JPH02269734A - Polyphenylene polymer and its manufacturing method - Google Patents
Polyphenylene polymer and its manufacturing methodInfo
- Publication number
- JPH02269734A JPH02269734A JP9147689A JP9147689A JPH02269734A JP H02269734 A JPH02269734 A JP H02269734A JP 9147689 A JP9147689 A JP 9147689A JP 9147689 A JP9147689 A JP 9147689A JP H02269734 A JPH02269734 A JP H02269734A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- polyphenylene
- formula
- alkyl group
- conductivity
- 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 abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 22
- 239000002904 solvent Substances 0.000 abstract description 15
- 150000002220 fluorenes Chemical class 0.000 abstract description 10
- 239000012769 display material Substances 0.000 abstract description 5
- 229920006351 engineering plastic Polymers 0.000 abstract description 5
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- LQQKFGSPUYTIRB-UHFFFAOYSA-N 9,9-dihexylfluorene Chemical compound C1=CC=C2C(CCCCCC)(CCCCCC)C3=CC=CC=C3C2=C1 LQQKFGSPUYTIRB-UHFFFAOYSA-N 0.000 abstract description 2
- 229910013075 LiBF Inorganic materials 0.000 abstract 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- LZHSIVAEFPMRNK-UHFFFAOYSA-N 9-hexyl-9h-fluorene Chemical compound C1=CC=C2C(CCCCCC)C3=CC=CC=C3C2=C1 LZHSIVAEFPMRNK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910019785 NBF4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 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
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 239000013067 intermediate product Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 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
- 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
- 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
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000009751 slip forming 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
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 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】
［産業上の利用分野］
本発明は溶剤可溶性、熱可塑性を有し、かつ導電性に優
れ、表示材料、エンジニアリングプラスチックなどに適
した新規なポリフェニレン系重合体およびその効率的な
製造法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a novel polyphenylene polymer that is solvent soluble, thermoplastic, and has excellent conductivity, and is suitable for display materials, engineering plastics, etc., and its efficiency. related to manufacturing methods.
［従来の技術及び発明が解決しようとする課題］芳香環
が単結合で連結されたポリフェニレン系重合体はポリア
セチレｌ、ポリチオフェンとともに導電性高分子を代表
するものとして知られている。また、該ポリフェニレン
系重合体は耐熱性に優れ、エンジニアリングプラスチッ
クスとしても期待されている。[Prior Art and Problems to be Solved by the Invention] Polyphenylene polymers in which aromatic rings are connected by single bonds are known as representative conductive polymers, along with polyacetylene and polythiophene. Furthermore, the polyphenylene polymer has excellent heat resistance and is expected to be used as an engineering plastic.
このポリフェニレン系重合体は、例えばフリーデルタラ
フト触媒を用い、ベンゼンを直接酸化重合することによ
り得られる（Ｋａｖａｃｉｃら、Ｊ、＾ＬＣｈｅｍ、
Ｓｃｉ、、 ８５．４５４（１９６３））。This polyphenylene polymer can be obtained, for example, by direct oxidative polymerization of benzene using a Friedelta raft catalyst (Kavacic et al., J, ^LChem,
Sci., 85.454 (1963)).
このポリフェニレン系重合体は耐熱５５０℃の赤褐色粉
末であるが、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。This polyphenylene polymer is a reddish-brown powder with a heat resistance of 550° C., but it has the disadvantage of being insoluble in solvents and thermally infusible.
一方、ベンゼンを特定の電解質を用い、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
、 （：ｈｅｍ、 Ｓｏｃ、 Ｃｈｅｍ、 Ｃｏｍｍｕ
ｎ、、 １６２９しかしながら、この方法で得られるポ
リフェニレン系重合体も溶剤に不溶であり、しかも熱的
に不溶であるという欠点がある。On the other hand, 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
, (:hem, Soc, Chem, Commu
However, the polyphenylene polymer obtained by this method also has the disadvantage of being insoluble in solvents and thermally insoluble.
したがって、いずれの方法によっても溶剤可溶性、熱可
塑性を有するポリフェニレン系重合体は得られず、この
ため成形加工が困難であり、実用化されるに至っていな
い。Therefore, a polyphenylene polymer having solvent solubility and thermoplasticity cannot be obtained by any of the methods, and therefore molding is difficult, and it has not been put into practical use.
［課題を解決するための手段］
本発明者らは、従来のポリフェニレン系重合体に比べ溶
剤可溶性、熱可塑性等に優れたポリフェニレン系重合体
を提供するため鋭意研究を重ねた。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得られる重合体が新規
なものであり、しかもこの重合体が溶剤に可溶であり、
製膜性を有し、しかもある温度以上で熱可塑性を有する
など極めて優れた性質を有するものであることを見出し
、この知見に基いて本発明を完成するに至った。[Means for Solving the Problems] The present inventors have conducted extensive research in order to provide a polyphenylene polymer that is superior in solvent solubility, thermoplasticity, etc. compared to conventional polyphenylene polymers. As a result, the polymer obtained by chemical oxidative polymerization or electrochemical oxidative polymerization of a fluorene derivative having a specific structure is novel, and moreover, this polymer is soluble in a solvent.
It was discovered that it has extremely excellent properties such as film-forming properties and thermoplasticity above a certain temperature, and based on this knowledge, the present invention was completed.
すなわち本発明は、
一般式
［式中、Ｒ１は水素原子または炭素数１〜３０のアルキ
ル基、Ｒ２は炭素数３〜３０のアルキル基を示し、Ｒ１
，Ｒ２は同じものであっても異なったものでもよい。コ
で０表わされる繰り返し単位を有し、かつ重量平均分子
量が３００溌あるポリフェニレン系重合体を提供すると
ともに、
一般式
［式中、Ｒ′は水素原子または炭素数１〜３０のアルキ
ル基、Ｒ２は炭素数３〜３０．のアルキル基を示し、Ｒ
１，Ｒ２は同じ″ものであっても異なったものでもよい
。］
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
なポリフェニレン系重合体の製造法を提供するものであ
る。That is, the present invention is based on the general formula [wherein R1 represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, R2 represents an alkyl group having 3 to 30 carbon atoms, and R1
, R2 may be the same or different. Provided is a polyphenylene polymer having a repeating unit represented by 0 and having a weight average molecular weight of 300. has 3 to 30 carbon atoms. represents an alkyl group, R
1, R2 may be the same or different.] The novel polyphenylene polymer described above is produced by chemically oxidatively polymerizing or electrochemically oxidizing a fluorene derivative represented by It provides a manufacturing method.
本発明の新規ポリフェニレン系重合体は、上記−数式Ｃ
Ｉ）で表わされる繰り返し単位を有するものである。上
記−数式（Ｉ）において Ｒ１は水素原子または炭素数
１〜３０の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、プロピル基、ブチル基
、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、
ノニル基。The novel polyphenylene polymer of the present invention has the above formula C
It has a repeating unit represented by I). In the above formula (I), R1 represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, and specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, heptyl group, octyl group,
Nonyl group.
デシル基、ウンデシル基、ドデシル基、ヘキサデシル基
、トコシル基、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。Examples include a decyl group, an undecyl group, a dodecyl group, a hexadecyl group, a tocosyl group, a cyclohexyl group, and an alkyl group having 5 or more carbon atoms is particularly preferred.
また、上記−数式（Ｉ）において、Ｒ２は炭素数３〜３
０のアルキル基、好ましくは炭素数５〜２５のアルキル
基を示している。In addition, in the above formula (I), R2 has 3 to 3 carbon atoms.
0 alkyl group, preferably an alkyl group having 5 to 25 carbon atoms.
なお、上記Ｒ１，Ｒ２においてアルキル基としては、直
鎮状１分枝状、環状いずれの構造のものであってもよい
。The alkyl group in R1 and R2 above may have either a straight monobranched structure or a cyclic structure.
また、ｔｔｌ、 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（お、重量平均分子量が３０００以上で
あるものが有用性が高い。重量平均分子量が３０００未
満では熱的性質１機械的性質がともに十分でない。Further, ttl and R2 may be the same or different. Furthermore, the polyphenylene polymers of the present invention (those having a weight average molecular weight of 3,000 or more are highly useful).If the weight average molecular weight is less than 3,000, both thermal properties and mechanical properties are insufficient.
以上の如き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 as described above can be produced, for example, as follows.
本発明においては、原料物質として前記−数式（ＩＩ）
で表わされるフルオレン誘導体を用いる。In the present invention, the above-mentioned formula (II) is used as a raw material.
A fluorene derivative represented by is used.
−数式（１１）中におけるＲ１． Ｒ２は前記−数式（
Ｉ）における説明中で記載した通りである。- R1 in formula (11). R2 is the above-mentioned formula (
This is as described in the explanation in I).
本発明で用いられる、前記−数式（ＩＩ ）で表わされ
るフルオレン誘導体は、フルオレンの９位の２個の水素
原子の一方あるいは両方をアルキル基で置換したもので
ある。このような前記−数式（ＩＩ）で表わされるフル
すレン誘導体（モノアルキル体とジアルキル体）は、例
えば次の如くして得ることができる。The fluorene derivative represented by formula (II) used in the present invention is one in which one or both of the two hydrogen atoms at the 9-position of fluorene are substituted with an alkyl group. Such fullene derivatives (monoalkyl derivatives and dialkyl derivatives) represented by the above formula (II) can be obtained, for example, as follows.
まずモノアルキルフルオレンモノマーであるが、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モノアルキル体を得る。First, regarding the monoalkylfluorene monomer, a monoalkyl compound is obtained by reacting fluorene as shown in the following formula while stirring the fluorene at room temperature under an argon atmosphere.
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。In this case, the blending ratio (molar ratio, hereinafter the same) of fluorene and BuLi (n-butyllithium) is former/latter = 1
．． 0 to 0.5, preferably 0.9 to 0.75, and 1
Stirring (reaction) is carried out for ~2 hours.
また、リチウムフルオレンに加えるＲ’Ｂｒ （ｎ −
ブロムアルキル）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、３〜１０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、Ｒ１は前記と同様である。Also, R'Br (n −
The blending ratio of bromoalkyl) is former/latter = 1.0 to 0.
．． 5, preferably 0.9 to 0.75, and a monoalkyl compound can be obtained by stirring (reacting) for 3 to 10 hours. Note that R1 is the same as described above.
一方、ジアルキルフルオレンモノマーを得る方法は種々
あるが、上記の如くして得られたモノアルキル体から次
の様にして合成することができる。On the other hand, although there are various methods for obtaining a dialkylfluorene monomer, it can be synthesized from the monoalkyl body obtained as described above in the following manner.
この場合モノアルキル体と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（リチウムそジアルキル体）とＲ”
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）時間はモノアルキル体
を得た場合と同様である。なお、Ｒ１，Ｒ２は前記と同
様である。In this case, the blending ratio of the monoalkyl body and BuLi is former/latter = 1.0 to 0.5, preferably 0.9 to 0.75.
, and the intermediate product (lithium sodialkyl form) and R”
The blending ratio of Br is 1.0 to 0.5, preferably 0.9
~0.75, and the stirring (reaction) time is the same as in the case of obtaining the monoalkyl compound. Note that R1 and R2 are the same as described above.
本発明においては、上記の如くして得られる、前記−数
式（ＩＩ）で表わされるフルオレン誘導体（モノアルキ
ル体とジアルキル体）を原料物質とし、このフルオレン
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
。これにより前記−数式（Ｉ）で表わされる繰り返し単
位を有するポ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, the fluorene derivatives (monoalkyl and dialkyl) represented by formula (II) obtained as described above are used as raw materials, and this fluorene derivative is subjected to chemical oxidative polymerization or electrochemical oxidation. Polymerize. As a result, a polyphenylene polymer having a repeating unit represented by formula (I) above 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ＦｅＣｌ２．
ＭｏＣ１’ｓ、 ＷＣｉ’ｓなど酸化剤単独であって
もよいが、ＡｊＣＩｌｓ−Ｃｕ（ＩＩ２． ＡＮＣＮ３
−ＭｎＯｚなどルイス酸と組合せたものを用いてもよい
。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溶解させ、これを、上記、モ
ノあるいはジアルキルフルオレンに加え、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５０〜１００時間攪拌して
重合反応を行なう。このようにして得られた反応液をメ
タノール、水などに投入して重合物を炉別する。さらに
、この重合物を再度クロロホルムなどに溶解し、メタノ
ールなどに投入してン戸別することにより、本発明の新
規ポリフェニレン系重合体を得ることができる。Here, chemical oxidative polymerization is a method using an oxidizing agent as a polymerization catalyst. Such oxidizing agents include FeCl2.
An oxidizing agent such as MoC1's or WCi's may be used alone, but AjCIls-Cu(II2.ANCN3
-MnOz in combination with a Lewis acid may also be used. These oxidizing agents (catalysts) are dissolved in a halogenated solvent such as chloroform or methylene chloride, and this is added to the above mono- or dialkylfluorene, and the mixture is heated at a temperature of 0 to 100°C, preferably 20 to 50°C, under an argon atmosphere. ,
The polymerization reaction is carried out by stirring for 5 to 200 hours, preferably 50 to 100 hours. The reaction solution thus obtained is poured into methanol, water, etc., and the polymer is separated in a furnace. Furthermore, the novel polyphenylene polymer of the present invention can be obtained by dissolving this polymer again in chloroform or the like, pouring it into methanol or the like, and separating it.
一方、電気化学的酸イし重合は上記、モノあるいはジア
ルキルフルオレンと電解質を溶媒に溶かし、その中に１
対の電極を浸漬させこの電極間に電圧（３〜２０Ｖ）を
印加し、通電することによりｌＩ！極表面に重合体を生
成せしめるものである。On the other hand, electrochemical acid polymerization involves dissolving mono- or dialkylfluorene and an electrolyte in a solvent.
By immersing the pair of electrodes and applying a voltage (3 to 20 V) between the electrodes and energizing, lI! This produces a polymer on the extreme surface.
ここで用いる電解質としては種々のものが用いられるが
例えばＬｉＢＦ４． ＬｉＡｓＦａ、 ＬＩＧ１０４．
（ｎ−Ｂｕ）＜ＮＢＦ４． （Ｅｔ）ＪＣ１！０４
などが挙げられ、特にＬｆ８Ｆ４゜Ｌｉ（ＪＯｌｌ
が好ましい。また、溶媒としてはアセトニトリル、ベン
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 electrolytes can be used here, including LiBF4. LiAsFa, LIG104.
(n-Bu)<NBF4. (Et)JC1!04
etc., especially Lf8F4゜Li (JOll
is preferred. Further, as a solvent, acetonitrile, benzonitrile, propylene carbonate, dimethyl sulfoxide, nitromethane, etc. can be used.
叙上のようにして陽極表面に連続的に生成する重合体は
電解槽に沈殿する。この沈殿物を炉別。The polymer that is continuously formed on the anode surface as described above is precipitated in the electrolytic cell. Separate this precipitate by furnace.
洗浄して本発明のポリフェニレン系重合体を得ることが
できる。The polyphenylene polymer of the present invention can be obtained by washing.
このようにして化学的あるいは電気化学的に得られた本
発明のポリフェニレン系重合体はクロロホルム、塩化メ
チレン、テトラヒドロフラン、ジオキサン等、常用の溶
媒に可溶であり、メタノールに不溶であるため、再沈法
により容易に精製することができる。The polyphenylene polymer of the present invention obtained chemically or electrochemically in this way is soluble in commonly used solvents such as chloroform, methylene chloride, tetrahydrofuran, dioxane, etc., and is insoluble in methanol, so it can be reprecipitated. It can be easily purified by the method.
以上の如くして、重量平均分子量３，０００〜１５０．
０００程度の新規ポリフェニレン系重合体を製造するこ
とができる。As described above, the weight average molecular weight is 3,000 to 150.
000 new polyphenylene polymers can be produced.
［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） ９．９−ジヘキシルフルオレンの合成フルオレ
ン１０ｇをエーテルに溶かし、ｎ−ブチルリチウム（１
５％ヘキサン溶液、半井化学■製）３０ｍＪ２を加え、
アルゴン雰囲気１１時間攪拌した。Example 1 (1) Synthesis of 9.9-dihexylfluorene 10 g of fluorene was dissolved in ether, and n-butyllithium (1
Add 30 mJ2 of 5% hexane solution (manufactured by Hani Kagaku ■),
The mixture was stirred in an argon atmosphere for 11 hours.
その後、ｎ−ブロモヘキサンｌ１ｇを滴下し、さらに、
４時間攪拌した。減圧蒸留により、９−モノへキシルフ
ルオレンｌ１ｇを得た。再度同じ反応を繰り返したのち
、減圧蒸留（１８６℃、 ６ ｍｍＨｇ）によって９
．９−ジヘキシルフルオレン１３ｇを得た。Then, 1 g of n-bromohexane was added dropwise, and further,
Stirred for 4 hours. By distillation under reduced pressure, 1 g of 9-monohexylfluorene was obtained. After repeating the same reaction again, 9
．． 13 g of 9-dihexylfluorene was obtained.
（２） ９．９−ジヘキシルフルオレンの重合（化学的
酸化重合）
クロロホルム１００ｍ１ｌ中に無水塩化第二鉄１３ｇを
入れ、９．９−ジヘキシルーフルオレン６．７ｇを滴下
し、室温にて７０時間攪拌し反応させた。この反応液を
メタノール８００ｍｊ）に加え、重合物を沈殿させた。(2) Polymerization of 9.9-dihexylfluorene (chemical oxidative polymerization) 13 g of anhydrous ferric chloride was placed in 100 ml of chloroform, 6.7 g of 9.9-dihexylfluorene was added dropwise, and the mixture was stirred at room temperature for 70 hours. and reacted. This reaction solution was added to methanol (800mj) to precipitate a polymer.
その後、この沈殿物を取り出し、再度クロロホルムに溶
かした後メタノールに投入し、再沈精製を行ない、重合
精製物６ｇを得た。Thereafter, this precipitate was taken out, dissolved in chloroform again, and then poured into methanol for reprecipitation purification to obtain 6 g of a purified polymer.
得られたポリフェニレン系重合体の核磁気共鳴（１’ｃ
−ＮＭＲ）スペクトル（溶媒： ＣＤＣｌ！ｓ）を第１
図に、核磁気共Ｑ （’Ｈ−ＮＭＲ）スペクトル（溶媒
：ＣＤＣｆ３）を第２図にそれぞれ示す。この結果より
、この重合体は下記の繰り返し単位を有しており、重量
平均分子量は３１，０００であることが判った。Nuclear magnetic resonance (1'c) of the obtained polyphenylene polymer
-NMR) spectrum (solvent: CDCl!s) as the first
The nuclear magnetic co-Q ('H-NMR) spectra (solvent: CDCf3) are shown in FIG. 2, respectively. The results revealed that this polymer had the following repeating units and had a weight average molecular weight of 31,000.
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、メタノールには不溶であった。この重
合体はクロロホルムに溶かしキャスティングすることに
より、フィルムとすることができ、１００℃付近迄昇温
したとこる溶融軟化した。このフィルムの室温における
電導度は１０−” ５７ｃｍ以下であフたがヨウ素をド
ープすることにより電導度は１０−’Ｓ／ａｍとなった
。また、こめキャストフィルムをホウフッ化リチウム−
プロピレンカーボネート電解液中で電気的にドープする
と、ドープ前の黄色のフィルムが紫色に変化し、脱ドー
プすると再びもとの黄色へと戻り、可逆的な変化を示し
た。上記のようにドープした直後、空気中にフィルムを
取り出し、電導度を測定したところ１０−’Ｓ／ｃｍで
あった。Furthermore, this polymer was soluble in chloroform, methylene chloride, etc., but insoluble in water and methanol. This polymer could be made into a film by dissolving it in chloroform and casting it, and it melted and softened when the temperature was raised to around 100°C. The conductivity of this film at room temperature was less than 10"57 cm, and by doping with iodine, the conductivity became 10"S/am.
When electrically doped in a propylene carbonate electrolyte, the yellow film before doping turned purple, and when dedoped it returned to its original yellow color, indicating a reversible change. 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２（電気化学的酸化重合）
ホウフッ化リチウム０．５ｇ、実施例１（１）で得られ
た９、９−ジヘキシルフルオレン１．５ｇをベンゾニト
リル５０＋ｎＪに溶かした。これに１対の電極を浸漬し
、この電極間に７Ｖを印加した。陽極板上に生成した重
合体が電解槽下層部に沈殿した。Example 2 (Electrochemical Oxidative Polymerization) 0.5 g of lithium borofluoride and 1.5 g of 9,9-dihexylfluorene obtained in Example 1 (1) were dissolved in 50+nJ of benzonitrile. A pair of electrodes was immersed in this, and 7V was applied between the electrodes. The polymer formed on the anode plate precipitated in the lower layer of the electrolytic cell.
５ク一ロン通電して反応を止め、重合体をン戸別した後
、クロロホルムに溶かし、蒸留水で洗浄し、乾燥、濃縮
して重合体０．５ｇを得た。得られたポリフェニレン系
重合体は、”Ｃ−ＮＭＲ，’Ｈ−Ｎ閘Ｒ分析。The reaction was stopped by passing a current of 5 kg, and the polymer was separated, dissolved in chloroform, washed with distilled water, dried, and concentrated to obtain 0.5 g of a polymer. The obtained polyphenylene polymer was subjected to "C-NMR, 'H-N R analysis.
元素分析［炭素二水素＝８９．５％： １０．０％］の
結果より、実施例１と同じ繰り返し単位を有するものと
認められた。また、この重合体の重量平均分子量は３０
００であった。From the results of elemental analysis [carbon dihydrogen = 89.5%: 10.0%], it was recognized that it had the same repeating unit as in Example 1. Moreover, the weight average molecular weight of this polymer is 30
It was 00.
このものは実施例１で得られた重合体と同様の性状を示
した。This product showed properties similar to those of the polymer obtained in Example 1.
実施例３〜７
実施例１において、フルオレン誘導体として用いた９、
９−ジヘキシルフルオレンの代わりに、第１表に示すア
ルキルフルオレンを用い、実施例１と同様に重合を行な
った。結果を第１表に示す。Examples 3 to 7 9 used as a fluorene derivative in Example 1,
Polymerization was carried out in the same manner as in Example 1, using alkylfluorene shown in Table 1 instead of 9-dihexylfluorene. The results are shown in Table 1.
／
／
／
／
／
第
表
傘ｌ
室温での測定値
［発明の効果］
本発明の新規なポリフェニレン系重合体は従来の、ポリ
フェニレン系重合体に比べ溶剤可溶性、熱可塑性に優れ
ているためにフィルムなどに加工することが容易であり
、しかも、優れた導電性を有する上に、ドープ、脱ドー
プにより色、電導度を変化させることができる。/ / / / / Table Umbrella l Measured values at room temperature [Effects of the invention] The novel polyphenylene polymer of the present invention has superior solvent solubility and thermoplasticity compared to conventional polyphenylene polymers, so it can be used as a film. In addition to having excellent conductivity, the color and conductivity can be changed by doping and dedoping.
さらに詳しく述べると、本発明のポリフェニレン系重合
体は、クロロホルム、塩化メチレン等、常用の溶媒に可
溶であり、また、比較的低温度においても熱可塑性を示
し、例えば、１００℃で溶融軟化するものもあり、従っ
て、この重合体を用いて成形することは極めて容易であ
り、エンジニアリングプラスチックとしても適したもの
が得られる。More specifically, the polyphenylene polymer of the present invention is soluble in commonly used solvents such as chloroform and methylene chloride, and also exhibits thermoplasticity even at relatively low temperatures; for example, it melts and softens at 100°C. Therefore, it is extremely easy to mold using this polymer, and products suitable as engineering plastics can be obtained.
さらに、本発明の新規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。Furthermore, the novel polymer of the present invention has electrical conductivity similar to polyacetylene, polythiophene, and the like.
例えば、本発明の９．９−ジヘキシル重合体（分子量３
１，０００）の場合には電導度は１０−”Ｓ／ｃｍ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１
０−’Ｓ／ｃｌＱ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、電導度を１
０−’Ｓ／ｃｍとすることができる。For example, the 9,9-dihexyl polymer of the present invention (molecular weight 3
1,000), the conductivity is about 10-''S/cm, but when it is doped with iodine, the conductivity decreases to 1.
0-'S/clQ. In addition, by electrochemically doping LiBF4, the conductivity can be increased to 1
0-'S/cm.
また、上記ドープ、脱ドープ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。In addition, color changes may occur during the above doping and dedoping,
Since the conductivity changes, it is also possible to use this property as a display material.
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、エンジニアリングプラスチックなど
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 many industrial fields such as conductive materials, display materials, and engineering plastics.
また、本発明の製造方法を用いれば、上記、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 is an extremely useful method in industry.
第１図は本発明の実施例１で得られたポリフェニレン系
重合体の核磁気共鳴（”（ニーＮＭＲ）スペクトルを示
すものであり、第２図は同じ〈実施例１で得られたポリ
フェニレン系重合体の核磁気共鳴（’Ｈ−ＮＭＲ）スペ
クトルを示すものである。Figure 1 shows the nuclear magnetic resonance (NMR) spectrum of the polyphenylene polymer obtained in Example 1 of the present invention, and Figure 2 shows the same (NMR) spectrum of the polyphenylene polymer obtained in Example 1. It shows a nuclear magnetic resonance ('H-NMR) spectrum of a polymer.
Claims (2)
キル基、Ｒ＾２は炭素数３〜３０のアルキル基を示し、
Ｒ＾１，Ｒ＾２は同じものであっても異なったものでも
よい。］ 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３０００以上であるポリフェニレン系重合体。(1) General formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, R^1 represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, R^2 represents an alkyl group having 3 to 30 carbon atoms,
R^1 and R^2 may be the same or different. ] A polyphenylene polymer having a repeating unit represented by the following and having a weight average molecular weight of 3000 or more.
キル基、Ｒ＾２は炭素数３〜３０のアルキル基を示し、
Ｒ＾１，Ｒ＾２は同じものであっても異なったものでも
よい。］ 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 represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, R^2 represents an alkyl group having 3 to 30 carbon atoms,
R^1 and R^2 may be the same or different. ] 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 |
|---|---|---|---|
| JP9147689A JPH02269734A (en) | 1989-04-11 | 1989-04-11 | Polyphenylene polymer and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9147689A JPH02269734A (en) | 1989-04-11 | 1989-04-11 | Polyphenylene polymer and its manufacturing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02269734A true JPH02269734A (en) | 1990-11-05 |
Family
ID=14027451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9147689A Pending JPH02269734A (en) | 1989-04-11 | 1989-04-11 | Polyphenylene polymer and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02269734A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997033323A1 (en) * | 1996-03-04 | 1997-09-12 | Uniax Corporation | Polyfluorenes as materials for photoluminescence and electroluminescence |
| JPH11510535A (en) * | 1995-07-28 | 1999-09-14 | ザ ダウ ケミカル カンパニー | 2,7-Aryl-9-substituted fluorene and 9-substituted fluorene oligomers and polymers |
| KR100411465B1 (en) * | 2001-10-26 | 2003-12-18 | 한국과학기술연구원 | Fluorene-based compounds and their polymers having polyphenylenes, and el element comprising the same |
| JP2005225953A (en) * | 2004-02-12 | 2005-08-25 | Sony Chem Corp | Electric conversion luminescent polymer and organic electroluminescent element |
| KR100528906B1 (en) * | 1999-05-31 | 2005-11-16 | 삼성에스디아이 주식회사 | Blue light-emitting compound and display device adopting blue light-emitting compound as color-developing substance |
-
1989
- 1989-04-11 JP JP9147689A patent/JPH02269734A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11510535A (en) * | 1995-07-28 | 1999-09-14 | ザ ダウ ケミカル カンパニー | 2,7-Aryl-9-substituted fluorene and 9-substituted fluorene oligomers and polymers |
| WO1997033323A1 (en) * | 1996-03-04 | 1997-09-12 | Uniax Corporation | Polyfluorenes as materials for photoluminescence and electroluminescence |
| KR100528906B1 (en) * | 1999-05-31 | 2005-11-16 | 삼성에스디아이 주식회사 | Blue light-emitting compound and display device adopting blue light-emitting compound as color-developing substance |
| KR100411465B1 (en) * | 2001-10-26 | 2003-12-18 | 한국과학기술연구원 | Fluorene-based compounds and their polymers having polyphenylenes, and el element comprising the same |
| JP2005225953A (en) * | 2004-02-12 | 2005-08-25 | Sony Chem Corp | Electric conversion luminescent polymer and organic electroluminescent element |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wudl et al. | Poly (isothianaphthene) | |
| US5648453A (en) | Electroconductive polymer and process for producing the polymer | |
| JP3413956B2 (en) | Method for producing conductive polymer | |
| KR0162864B1 (en) | Manufacturing method of soluble electrically conductive polypyrrole | |
| US5061401A (en) | Electrically conductive composition of polyheteroaromatic compounds and polymeric sulfates | |
| US5688873A (en) | Electroconductive polymer and process for producing the polymer | |
| JP3149290B2 (en) | Method for producing conductive polymer | |
| JP2892681B2 (en) | Radical polymerizable composition | |
| JP2703039B2 (en) | Polymer having isothianaphthene structure and method for producing the same | |
| JPH02269734A (en) | Polyphenylene polymer and its manufacturing method | |
| US5548048A (en) | Process for manufacturing alkyl-substituted poly (2,2'-diyl) bipyridine-5,5'-diyl | |
| KR980009325A (en) | Method for preparing electrically conductive polyaniline | |
| JP2001247576A (en) | Thiophene derivative and its polymer | |
| JP4283815B2 (en) | Aqueous solution and organic solution containing conductive polymer, and support containing conductive polymer obtained from the solution | |
| JP2535563B2 (en) | Method of molding conductive polymer compound | |
| JPH026767B2 (en) | ||
| Pittman et al. | Synthesis of polyesters containing tetrathiafulvalene groups in the backbone | |
| JP3058735B2 (en) | Polypyrrole derivative and method for producing the same | |
| JP3536546B2 (en) | Water-soluble conductive polymer and method for producing the same | |
| JPH0317120A (en) | Polyphenylene-based polymer and production thereof | |
| JPS61254620A (en) | Polymer having naphtho(2,3-c)thiophene structure | |
| JP3825001B2 (en) | Aqueous solution and organic solution containing conductive polymer, and support containing conductive polymer obtained from the solution | |
| Tanaka et al. | The preparation of poly (3-methoxy-2, 5-thiophenediyl) with iron (III) chloride and its properties. | |
| JP2768441B2 (en) | Manufacturing method of anisotropic conductor | |
| US20220109157A1 (en) | Conducting redox oligomers |