JPS62260804A - Production of fluorine-containing polyphenylacetylene - Google Patents
Production of fluorine-containing polyphenylacetyleneInfo
- Publication number
- JPS62260804A JPS62260804A JP10571986A JP10571986A JPS62260804A JP S62260804 A JPS62260804 A JP S62260804A JP 10571986 A JP10571986 A JP 10571986A JP 10571986 A JP10571986 A JP 10571986A JP S62260804 A JPS62260804 A JP S62260804A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- polymerization catalyst
- tungsten hexachloride
- formula
- polymerization
- 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000011737 fluorine Substances 0.000 title claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 12
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims abstract description 12
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 9
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 9
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 3
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims abstract 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims abstract 2
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 claims description 4
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 claims description 4
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 claims description 2
- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 claims description 2
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 12
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 239000004065 semiconductor Substances 0.000 abstract description 2
- OOZKONVIIMFOKW-UHFFFAOYSA-N 1-ethynyl-2-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=CC=C1C#C OOZKONVIIMFOKW-UHFFFAOYSA-N 0.000 abstract 1
- 229910015221 MoCl5 Inorganic materials 0.000 abstract 1
- 229910003091 WCl6 Inorganic materials 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920006158 high molecular weight polymer Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- -1 triethylaluminalum Chemical compound 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DBGPLCIFYUHWKA-UHFFFAOYSA-H hexachloromolybdenum Chemical compound Cl[Mo](Cl)(Cl)(Cl)(Cl)Cl DBGPLCIFYUHWKA-UHFFFAOYSA-H 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- SBXWFLISHPUINY-UHFFFAOYSA-N triphenyltin Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)C1=CC=CC=C1 SBXWFLISHPUINY-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、フッ素またはトリフルオロメチル基を有する
ポリフェニルアセチレン類の製法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing polyphenylacetylenes having fluorine or trifluoromethyl groups.
フッ素またはトリフルオロメチル基を有するポリフェニ
ルアセチレン類は、従来のポリアセチレン類に比べて耐
熱性に優れており、半導体や気体分離膜等多くの方面に
応用することができる有用な化合物である。Polyphenylacetylenes having fluorine or trifluoromethyl groups have better heat resistance than conventional polyacetylenes, and are useful compounds that can be applied to many fields such as semiconductors and gas separation membranes.
従来含フッ素ポリフェニルアセチレン類の製法としては
、（１）触媒にタングステンカルボニルを使用し、紫外
線を照射した後、モノマーを重合する方法（２）ＣＯ−
６０を線源としてγ線をモキマーに照射して重合させる
方法（３）モノマーを１００℃から２００℃で加熱して
熱重合させる方法等（特開昭６０−１６６３０９号公報
）が知られている０例えば、これらの製法により一般式
％式％
（式中、Ｐｈ’ｆは１ないし２個のフッ素またはトリフ
ルオロメチル基を表す、）
で示される化合物を重合して、−ａ式
％式％
（式中、Ｐｈｆは前記と同意義、ｎは２以上の整数を表
す、）
で示される含フッ素ポリフェニルアセチレンが得られる
ことが知られている（同公報）。Conventional methods for producing fluorine-containing polyphenylacetylenes include (1) using tungsten carbonyl as a catalyst and polymerizing monomers after irradiation with ultraviolet rays (2) CO-
A method of polymerizing moquimer by irradiating gamma rays using 60 as a radiation source (3) A method of thermally polymerizing a monomer by heating it at 100°C to 200°C (Japanese Unexamined Patent Publication No. 166309/1983) is known. 0 For example, by polymerizing a compound represented by the general formula % formula % (in the formula, Ph'f represents 1 or 2 fluorine or trifluoromethyl groups) using these production methods, -a formula % formula % (In the formula, Phf has the same meaning as above, and n represents an integer of 2 or more.) It is known that a fluorine-containing polyphenylacetylene represented by the following formula can be obtained (the same publication).
しかし、上記（１）の方法は、重合溶媒に四塩化炭素以
外使用できず、また光反応であるため、光の照射量によ
り得られるポリマーの分子量が異なるなど再現性に問題
があった。また、上記（２）および（３）の方法は収率
が低く実用的な製法ではない。However, the above method (1) cannot use anything other than carbon tetrachloride as the polymerization solvent, and since it is a photoreaction, there are problems with reproducibility, such as the molecular weight of the obtained polymer varying depending on the amount of light irradiation. Furthermore, the above methods (2) and (3) have low yields and are not practical production methods.
本発明の目的は、収率が良く、容易にフッ素またはトリ
フルオロメチル基を存するポリフェニルアセチレン類を
得ることができる製法を提供することにある。An object of the present invention is to provide a production method that can easily produce polyphenylacetylenes containing fluorine or trifluoromethyl groups with good yield.
本発明の要旨は、一般式
％式％
（式中、Ｐｈｆは１ないし２個のフッ素原子またはトリ
フルオロメチル基を有するフェニル基を表す、）
で示される化合物を重合触媒に五塩化モリブデンもしく
は六塩化タングステンを単独で、または五塩化モリブデ
ンもしくは六塩化タングステンを有機金属化合物と共に
使用することを特徴とする含フッ素ポリフェニルアセチ
レン類の製法である。The gist of the present invention is to use molybdenum pentachloride or molybdenum hexachloride as a polymerization catalyst using a compound represented by the general formula % (in the formula, Phf represents a phenyl group having 1 or 2 fluorine atoms or a trifluoromethyl group). This is a method for producing fluorine-containing polyphenylacetylenes, characterized by using tungsten chloride alone or molybdenum pentachloride or tungsten hexachloride together with an organometallic compound.
本発明で使用するモノマー化合物は、フッ素またはトリ
フルオロメチル基をベンゼン環に有するβ、β−ジクロ
ロ−α−フルオロスチレン類をアルキルリチウムと反応
させて合成することができる（特公昭５９−４６９３１
号公報）。The monomer compound used in the present invention can be synthesized by reacting β,β-dichloro-α-fluorostyrene having a fluorine or trifluoromethyl group in the benzene ring with an alkyllithium (Japanese Patent Publication No. 59-46931
Publication No.).
本発明で重合触媒として使用する五塩化モリブデンまた
は六塩化タングステンはそれぞれ単独で重合触媒として
作用し、本発明の目的を達成しうるが、これらの重合触
媒のそれぞれと有機金属化合物を併用して共触媒系で使
用することにより触媒活性を増大させ、更に高収率で高
分子量のポリマーを得ることができる。Molybdenum pentachloride or tungsten hexachloride used as a polymerization catalyst in the present invention each acts as a polymerization catalyst alone and can achieve the object of the present invention, but it is possible to achieve the purpose of the present invention by using each of these polymerization catalysts in combination with an organometallic compound. By using it in a catalyst system, the catalytic activity can be increased and high molecular weight polymers can be obtained in higher yields.
本発明で使用する好ましい有機金属化合物としては、テ
トラフェニルスズ、テトラブチルスズ、トリフェニルシ
ラン、トリエチルアルミナラム、トリエチルシラン、ト
リフェニルアンチモン、およびトリフェニルビスマス等
を例示することができる。特に高分子量のポリマーを製
造しようとする場合は、テトラフェニルスズ、トリフェ
ニルシランおよびトリフェニルスズが好ましい。Preferred organometallic compounds used in the present invention include tetraphenyltin, tetrabutyltin, triphenylsilane, triethylaluminalum, triethylsilane, triphenylantimony, and triphenylbismuth. Particularly when high molecular weight polymers are to be produced, tetraphenyltin, triphenylsilane and triphenyltin are preferred.
触媒濃度は、モノマーおよび溶剤に対して通常５〜１０
０ミリモル／ｌの範囲であるが、１０ミリモル／１前後
のときに特に高分子量のポリマーが得られる。Catalyst concentration is usually 5 to 10% relative to monomer and solvent.
It is in the range of 0 mmol/l, but particularly high molecular weight polymers are obtained when it is around 10 mmol/l.
有機金属化合物を併用する場合の、五塩化モリブデンも
しくは六塩化タングステンと有機金属化合物との使用割
合は、モル比で通常１：０．１〜１：１０、最も好まし
くはｔｉｔである。When an organometallic compound is used in combination, the molar ratio of molybdenum pentachloride or tungsten hexachloride to the organometallic compound is usually 1:0.1 to 1:10, most preferably tit.
重合温度は、通常−３０〜８０℃であるが、タングステ
ン系触媒を使用した場合は、０〜３０℃、モリブデン系
触媒を使用した場合は、３０〜６０℃が好ましい。The polymerization temperature is usually -30 to 80°C, preferably 0 to 30°C when a tungsten catalyst is used, and 30 to 60°C when a molybdenum catalyst is used.
重合は通常、溶媒存在下に行われ、重合溶媒としては、
トルエンやシクロヘキサン等の炭化水素や、四塩化炭素
等のハロゲン化炭化水素が好ましい。Polymerization is usually carried out in the presence of a solvent, and the polymerization solvent is
Hydrocarbons such as toluene and cyclohexane, and halogenated hydrocarbons such as carbon tetrachloride are preferred.
本発明の製法においてモノマー濃度は溶媒に対して通常
０．１〜５モル／１、好ましくは０．２５〜１．０モル
／ｌである。In the production method of the present invention, the monomer concentration is usually 0.1 to 5 mol/l, preferably 0.25 to 1.0 mol/l, relative to the solvent.
重合反応後得られた重合体の精製は、通常重合体溶液を
大量のメタノール等の溶媒に加え、重合体を沈澱させ、
濾別、乾燥することにより行われる。Purification of the polymer obtained after the polymerization reaction usually involves adding a polymer solution to a large amount of a solvent such as methanol to precipitate the polymer.
This is done by filtering and drying.
以下、実施例により本発明を更に具体的に説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
攪拌機、温度計及び窒素導入管を備えた５ ０ｍｊ！容
の三ロフラスコに六塩化タングステン７９ｍｇ（０，２
ｍｍｏ ｌ）を仕込み、次いで水素化カルシウムで乾燥
したトルエン２Ｑ ｍ ｊ！を窒素気流下で仕込んだ、
３０℃で１０分間撹拌した後、精密（純度９９．９％）
した〇−トリフルオロメチルフェニルアセチレン３．５
ｇ （２０，６ｍｍｏ Ｉ）を加え、同温度で２４時
間反応させた０反応終了後、反応液を多量のメタノール
に注ぎ、沈澱したポリマーを濾別回収した。得られたポ
リマーをテトラヒドロフラン（ＴＨＦ）−メタノールで
再沈積製後、室温で２４時間乾燥を行い、１．９ｇ（収
率５４％）の赤褐色固体のポリマーを得た。Example 1 50mj equipped with stirrer, thermometer and nitrogen inlet tube! 79 mg of tungsten hexachloride (0,2
mmol l) and then dried with calcium hydride toluene 2Q m j! was prepared under a nitrogen stream,
After stirring at 30℃ for 10 minutes, precision (purity 99.9%)
〇-Trifluoromethylphenylacetylene 3.5
After the reaction was completed, the reaction solution was poured into a large amount of methanol, and the precipitated polymer was collected by filtration. The obtained polymer was reprecipitated with tetrahydrofuran (THF)-methanol and then dried at room temperature for 24 hours to obtain 1.9 g (yield 54%) of a reddish brown solid polymer.
生成ポリマーの分子量は、ＧＰＣ（ゲルパーミエイショ
ン クロマトグラフィ：ＴＨＦ溶媒、ポリスチレン換算
）により、Ｍ、１（重量平均分子量）３３Ｘ１０’、Ｍ
、（数平均分子量）が１４Ｘ１０’であった。また、ポ
リマーの極限粘度〔η〕 （溶媒ＴＨＦ、３５℃）は０
．９３９ ｄ ｊ！／ｇであった。The molecular weight of the produced polymer was determined by GPC (gel permeation chromatography: THF solvent, polystyrene equivalent) to be M, 1 (weight average molecular weight) 33X10', M
, (number average molecular weight) was 14×10′. In addition, the intrinsic viscosity of the polymer [η] (solvent THF, 35°C) is 0
．． 939 d j! /g.
（以下余白）
実施例２
重合触媒に五塩化モリブデン５５ｍｇ （０，２ｍｍｏ
ｌ）を使用したことを除いては実施例１と同一条件で反
応させた。結果を第１表に示す。(Left below) Example 2 55 mg of molybdenum pentachloride (0.2 mmo
The reaction was carried out under the same conditions as in Example 1 except that 1) was used. The results are shown in Table 1.
実施例３
重合触媒に五塩化モリブデン’１３ｍｇ （０，１ｍｍ
ｏｌ）及びテトラフェニルスズ４３ｍｇ（０，１ｍｍｏ
りを使用したことを除いては実施例１と同一条件で反応
させた。結果を第１表に示す。Example 3 13 mg of molybdenum pentachloride (0.1 mm
ol) and tetraphenyltin 43 mg (0,1 mmo
The reaction was carried out under the same conditions as in Example 1, except that the reaction mixture was used. The results are shown in Table 1.
実施例４
重合触媒に六塩化タングステン４０ｍｇ （０，１ｍｍ
ｏ＋）及びテトラフェニルスズ４３ｍｇ（０，１ｍｍｏ
ｌ）を使用し、重合温度を０℃としたことを除き実施例
１と同一条件で反応させた。Example 4 40 mg of tungsten hexachloride (0.1 mm) as a polymerization catalyst
o+) and tetraphenyltin 43 mg (0,1 mmo
1) and the reaction was carried out under the same conditions as in Example 1 except that the polymerization temperature was 0°C.
結果を第１表に示す。The results are shown in Table 1.
実施例５
重合触媒に六塩化タングステン４０ｍｇ （０，１ｍｍ
ｏｌ）及びトリフェニルシラン２６ｍｇ （Ｑ、１ｍ
ｍｏｌ）を使用したことを除き実施例４と同一条件で反
応させた。結果を第１表に示す。Example 5 40 mg of tungsten hexachloride (0.1 mm
ol) and triphenylsilane 26 mg (Q, 1 m
The reaction was carried out under the same conditions as in Example 4 except that mol) was used. The results are shown in Table 1.
実施例６
重合触媒に六塩化タングステン４０ｍｇ （０，１ｍｍ
ｏｌ）及び）リフェニルアンチモン３５ｍｇ（０，１ｍ
ｍｏ ｌ）を使用したことを除き実施例４と同一条件で
反応させた。結果を第１表に示す。Example 6 40 mg of tungsten hexachloride (0.1 mm) as a polymerization catalyst
ol) and) Riphenylantimony 35 mg (0,1 m
The reaction was carried out under the same conditions as in Example 4 except that mol) was used. The results are shown in Table 1.
比較例１
重合触媒に五塩化ニオブ５４ｍｇ （０，２ｍｍｏ ｌ
）を使用したことを除いては実施例１と同一条件で反応
させた０重合体は得られなかった。Comparative Example 1 54 mg (0.2 mmol) of niobium pentachloride was added to the polymerization catalyst.
) was reacted under the same conditions as in Example 1 except that 0 polymer was not obtained.
比較例２
重合触媒に五塩化タンタルを１２ｍｇ （０，２ｍｍｏ
ｌ）を使用したことを除いては実施例１と同一条件で反
応させた０重合体は得られなかった。Comparative Example 2 12 mg of tantalum pentachloride (0.2 mmo
No polymer was obtained when the reaction was carried out under the same conditions as in Example 1 except that 1) was used.
Ｃ発明の効果〕
本発明の製法によれば、容易にフッ素またはトリフルオ
ロメチル基を有するポリフェニルアセチレン類を高収率
で得ることができる。C Effects of the Invention] According to the production method of the present invention, polyphenylacetylenes having fluorine or trifluoromethyl groups can be easily obtained in high yield.
以 上that's all
Claims (1)
フルオロメチル基を有するフェニル基を表す。） で示される化合物を重合するに際して重合触媒として五
塩化モリブデンもしくは六塩化タングステンを単独で、
または五塩化モリブデンもしくは六塩化タングステンを
有機金属化合物と共に使用することを特徴とする含フッ
素ポリフェニルアセチレン類の製法。 ２、有機金属化合物が、テトラフェニルスズ、テトラブ
チルスズ、トリフェニルシラン、トリエチルアルミニウ
ム、トリエチルシラン、トリフェニルアンチモン、トリ
フェニルビススマスよりなる群から選ばれた化合物であ
る特許請求の範囲第１項記載の製法。 ３、一般式（Ｉ）で示される化合物が。−（トリフルオ
ロメチル）フェニルアセチレンである特許請求の範囲第
１項記載の製法。[Claims] 1. As a polymerization catalyst when polymerizing a compound represented by the general formula CH≡CPhf (in the formula, Phf represents a phenyl group having 1 or 2 fluorine atoms or a trifluoromethyl group). Molybdenum pentachloride or tungsten hexachloride alone,
Or, a method for producing fluorine-containing polyphenylacetylenes, characterized by using molybdenum pentachloride or tungsten hexachloride together with an organometallic compound. 2. Claim 1, wherein the organometallic compound is a compound selected from the group consisting of tetraphenyltin, tetrabutyltin, triphenylsilane, triethylaluminum, triethylsilane, triphenylantimony, and triphenylbismuth. manufacturing method. 3. A compound represented by general formula (I). -(trifluoromethyl)phenylacetylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10571986A JPS62260804A (en) | 1986-05-07 | 1986-05-07 | Production of fluorine-containing polyphenylacetylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10571986A JPS62260804A (en) | 1986-05-07 | 1986-05-07 | Production of fluorine-containing polyphenylacetylene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62260804A true JPS62260804A (en) | 1987-11-13 |
Family
ID=14415137
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10571986A Pending JPS62260804A (en) | 1986-05-07 | 1986-05-07 | Production of fluorine-containing polyphenylacetylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62260804A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01275613A (en) * | 1988-04-28 | 1989-11-06 | Matsushita Electric Ind Co Ltd | Production of extraordinarily long polyacetylene or polyacene conjugated polymer |
| US4987209A (en) * | 1987-09-28 | 1991-01-22 | The President And Fellows Of Harvard | Diethynyl monomers and polymers thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4948778A (en) * | 1972-09-11 | 1974-05-11 | ||
| JPS5365384A (en) * | 1976-11-24 | 1978-06-10 | Toshinobu Higashimura | Polymerization process of phenyl acetylenes |
| JPS60166309A (en) * | 1984-02-09 | 1985-08-29 | Agency Of Ind Science & Technol | Polyphenylacetylene compound having fluorine or trifluoromethyl group |
-
1986
- 1986-05-07 JP JP10571986A patent/JPS62260804A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4948778A (en) * | 1972-09-11 | 1974-05-11 | ||
| JPS5365384A (en) * | 1976-11-24 | 1978-06-10 | Toshinobu Higashimura | Polymerization process of phenyl acetylenes |
| JPS60166309A (en) * | 1984-02-09 | 1985-08-29 | Agency Of Ind Science & Technol | Polyphenylacetylene compound having fluorine or trifluoromethyl group |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4987209A (en) * | 1987-09-28 | 1991-01-22 | The President And Fellows Of Harvard | Diethynyl monomers and polymers thereof |
| JPH01275613A (en) * | 1988-04-28 | 1989-11-06 | Matsushita Electric Ind Co Ltd | Production of extraordinarily long polyacetylene or polyacene conjugated polymer |
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