JPS63110214A - Production of polyphenylene based polymer - Google Patents
Production of polyphenylene based polymerInfo
- Publication number
- JPS63110214A JPS63110214A JP25356286A JP25356286A JPS63110214A JP S63110214 A JPS63110214 A JP S63110214A JP 25356286 A JP25356286 A JP 25356286A JP 25356286 A JP25356286 A JP 25356286A JP S63110214 A JPS63110214 A JP S63110214A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- polyphenylene
- chloride
- present
- production
- 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 25
- 229920000265 Polyparaphenylene Polymers 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- -1 polyphenylene Polymers 0.000 title claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 7
- LTEQMZWBSYACLV-UHFFFAOYSA-N Hexylbenzene Chemical compound CCCCCCC1=CC=CC=C1 LTEQMZWBSYACLV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004020 conductor Substances 0.000 abstract description 3
- 239000002841 Lewis acid Substances 0.000 abstract description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 abstract description 2
- 150000007517 lewis acids Chemical class 0.000 abstract description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 239000003849 aromatic solvent Substances 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000006165 cyclic alkyl 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
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 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
- 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
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 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
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 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
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、新規なポリフェニレン系重合体の製造方法、
特に溶剤に可溶であり、成形加工性に優れたポリフェニ
レン系重合体の製造方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a novel method for producing a polyphenylene polymer,
In particular, the present invention relates to a method for producing a polyphenylene polymer that is soluble in solvents and has excellent moldability.
主鎖に芳香環が連なった構造を有するポリフェニレン系
重合体は耐熱性に優れ、エンジニアリングプラスチック
として有用で有ると考えられている。最近の研究によれ
ばポリ−パラ−フェニレンに５フン化ヒ素等のドーパン
ト−をドープすることにより、４電体としても、優れた
性質を有することが知られている。Polyphenylene polymers having a structure in which aromatic rings are connected in the main chain have excellent heat resistance and are considered to be useful as engineering plastics. According to recent research, it is known that by doping poly-para-phenylene with a dopant such as arsenic pentafluoride, it has excellent properties as a tetraelectric material.
ポリ−パラ−フェニレンはフリーデルタラフト触媒を用
い、ベンゼンを重合して得られるポリマーであり、その
粉末は不活性ガス中、５００℃迄も安定である（たとえ
ば、Ｐ、ＫｏｖａｃｉＣら、Ｊ、Ｐｏｌｙｍｅｒ、ｓｃ
ｉ、、Ａ−１４ｐ１４４５（１９６６年））、また、フ
リーデルタシフト触媒以外に、電気化学的酸化重合方法
によりベンゼンの重合体を製造する方法も知られている
（例えば住込ら、Ｐｏｌｙｍｅｒ ｃｏｍｍｕｎ、
１９Ｂ５年Ｖｏ１．２６ ｐ３５６） 。Poly-para-phenylene is a polymer obtained by polymerizing benzene using a Friedelta raft catalyst, and its powder is stable up to 500°C in an inert gas (for example, P. Kovaci et al., J. Polymer , sc
In addition to free delta shift catalysts, methods for producing benzene polymers by electrochemical oxidative polymerization are also known (for example, Sumi et al., Polymer comm.
19B5 Vo1.26 p356).
しかしながら、上記の方法で得られる重合体は不融、不
溶の重合体であるため、成形加工ができず、実用上、使
用されるに至っていない。However, since the polymer obtained by the above method is an infusible and insoluble polymer, it cannot be molded and has not been used practically.
本発明は従来のポリフェニレン系重合体に比べ成形加工
性に優れたポリフェニレン系重合体を提供する事を目的
とするものである。The object of the present invention is to provide a polyphenylene polymer that has superior moldability compared to conventional polyphenylene polymers.
本発明者らは、上記問題点を解決するために鋭意検討し
たところ、特定の構造を有するベンゼン誘導体を酸化剤
で処理することによって得られるポリフェニレン系重合
体が溶剤に溶解可能であり、さらに優れた製膜性を有す
るなど、極めて優れた性質を有する事を見出し、本発明
を完成させた。The inventors of the present invention conducted intensive studies to solve the above problems, and found that a polyphenylene polymer obtained by treating a benzene derivative with a specific structure with an oxidizing agent can be dissolved in a solvent, and is even more superior. They discovered that it has extremely excellent properties, such as excellent film-forming properties, and completed the present invention.
即ち、本発明は一般式
（式中Ｒは炭素数５以上のアルキル基を示す、）で表さ
れる化合物を、酸化剤で処理することを特徴とするポリ
フェニレン系重合体の製造方法である。That is, the present invention is a method for producing a polyphenylene polymer, which comprises treating a compound represented by the general formula (wherein R represents an alkyl group having 5 or more carbon atoms) with an oxidizing agent.
本発明で用いられる化合物はベンゼン核上に炭素数５以
上のアルキル基を有するものである。このようなアルキ
ル基としては、ペンチル−、ヘキシル−、ヘプチル−、
オクチル−、ノニル−、デシル−、ウンデシル−、ドデ
シル−等の直鎖アルキル基の他、シクロヘキシル基のよ
うな環状アルキル基、或は分校構造を有するアルキル基
などが挙げられる。これらの化合物は工業的に入手可能
である。The compound used in the present invention has an alkyl group having 5 or more carbon atoms on the benzene nucleus. Such alkyl groups include pentyl, hexyl, heptyl,
Examples include linear alkyl groups such as octyl, nonyl, decyl, undecyl, and dodecyl, as well as cyclic alkyl groups such as cyclohexyl, and alkyl groups having a branched structure. These compounds are commercially available.
本発明による重合体は、炭素数５以上のアルキル基を有
するアルキルベンゼンの酸化的カンプリング反応によっ
て製造される。The polymer according to the present invention is produced by an oxidative camping reaction of an alkylbenzene having an alkyl group having 5 or more carbon atoms.
具体的な方法としては酸化触媒を用いて重合する方法、
電気化学的に重合する方法等が挙げられるが、なかでも
触媒を用いて重合する方法が重合体を安価に容易に得る
手段として好ましい。Specific methods include polymerization using an oxidation catalyst;
Examples include electrochemical polymerization methods, among which polymerization methods using catalysts are preferred as a means for easily obtaining the polymer at low cost.
本発明で用いられる酸化剤とは、これらの重合用触媒と
して用いられる物であり、塩化アルミニウム、塩化鉄、
塩化モリブデン、塩化タングステン、塩化錫、塩化アン
チモン等のルイス酸として知られている化合物が挙げら
れる。これらのうち、塩化アルミニウムのように酸化力
を持たないものや酸化力の弱いものは、塩化第二銅や二
酸化マンガン、酸素などのような酸化剤を共用して使用
される。The oxidizing agent used in the present invention is a substance used as a catalyst for these polymerizations, and includes aluminum chloride, iron chloride,
Examples include compounds known as Lewis acids such as molybdenum chloride, tungsten chloride, tin chloride, and antimony chloride. Among these, those that do not have oxidizing power or have weak oxidizing power, such as aluminum chloride, are used in combination with oxidizing agents such as cupric chloride, manganese dioxide, and oxygen.
これらの触媒を、上記アルキルベンゼン中に添加するこ
とにより室温下で容易に本発明のポリフェニレン系重合
体を得ることができる。必要に応じて、この反応系中に
不活性溶媒を加えることもできる。By adding these catalysts to the alkylbenzene described above, the polyphenylene polymer of the present invention can be easily obtained at room temperature. If necessary, an inert solvent can also be added to this reaction system.
本発明方法による重合体は、アルコール類や水に溶解し
にくいので、上記反応混合物を水やアルコール、さらに
必要に応じて塩酸や硫酸で洗浄することによって重合触
媒と分離してポリフェニレン系重合体を得ることが出来
る０通常このようにして得られた重合体中には、溶媒に
不溶性の化合物が含まれている事があるので、さらにテ
トラヒドロフランやクロロホルム等の溶媒に溶解し、ろ
過等の方法によって不溶物を除去し、ろ液を再びアルコ
ール中に投入することにより本発明のポリフェニレン系
重合体を得ることができる。Since the polymer obtained by the method of the present invention is difficult to dissolve in alcohols and water, the reaction mixture is washed with water or alcohol, and if necessary, with hydrochloric acid or sulfuric acid to separate it from the polymerization catalyst and produce the polyphenylene polymer. Normally, the polymer obtained in this way may contain compounds that are insoluble in the solvent, so it is further dissolved in a solvent such as tetrahydrofuran or chloroform, and then removed by a method such as filtration. The polyphenylene polymer of the present invention can be obtained by removing insoluble matter and pouring the filtrate back into alcohol.
本発明方法を実施して得られるポリフェニレン系重合体
は溶媒に可溶であり、この重合体を溶解する１容媒とし
ては、テトラヒドロフラン、ジオキサンなどのエーテル
系溶媒、ベンゼン、トルエン、キシレン等の芳香族系溶
媒、ジクロロメタン、クロロホルム等のハロゲン化溶媒
アセトニトリル、ベンゾニトリル等のニトリル化合物、
ニトロメタン、ニトロベンゼン等の溶媒酢酸エチル、酢
酸ブチル等のエステル類等である。The polyphenylene polymer obtained by carrying out the method of the present invention is soluble in a solvent, and examples of the solvent for dissolving this polymer include ether solvents such as tetrahydrofuran and dioxane, aromatic solvents such as benzene, toluene, and xylene. family solvents, halogenated solvents such as dichloromethane and chloroform, nitrile compounds such as acetonitrile and benzonitrile,
These include solvents such as nitromethane and nitrobenzene, and esters such as ethyl acetate and butyl acetate.
本発明方法を実施して得られるポリフェニレン系重合体
は従来のポリフェニレン系化合物と比較して加工性に優
れており、成形加工可能な耐熱性材料或は導電性材料と
して用いることが出来る。The polyphenylene polymer obtained by carrying out the method of the present invention has excellent processability compared to conventional polyphenylene compounds, and can be used as a heat-resistant material or a conductive material that can be molded.
以下に実施例により更に本発明を説明する。 The present invention will be further explained below with reference to Examples.
実施例１
クロロホルム３０ｋｌ中に無水塩化第二鉄４０ｇを入し
た後、１−フェニルヘキサンＬｏｇを加えて室温で５０
時間撹拌した。Example 1 After putting 40 g of anhydrous ferric chloride in 30 kl of chloroform, 1-phenylhexane Log was added and 50 g of ferric chloride was added at room temperature.
Stir for hours.
反応混合物を塩酸酸性のメタノール１０１００Ｏ中に加
えて良く攪拌した０重合体は不溶物となり、メタノール
より沈澱した。この沈澱物を、さらに濾過することによ
り組型合体をえた。組型合体はメタノール、希塩酸、水
で良く洗浄した後、テトラヒドロフラン２０抛ｌに溶解
し、不溶物をろ過した。ろ液は再びメタノール１０１０
０Ｏ中に加え、生成した沈澱をろ過により集め、メタノ
ール、希塩酸、アンモニア水を含むメタノール、蒸留水
で充分に洗浄して、減圧下、８０℃で１０時間乾燥し、
褐色の重合体６．５ｇを得た。得られた重合体の赤外吸
収スペクトルを第１図に示す。The reaction mixture was added to 10,100 O of methanol acidified with hydrochloric acid and stirred well. The 0 polymer became insoluble and precipitated from the methanol. This precipitate was further filtered to obtain a composite. After thoroughly washing the composite with methanol, dilute hydrochloric acid, and water, it was dissolved in 20 liters of tetrahydrofuran, and insoluble matter was filtered. The filtrate is mixed with methanol 1010 again.
The resulting precipitate was collected by filtration, thoroughly washed with methanol, dilute hydrochloric acid, methanol containing aqueous ammonia, and distilled water, and dried under reduced pressure at 80°C for 10 hours.
6.5 g of a brown polymer was obtained. The infrared absorption spectrum of the obtained polymer is shown in FIG.
また、第２図は窒素雰囲気下で測定した重合体の熱重量
分析の測定結果を示す。Moreover, FIG. 2 shows the measurement results of thermogravimetric analysis of the polymer measured under a nitrogen atmosphere.
また得られた重合体は、水、アルコールには不溶であっ
たがテトラヒドロフラン、ジオキサン、ベンゼン、トル
エン、キシレン、クロロホルム、ジクロロメタン、酢酸
エチル、アセトニトリル等の通常の溶媒に可溶であり、
キャストしてフィルムにしたり紙や繊維、多孔質板など
に吸収させて複合体とすることも可能であった。The obtained polymer was insoluble in water and alcohol, but soluble in common solvents such as tetrahydrofuran, dioxane, benzene, toluene, xylene, chloroform, dichloromethane, ethyl acetate, and acetonitrile.
It was also possible to make composites by casting them into films or absorbing them into paper, fibers, porous plates, etc.
実施例２
実施例１において１フエニルヘキサンのカワリにシクロ
ヘキシルベンゼンを用いて重合時間を３時間とした以外
は実施例１と同様にして重合をおこなった。収率は４３
％であり、第３図に得られた重合体の赤外吸収スペクト
ルを示す。Example 2 Polymerization was carried out in the same manner as in Example 1 except that cyclohexylbenzene was used as a substitute for phenylhexane and the polymerization time was changed to 3 hours. Yield is 43
%, and FIG. 3 shows the infrared absorption spectrum of the obtained polymer.
実施例３−６
実施例１において１フエニルヘキサンの代わりに表１に
示す種々のアルキルベンゼンを用いて実施例１と同様に
して重合を行ワたところ、それぞれ、表１に示すポリフ
ェニレン系重合体が得られた。 表１
実施例７
実施例１において無水塩化第二鉄の代わりに、三塩化ア
ルミニウム３３ｇと無水塩化第二銅１５ｇを用いて、ク
ロロホルムの代わりに二硫化炭素を溶媒として用いた以
外は実施例１と同様にして重合を行ったところ、実施例
１と同様の重合体７．２ｇを得た。Example 3-6 Polymerization was carried out in the same manner as in Example 1 using various alkylbenzenes shown in Table 1 instead of phenylhexane, resulting in the polyphenylene polymers shown in Table 1. was gotten. Table 1 Example 7 Example 1 except that 33 g of aluminum trichloride and 15 g of anhydrous cupric chloride were used instead of anhydrous ferric chloride in Example 1, and carbon disulfide was used as the solvent instead of chloroform. When polymerization was carried out in the same manner as in Example 1, 7.2 g of the same polymer as in Example 1 was obtained.
本発明の方法を実施することによって、従来のポリフェ
ニレン系重合体が有する欠点、溶剤への溶解性、加工性
を改良し、成形加工が可能な耐熱性高分子材料として、
また導電性材料として用いることができるものであり、
その工業的価値は極めて高い。By carrying out the method of the present invention, the disadvantages of conventional polyphenylene polymers, solubility in solvents, and processability are improved, and a heat-resistant polymer material that can be molded is produced.
It can also be used as a conductive material,
Its industrial value is extremely high.
第１図は実施例１により得た重合体の赤外吸収スペクト
ル図である。
第２図は実施例１により得た重合体を窒素雰囲気下で測
定した熱重量分析の測定図である。
第３図は実施例２により得た重合体の赤外吸収スペクト
ル図である。FIG. 1 is an infrared absorption spectrum diagram of the polymer obtained in Example 1. FIG. 2 is a graph of thermogravimetric analysis of the polymer obtained in Example 1 under a nitrogen atmosphere. FIG. 3 is an infrared absorption spectrum diagram of the polymer obtained in Example 2.
Claims (1)
れる化合物を、酸化剤で処理することを特徴とするポリ
フェニレン系重合体の製造方法。(1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents an alkyl group having 5 or more carbon atoms.) A polyphenylene system characterized by treating a compound represented by the following with an oxidizing agent. Method for producing polymers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25356286A JPH0676479B2 (en) | 1986-10-27 | 1986-10-27 | Method for producing polyphenylene polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25356286A JPH0676479B2 (en) | 1986-10-27 | 1986-10-27 | Method for producing polyphenylene polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63110214A true JPS63110214A (en) | 1988-05-14 |
| JPH0676479B2 JPH0676479B2 (en) | 1994-09-28 |
Family
ID=17253091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25356286A Expired - Lifetime JPH0676479B2 (en) | 1986-10-27 | 1986-10-27 | Method for producing polyphenylene polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0676479B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04507263A (en) * | 1989-08-23 | 1992-12-17 | マックスデム インコーポレイテッド | rigid polymer |
| US5756581A (en) * | 1988-02-17 | 1998-05-26 | Maxdem Incorporated | Rigid-rod polymers |
-
1986
- 1986-10-27 JP JP25356286A patent/JPH0676479B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5756581A (en) * | 1988-02-17 | 1998-05-26 | Maxdem Incorporated | Rigid-rod polymers |
| US5760131A (en) * | 1988-02-17 | 1998-06-02 | Maxdem Incorporated | Rigid-rod polymers |
| US5789521A (en) * | 1988-02-17 | 1998-08-04 | Maxdem Incorporated | Rigid-rod polymers |
| US5976437A (en) * | 1988-02-17 | 1999-11-02 | Maxdem Incorporated | Rigid-rod polymers |
| US6087467A (en) * | 1988-02-17 | 2000-07-11 | Maxdem Incorporated | Rigid-rod polymers |
| JPH04507263A (en) * | 1989-08-23 | 1992-12-17 | マックスデム インコーポレイテッド | rigid polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0676479B2 (en) | 1994-09-28 |
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