bis(9'-hexadecylfluorenyl)decane 8.3 g of fluorene was dissolved in ether, 30+m2 of n-butyllithium (15% hechitin solution) was added, and an argon atmosphere was added. The mixture was stirred for 1 hour. Then, 18 g of n-promohexadecane was added dropwise, and the mixture was further stirred for 4 hours.
ヘキサンにより再結晶し、９−ヘキサデシルフルオレン
１６ｇを得た，，９−ヘキサデシルフルオレン２４ｇを
エーテルに溶かし、ｎ−ブチルリチウム３６ｍ！ｌを加
え、アルゴン雰囲気下、１時間攪拌した。その一後、ジ
ブロモデカン８，８ｇを滴下し、さらに４時間攪拌した
。ヘキサンにより再結晶し、次式で示される１．１０−
ビス（９′ヘキサデシルフルオレニル）デカン５．１ｇ
を得た。Recrystallization from hexane yielded 16 g of 9-hexadecylfluorene.24 g of 9-hexadecylfluorene was dissolved in ether, and 36 m of n-butyllithium was obtained. 1 was added, and the mixture was stirred for 1 hour under an argon atmosphere. After that, 8.8 g of dibromodecane was added dropwise, and the mixture was further stirred for 4 hours. Recrystallized from hexane, 1.10-
Bis(9'hexadecylfluorenyl)decane 5.1g
I got it.
（２） １．１０−ビス（９′−ヘキサデシルフルオレ
ニル）デカン重合体の合或［化学的酸化重合法〕クロロ
ホルム１００ｍｉ’中に塩化第二鉄５．７ｇと上記（１
）で得られた１．１０−ビス（９′−ヘキサデシルフル
オレニル）デカン４ｇを入れ、室温にて１０時間攪拌し
た。反応液の流動性が増大する直前に反応を停止し、反
応液を大量のメタノール中に注入して重合体を炉別回収
した。この重合体は、再度クロロホルムに溶解し、メタ
ノール中に注入して精製された重合体３．８ｇを得た。(2) 1. Coordination of 10-bis(9'-hexadecylfluorenyl)decane polymer [Chemical oxidative polymerization method] 5.7 g of ferric chloride and the above (1
4 g of 1.10-bis(9'-hexadecylfluorenyl)decane obtained in ) was added, and the mixture was stirred at room temperature for 10 hours. The reaction was stopped just before the fluidity of the reaction solution increased, the reaction solution was poured into a large amount of methanol, and the polymer was recovered by furnace. This polymer was again dissolved in chloroform and poured into methanol to obtain 3.8 g of purified polymer.
さらに、この重合体をクロロホルムを溶媒とするソック
スレー抽出を行ない、ゲル戒分を完全に除去した重合体
３．５ｇを得た。Furthermore, this polymer was subjected to Soxhlet extraction using chloroform as a solvent to obtain 3.5 g of a polymer from which gel components had been completely removed.
ここで得られた重合体の核磁気共鳴スペクトルを第ｌ図
（ ”Ｃ−ＮＭＲ） ．および第２図（’Ｈ−ＮＭＲ）
に、また赤外線吸収スペクトルを第３図に示す．これら
測定結果より、この重合体は、千ノマー単位あたりベン
ゼン環水素４個が脱離していることが認められ、下記の
繰り返し単位を有するものと認められた。The nuclear magnetic resonance spectra of the polymer obtained here are shown in Figure 1 ('C-NMR) and Figure 2 ('H-NMR).
Figure 3 also shows the infrared absorption spectrum. From these measurement results, it was found that this polymer had 4 benzene ring hydrogen atoms removed per 1,000 nomer unit, and was found to have the following repeating units.
また、この重合体についてゲルバーミエション・クロマ
トグラフィーはよる分子量を測定したところ、重量平均
分子量が１１０，０００であり、数平均分子量は３２，
０００であった。さらに、元素分析結果は、炭素：水素
ズ８８．２ ： １０．５ ［理論値は８９．３ ：１
０．７］であった。In addition, when the molecular weight of this polymer was measured using gel vermiaction chromatography, the weight average molecular weight was 110,000, and the number average molecular weight was 32,000.
It was 000. Furthermore, the elemental analysis results show that carbon:hydrogen is 88.2:10.5 [theoretical value is 89.3:1]
0.7].
また、この重合体は、クロロホルム．塩化メチレンなど
に可溶であり、水．メタノールに不溶である。この重合
体のクロロホルム溶液からキャスティングフィルムが得
られ、このフィルムは６０℃付近で溶融軟化した。また
、このフィルムの室温における電導度は１０−”Ｓ／ｃ
ｍ以下であるが、ヨウ素によりドーブすることによって
、１０−’Ｓ／ｃｍに向上した。さらに、このフィルム
をホウフッ化リチウムープロピレンカーボネート電解液
中で電気的にドーブすると、ドーブ前の黄色のフィルム
が紫色に変化し、脱ドーブすると再び黄色に戻った。In addition, this polymer can be used in chloroform. It is soluble in methylene chloride, etc., and water. Insoluble in methanol. A cast film was obtained from a chloroform solution of this polymer, and this film melted and softened at around 60°C. Also, the electrical conductivity of this film at room temperature is 10-”S/c
m or less, but it was improved to 10-'S/cm by doping with iodine. Furthermore, when this film was electrically doped in a lithium borofluoride-propylene carbonate electrolyte, the yellow film before doping turned purple, and after dedoping, it returned to yellow again.
また、このドーブの直後、空気中にフィルムを取出して
７ＦＬ導度を測定したところ、１０−’Ｓ／ｃｍであっ
た。Immediately after this dove, the film was taken out into the air and the 7FL conductivity was measured, and it was found to be 10-'S/cm.
実施例２
＋１） １．１０−ビス（９′−ヘキサデシルフルオレ
ニル）デカンの合戊
実施例１の（１）と同様にした。Example 2 +1) 1. Synthesis of 10-bis(9'-hexadecylfluorenyl)decane The same procedure as in Example 1 (1) was carried out.
（２） １，１０−ビス（９′−ヘキサデシルフルオレ
ニル）デカンの三次元重合体の合成
クロロホルム ｌｏｏｍｉｌ中に、塩化第二鉄５．７ｇ
と１．１０−ビス（９′−ヘキサデシルフルオレニル）
デカン４ｇを入れ、室温にて７０時間攪拌した。攪拌の
途中より溶液の流動性が消失し、弾性が現われ、ゲル状
の重合体の生成が確認ざれた。生成物を大量のメタノー
ルで洗浄し、クロロホルムで膨潤させたのち、メタノー
ルを投入して洗浄し、ｌ２時間乾燥して粉末状の瓜合体
３、８ｇを得た。ついで、この重合体より、クロロホル
ムを溶媒とするソックスレー抽出により、クロロホルム
可溶分を除去し、ゲル状重合体３．４ｇを得た。この重
合体の元素分析値は、炭素二水素＝ ８８．４ ７ １
１。Ｏであり、モノマー単位あたり、５個以上の水素が
脱離し、その部位が架橋化反応に関与しているものと認
められる。(2) Synthesis of three-dimensional polymer of 1,10-bis(9'-hexadecylfluorenyl)decane In chloroform loomil, 5.7 g of ferric chloride
and 1.10-bis(9'-hexadecylfluorenyl)
4 g of decane was added and stirred at room temperature for 70 hours. During stirring, the fluidity of the solution disappeared, elasticity appeared, and the formation of a gel-like polymer was confirmed. The product was washed with a large amount of methanol, swollen with chloroform, washed with methanol, and dried for 12 hours to obtain 3.8 g of powdered melon. Next, chloroform-soluble components were removed from this polymer by Soxhlet extraction using chloroform as a solvent, to obtain 3.4 g of a gel-like polymer. The elemental analysis value of this polymer is carbon dihydrogen = 88.4 7 1
1. O, and it is recognized that five or more hydrogens are eliminated per monomer unit, and that site is involved in the crosslinking reaction.
つぎに、この重合体をクロロホルムとエタノールの配合
割合を変化させた混合液と接触し、重合体の体積変化を
測定した。その結果を第４図に示す。なお、第４図中、
エタノール濃度（％）はで示されるものであり、ｖ０は
クロロホルム中での体積を示す。第４図より、エタノー
ル中でのこの重合体の体積は、クロロホルム中での体積
のｌ／ｌＯとなることがわかる。また、クロロホルム中
での重合体の体積を、温度を変えて測定した結果を第５
図に示す。なお、第５図中、ＶＯは室温中での体積を示
す。第５図より、−２０℃程度の温度より収縮が始まり
、−６０℃においては、室温での体積の７０％になるこ
とがわかる。Next, this polymer was brought into contact with a mixture of chloroform and ethanol in varying proportions, and changes in the volume of the polymer were measured. The results are shown in FIG. In addition, in Figure 4,
The ethanol concentration (%) is indicated by , and v0 indicates the volume in chloroform. From FIG. 4, it can be seen that the volume of this polymer in ethanol is 1/1O of the volume in chloroform. In addition, the results of measuring the volume of the polymer in chloroform at different temperatures are shown in the fifth section.
As shown in the figure. In addition, in FIG. 5, VO indicates the volume at room temperature. From FIG. 5, it can be seen that shrinkage begins at a temperature of about -20°C, and at -60°C, the volume becomes 70% of the volume at room temperature.
また、この重合体をクロロホルムにて膨潤させ、半ば乾
燥したところでプレスし、フィルムを得た。このフィル
ムの導電率を四端子法にて測定すると１０−”Ｓ／ｃｍ
であった。これを気相にてヨウ素ドーブしたところ導電
率は１０−’Ｓ／ｃｍまで増加した。また、このフィル
ムをホウフツ化リチウムーブロビレンカーボネート電解
液中で電気化学的Ｃドーピングを行なうとドーブ前黄色
のフイルムが黒褐色へと変化した。上記のようにドーブ
した直後、空気中にフィルムを取り出し、導電率を測定
すると１０−’Ｓ／ｃｍであった。Further, this polymer was swollen with chloroform, and when half-dried, it was pressed to obtain a film. The conductivity of this film was measured using the four-terminal method and was 10-”S/cm.
Met. When this was doped with iodine in the gas phase, the conductivity increased to 10-'S/cm. Furthermore, when this film was electrochemically doped with C in a lithium borofluoride-brobylene carbonate electrolyte, the yellow film before doping changed to blackish brown. Immediately after doping as described above, the film was taken out into the air and its conductivity was measured to be 10-'S/cm.
実施例３［電気化学的酸化重合法］
実施例１（ｌ）で得られた１．１０−ビス（９′−ヘキ
サデシルフルオレニル）デカン １．５ｇとホウフッ化
リチウム０，５ｇをペンゾニトリル５０ｍｌに溶かした
。これに１対のＮｉ電極を浸漬し、電極間に７ｖの電圧
を印加したところ陽極板上に重合物が析出した。得られ
た重合体をクロロホルムを溶媒とするソックスレー抽出
をおこない、クロロホルム可溶重合体０．１ｇ，ゲル戊
分０．３ｇを得た。これらのうち、前者は、”Ｃ−ＮＭ
Ｒ， ’｝ｌ−ＮＭＲ ，赤外線吸収スペクトル，元素
分析結果が、実施例１の重合体と同様であり、重量平均
分子量が１５，０００の重合体であった。また、後者は
実施例２の重合体と同様のものであった．
実施例４〜８
実施例１において、１．１０−ビス（９′−ヘキサデシ
ルフルオレニル）デカンの代わりに、下記に示す一般式
（Ｖ′）中のＲ’， Ｒ２， Ｘが第１表中に示すもの
であるモノマーを用いて実施例１と同様に重合を行なっ
た。結果を第１表に示す。Example 3 [Electrochemical oxidative polymerization method] 1.5 g of 1.10-bis(9'-hexadecylfluorenyl)decane obtained in Example 1 (l) and 0.5 g of lithium borofluoride were added to 50 ml of benzonitrile. It was dissolved in When a pair of Ni electrodes was immersed in this and a voltage of 7 V was applied between the electrodes, a polymer was deposited on the anode plate. The obtained polymer was subjected to Soxhlet extraction using chloroform as a solvent to obtain 0.1 g of a chloroform-soluble polymer and 0.3 g of a gel fraction. Among these, the former is “C-NM
The R,'}l-NMR, infrared absorption spectrum, and elemental analysis results were the same as those of the polymer of Example 1, and the polymer had a weight average molecular weight of 15,000. Moreover, the latter was similar to the polymer of Example 2. Examples 4 to 8 In Example 1, in place of 1.10-bis(9'-hexadecylfluorenyl)decane, R', R2, and Polymerization was carried out in the same manner as in Example 1 using the monomers shown in the table. The results are shown in Table 1.
第１表
シルフルオレニル）デカンの代わりに、−１ｉＱ式（Ｖ
′）中のＲ’， Ｒ”， Ｘが第２表中に示すものであ
るモノマーを用いて、実施例２と同様に重合を行なった
。結果を第２表に示す。-1iQ formula (V
Polymerization was carried out in the same manner as in Example 2 using monomers in which R', R", and X in ') are shown in Table 2. The results are shown in Table 2.
第２表
実施例９〜ｌ３
実施例２における１，ｔｏ−ビス（９′−ヘキサデ［発
明の効果］
本発明の新規なポリフェニレン系重合体は成形加工性が
よく、かつ導電性を有する上に、ドーピングにより色，
電導度を変化させることができるので、光学的一電子的
機能材料として用いることができる。Table 2 Examples 9 to 13 1,to-bis(9'-hexade in Example 2 [Effects of the invention] The novel polyphenylene polymer of the present invention has good moldability and conductivity. , color due to doping,
Since the electrical conductivity can be changed, it can be used as an optically and electronically functional material.
さらに詳しく述べると、本発明の新規ポリフェニレン系
重合体はポリアセチレン．ポリチオフェン等と同様に導
電性を有する。例えば、本発明の１．１０−ビス（９′
−ヘキサデシルフルオレニル）デカン重合体の場合には
、電導度は１０−”Ｓ／ｃＩＩ１程度であるが、これに
ヨウ素をドープした場合には電導度を１０−’Ｓ／ｃｍ
とすることができる。また、電気化学的にＬｉＢＦ４を
ドープすることによって，電卓度を１０−’Ｓ／ｃｍと
することができる。More specifically, the novel polyphenylene polymer of the present invention is polyacetylene. It has electrical conductivity like polythiophene. For example, the 1,10-bis(9′) of the present invention
-Hexadecylfluorenyl)decane polymer has an electrical conductivity of about 10-'S/cII1, but when it is doped with iodine, the electrical conductivity increases to 10-'S/cm.
It can be done. Further, by electrochemically doping LiBF4, the degree of calculation can be set to 10-'S/cm.
また、上記ドーピングの際に色変化が生じたり、電導度
が変化するために、この性質を利用して表示材料として
用いることも可能である。Furthermore, since color changes and electrical conductivity change during the doping process, it is also possible to use these properties as display materials.
さらに、上記ドーピングの際または液状の媒体の種類に
よりゲルの体積が変化するため、化学エネルギーを機械
的仕事に変換するアクチェータとしての利用が可能であ
る。Furthermore, since the volume of the gel changes during the doping process or depending on the type of liquid medium, it can be used as an actuator that converts chemical energy into mechanical work.
したがって、本発明のポリフェニレン系重合体は、導電
性材料１表示材料，メカノケよカル材料などとして産業
上多分野で有益に用いることができる。Therefore, the polyphenylene polymer of the present invention can be usefully used in various industrial fields, such as conductive materials, display materials, and mechanical materials.
また、本発明の製造法を用いれば、上記の如き新規なポ
リフェニレン系重合体を純粋に効率良く、しかも容易に
製造することができ、産業上極めて有為な方法である。Further, by using the production method of the present invention, the above-mentioned novel polyphenylene polymer can be produced purely efficiently and easily, and it is an extremely useful method in industry.
第１図は本発明の実施例１で得られた１合体の核磁気共
Ｄｉ （ １３Ｃ−ＮＭＲ）スペクトルを示すものであ
り、第２図は同じく実施例１で得られた重合体の核磁気
共鳴（’Ｈ−ＮＭＲ）スペクトルを示すものであり、第
３図は同じく実施例ｌで得られた重合体の赤外線吸収（
ＩＲ）スペクトルを示すものである。
また、第４図は本発明の実施例２で得られた重合体の溶
媒変化による体積変化を示すグラフであり、第５図は同
じく実施例２で得られた重合体の温度変化による体積変
化を示すグラフである。Figure 1 shows the nuclear magnetic co-Di (13C-NMR) spectrum of the polymer obtained in Example 1 of the present invention, and Figure 2 shows the nuclear magnetic co-Di (13C-NMR) spectrum of the polymer also obtained in Example 1. Figure 3 shows the resonance ('H-NMR) spectrum of the polymer obtained in Example 1.
IR) spectrum. Moreover, FIG. 4 is a graph showing the volume change due to a change in solvent of the polymer obtained in Example 2 of the present invention, and FIG. 5 is a graph showing the volume change due to a change in temperature of the polymer obtained in Example 2. This is a graph showing.
Claims (2)
０のアルキル基、シクロアルキル基を示し、Ｒ＾１、Ｒ
＾２は同じものであっても異なったものでもよい。また
、ｎは１以上の実数である。］ で表わされる繰り返し単位を有し、かつ、重量平均分子
量が３，０００以上であるポリフェニレン系重合体。(1) General formula [wherein R^1 and R^2 are hydrogen atoms or carbon atoms 1 to 3]
0 alkyl group, cycloalkyl group, R^1, R
^2 may be the same or different. Further, n is a real number of 1 or more. ] A polyphenylene polymer having a repeating unit represented by the following and having a weight average molecular weight of 3,000 or more.
０のアルキル基、シクロアルキル基を示し、Ｒ＾１、Ｒ
＾２は同じものであつても異なったものでもよい。また
、ｎは１以上の実数である。］ で表わされるフルオレン誘導体を化学的酸化重合または
電気化学的酸化重合することを特徴とする請求項（１）
記載のポリフェニレン系重合体の製造法。(2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 and R^2 are hydrogen atoms or carbon atoms of 1 to 3
0 alkyl group, cycloalkyl group, R^1, R
^2 may be the same or different. Further, n is a real number of 1 or more. ] Claim (1) characterized in that the fluorene derivative represented by is subjected to chemical oxidative polymerization or electrochemical oxidative polymerization.
A method for producing the polyphenylene polymer described above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15055889A JPH0317120A (en) | 1989-06-15 | 1989-06-15 | Polyphenylene-based polymer and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15055889A JPH0317120A (en) | 1989-06-15 | 1989-06-15 | Polyphenylene-based polymer and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0317120A true JPH0317120A (en) | 1991-01-25 |
Family
ID=15499507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15055889A Pending JPH0317120A (en) | 1989-06-15 | 1989-06-15 | Polyphenylene-based polymer and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0317120A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006070848A1 (en) * | 2004-12-28 | 2006-07-06 | Sumitomo Chemical Company, Limited | Polymer compound and polymer light-emitting device using same |
-
1989
- 1989-06-15 JP JP15055889A patent/JPH0317120A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006070848A1 (en) * | 2004-12-28 | 2006-07-06 | Sumitomo Chemical Company, Limited | Polymer compound and polymer light-emitting device using same |
| GB2437213A (en) * | 2004-12-28 | 2007-10-17 | Sumitomo Chemical Co | Polymer compound and polymer light-emitting device using same |
| GB2437213B (en) * | 2004-12-28 | 2010-03-24 | Sumitomo Chemical Co | Polymer compound and polymer light emitting device using the same |
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