JPS63162633A - Production of fluorine-containing olefin - Google Patents
Production of fluorine-containing olefinInfo
- Publication number
- JPS63162633A JPS63162633A JP31064886A JP31064886A JPS63162633A JP S63162633 A JPS63162633 A JP S63162633A JP 31064886 A JP31064886 A JP 31064886A JP 31064886 A JP31064886 A JP 31064886A JP S63162633 A JPS63162633 A JP S63162633A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- general formula
- reaction
- compound
- formula
- 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
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 53
- 239000011737 fluorine Substances 0.000 title claims abstract description 47
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 150000001336 alkenes Chemical class 0.000 title claims description 30
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000011701 zinc Substances 0.000 claims abstract description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 29
- -1 perfluoroalkyl chloride Chemical compound 0.000 claims abstract description 28
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 125000006551 perfluoro alkylene group Chemical group 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 abstract description 16
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- 125000005739 1,1,2,2-tetrafluoroethanediyl group Chemical group FC(F)([*:1])C(F)(F)[*:2] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YDUSRVDVRPPCFI-UHFFFAOYSA-N [F].[Zn] Chemical compound [F].[Zn] YDUSRVDVRPPCFI-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
発明の技術分野
本発明は、含フッ素オレフィンの製造方法に関し、ざら
に詳しくは、テトラフルオロエチレンの１時に副生ずる
フルオロアルキルクロライドを原料とした含フッ素オレ
フィンの製造方法に関する。Technical Field of the Invention The present invention relates to a method for producing a fluorine-containing olefin, and more particularly, to a method for producing a fluorine-containing olefin using a fluoroalkyl chloride, which is a by-product of tetrafluoroethylene, as a raw material. .
発明の技術的背景ならびにその問題点
テトラフルオロエチレンの重合反応により得られるポリ
テトラフルオロエチレン（ＰＴＦＥ）は、耐化学薬品性
、耐熱性などの優れた特性を有しているため、広く用い
られている。Technical background of the invention and its problems Polytetrafluoroethylene (PTFE), which is obtained through the polymerization reaction of tetrafluoroethylene, is widely used because it has excellent properties such as chemical resistance and heat resistance. There is.
ところで従来、テトラフルオロエチレンを製造しようと
すると、末端に塩素が結合した、たとえばＩ−１（ＣＦ
２ ）ｍＣ１などで示されるフルオロアルキルクロライ
ドが副生ずることは避けられなかった。このフルオロア
ルキルクロライドは、反応性がないため、従来廃棄処分
されてきたが、このパーフルオロアルキルクロライドの
有効利用を図ることが強く望まれていた。By the way, in the past, when trying to produce tetrafluoroethylene, for example, I-1 (CF
2) It was inevitable that fluoroalkyl chloride such as mC1 would be produced as a by-product. Since this fluoroalkyl chloride has no reactivity, it has conventionally been disposed of as waste, but it has been strongly desired to effectively utilize this perfluoroalkyl chloride.
本発明者らは、従来有効利用が図られず廃棄されてぎた
Ｈ （ＣＦ２ ）□Ｃ１などで示されるフルオロアルキ
ルクロライドの有効利用を図るべく鋭意検討したところ
、この化合物を亜鉛金属および特定の溶媒の存在下で加
熱処理すると、種々の用途に用いられうる含フッ素オレ
フィンを製造しうろことを見出して、本発明を完成する
に至った。The present inventors have conducted intensive studies to effectively utilize fluoroalkyl chlorides such as H (CF2)□C1, which have conventionally been discarded without being effectively utilized. The present inventors have discovered that heat treatment in the presence of fluorine-containing olefins can produce fluorine-containing olefins that can be used for various purposes, and have completed the present invention.
なお、末端に臭素あるいはヨウ素を有するパーフルオロ
アルキルブロマイドあるいはパーフルオロアルキルヨー
ダイトは、反応性に富むことが知られており、これらの
化合物から含フッ素オレフィンを製造しうろことが、た
とえばＪ、Ａ、Ｃ。It should be noted that perfluoroalkyl bromide or perfluoroalkyl iodite having bromine or iodine at the terminal is known to be highly reactive, and it is possible to produce fluorine-containing olefins from these compounds by, for example, J, A. ,C.
Ｓ、７９．４１５９ （１９５７）に記載されている。S, 79.4159 (1957).
しかしながら、末端に塩素が結合したフルオロアルキル
クロライドに関しては、従来この化合物は反応性がない
と考えられていたためか、この化合物から含フッ素オレ
フィンを製造しうろことは全く知られていなかった。However, with respect to fluoroalkyl chloride with a chlorine bonded to the terminal, it was not known at all that fluorine-containing olefins could be produced from this compound, probably because this compound was previously thought to have no reactivity.
発明の目的
本発明は、上記のような点に鑑みて完成されたものであ
って、テトラフルオロエチレンの製造時に副生じ、反応
性がないため従来廃棄処分に付されていたフルオロアル
キルクロライドを有効に利用することによって、種々の
用途に用いられうるような含フッ素オレフィンの製造方
法を提供することを目的としている。Purpose of the Invention The present invention was completed in view of the above-mentioned points, and is an effective method to effectively utilize fluoroalkyl chloride, which is produced as a by-product during the production of tetrafluoroethylene and was previously disposed of due to its lack of reactivity. The object of the present invention is to provide a method for producing fluorine-containing olefins that can be used for various purposes.
発明の概要
本発明に係る第１の含フッ素オレフィンの製造方法は、
一般式［Ｉ］ＸＲｆＣＦ２ ＣＦ２ ＣＩ（式中、Ｘは
水素原子またはフッ素原子を示し、Ｒｆは分枝状または
直鎖状のパーフルオロアルキレン基を示す）で表わされ
るパーフルオロアルキルクロライドを、亜鉛金属および
エーテル結合含有炭化水素溶媒の存在下に反応させて、
一般式［ＩＩ］ＸＲｊ ＣＦ＝ＣＦ２ （式中、Ｘお
よびＲｆは上記と同様である）で表わされる含フッ素オ
レフィンを製造することを特徴としている。Summary of the Invention The first method for producing a fluorine-containing olefin according to the present invention includes:
A perfluoroalkyl chloride represented by the general formula [I] and reacting in the presence of an ether bond-containing hydrocarbon solvent,
It is characterized by producing a fluorine-containing olefin represented by the general formula [II]XRj CF=CF2 (wherein X and Rf are the same as above).
本発明に係る第２の含フッ素オレフィンの製造方法は、
一般式ＸＲｆＣＦ２ＣＦ２Ｃｌ（式中、Ｘは水素原子ま
たはフッ素原子を示し、Ｒｆは分枝状または直鎖状の
パーフルオロアルキレン基を示す）で表わされるフルオ
ロアルキルクロライドを、亜鉛金属およびエーテル結合
含有炭化水素溶媒の存在下に反応させて、
一般式［Ｉ１１］ ＸＲｆＣＦ２ＣＦ２−ＺｎＣｌ −
Ａ３’３ Ｊ： Ｕ ／ マタハ一般式［ＩＶ］ （Ｘ
Ｒｆｃｒ＝２ＣＦ２ ＞２ ”Ｚｎ”Ａ （式中、Ｘ、
Ｒｊは上記と同様であり、Ａは溶媒分子を示す）で表わ
される有機含フッ素亜鉛化合物とし、次いでこの有機含
フッ素亜鉛化合物を反応液から分離した後熱分解させて
、一般式［ＩＩ］ＸＲｆＣＦ＝ＣＦ２ （式中、Ｘおよ
びＲｆは上記と同様である）で表わされる含フッ素オレ
フィンを製造することを特徴としている。The second method for producing a fluorine-containing olefin according to the present invention includes:
General formula XRfCF2CF2Cl (wherein, X represents a hydrogen atom or a fluorine atom, and Rf represents a branched or linear
A fluoroalkyl chloride represented by (representing a perfluoroalkylene group) is reacted in the presence of zinc metal and an ether bond-containing hydrocarbon solvent to obtain the general formula [I11] XRfCF2CF2-ZnCl -
A3'3 J: U / Mataha general formula [IV] (X
Rfcr=2CF2 >2 “Zn”A (wherein, X,
Rj is the same as above and A represents a solvent molecule), and then this organic fluorine-containing zinc compound is separated from the reaction solution and then thermally decomposed to obtain the general formula [II]XRfCF It is characterized by producing a fluorine-containing olefin represented by =CF2 (wherein X and Rf are the same as above).
また本発明によれば一般式［Ｉ］ ＸＲｆＣＦ２ＣＦ
−ＺｎＣＩ−Ａ、一般式［ＩＶ］ （ＸＲｆ０Ｆ２Ｃ
Ｆ２ ）２ ”Ｚｎ−Ａ （式中、Ｘは水素原子または
フッ素原子を示し、Ｒｆは分枝状または直鎖状のパーフ
ルオロアルキレン基を示し、Ａは溶媒分子を示す）で表
わされる有機含フッ素亜鉛化合物が提供される。Further, according to the present invention, general formula [I] XRfCF2CF
-ZnCI-A, general formula [IV] (XRf0F2C
F2)2''Zn-A (wherein, X represents a hydrogen atom or a fluorine atom, Rf represents a branched or linear perfluoroalkylene group, and A represents a solvent molecule). A fluorine zinc compound is provided.
本発明に係る含フッ素オレフィンの製造方法によれば、
テトラフルオロエチレンの製造時に副生じ、従来廃棄処
分されていた末端に塩素を有する一般式［Ｉ］ＸＲ（Ｃ
Ｆ２ ＣＦ２ ＣＩで表わされるフルオロアルキルクロ
ライドから、種々の用途に用いられうる含フッ素オレフ
ィンを高収率かつ高選択率で製造することができる。According to the method for producing a fluorine-containing olefin according to the present invention,
General formula [I]XR(C
Fluorine-containing olefins that can be used for various purposes can be produced with high yield and high selectivity from fluoroalkyl chloride represented by F2 CF2 CI.
１更０且迷煎韮」
以下本発明に係る含フッ素オレフィンの製造方法につい
て具体的に説明する。The method for producing a fluorine-containing olefin according to the present invention will be specifically described below.
本発明で反応原料として用いられるフルオロアルキルク
ロライドは、一般式［Ｉ］゛
ＸＲｆＣＦ２ＣＦ２ＣＩ −［Ｉ］（式中、Ｘは水
素またはフッ素原子を示し、Ｒｆは分枝状または直鎖状
のパーフルオロアルキレン基を示す）で示される。The fluoroalkyl chloride used as a reaction raw material in the present invention has the general formula [I]'XRfCF2CF2CI-[I] (wherein, (indicates a group).
このパーフルオロアルキルクロライドは、テトラフルオ
ロエチレンの製造時に副生し、従来利用されずに廃棄処
分に付されてきた。This perfluoroalkyl chloride is a by-product during the production of tetrafluoroethylene, and has conventionally been disposed of without being used.
一般式［Ｉ］ ＸＲｆＣＦ２ ＣＦ２ ＣＩ で示すし
るパーフルオロアルキルクロライドとしては、具体的に
は、以下のような化合物が示される。Specifically, the perfluoroalkyl chloride represented by the general formula [I] XRfCF2 CF2 CI includes the following compounds.
Ｈ（ＣＦ２）、 ＣＩ、 Ｆ （ＣＦ２ ＞ｎＣ＋、（
ｎ＝３〜１２）
Ｈ（ＣＦ、）ＣＦ （ＣＦ２ ＞４ｃ＋Ｆ３
ＣＦ３
など。H(CF2), CI, F (CF2 >nC+, (
n=3-12) H(CF, )CF (CF2 >4c+F3 CF3 etc.
本発明に係る第１の含フッ素オレフィンの製造方法では
、上記一般式［Ｉ］で表わされるフルオロアルキルクロ
ライドを、亜鉛金属およびエーテル結合含有炭化水素溶
媒の存在下に反応させることによって、一般式［ＩＩ］
ＸＲｆＣＦ＝ＣＦ２（式中、ＸおよびＲｆは上記と同様
である）で表わされる含フッ素オレフィンを製造してい
る。In the first method for producing a fluorine-containing olefin according to the present invention, a fluoroalkyl chloride represented by the general formula [I] is reacted with the general formula [I] in the presence of zinc metal and an ether bond-containing hydrocarbon solvent. II]
A fluorine-containing olefin represented by XRfCF=CF2 (wherein X and Rf are the same as above) is produced.
フルオロアルキルクロライドと亜鉛金属との反応は、下
記に示すような式に従って進行すると考えられる。The reaction between fluoroalkyl chloride and zinc metal is thought to proceed according to the formula shown below.
ＸＲ（ＣＦ２ ＣＦ２ Ｃｌ ＋Ｚｎ
↓
ＸＲｆＣＦ２ ＣＦ２−・ｚｎｃ１
↓
ＸＲｆＣＦ＝ＣＦ２ ＋ＺｎＦＣＩ
または
２ＸＲ（ＣＦ２ ＣＦ２ ＣＩ＋２２ｎ↓
（ＸＲｆＣＦ２ ＣＦ２ ＞２２ｎ＋ＺｎＣｌ２↓
２ＸＲ（ＣＦ＝ＣＦ２ ＋ＺｎＦ２ −反応過程に
おいて、ＸＲｆＣＦ２ＣＦ２・ＺｎＣＩまたは（ＸＲｙ
ＣＦ２ ＣＦ２ ）２ Ｚｎが中間体として生成し、
この中間体が、反応系中で熱分解することによって、ｘ
ＲｆＣＦ＝ＣＦ２で表ねされる含フッ素オレフィンが生
成する。XR(CF2 CF2 Cl +Zn ↓ XRfCF2 CF2-・znc1 ↓ XRfCF=CF2 +ZnFCI or 2XR(CF2 CF2 CI+22n↓ =CF2 +ZnF2 - In the reaction process, XRfCF2CF2・ZnCI or (XRy
CF2 CF2 )2 Zn is produced as an intermediate,
By thermally decomposing this intermediate in the reaction system, x
A fluorine-containing olefin represented by RfCF=CF2 is produced.
金属亜鉛は、フルオロアルキルクロライド１モルに対し
て０．３〜３０グラム原子好ましくは１〜６グラム原子
の量で用いられる。Metallic zinc is used in an amount of 0.3 to 30 gram atoms, preferably 1 to 6 gram atoms per mole of fluoroalkyl chloride.
金属亜鉛は、市販品をそのまま使用することもできるが
、表面の金属酸化物を除去してから反応に用いることが
好ましい。金属亜鉛の表面の酸化物を除去するためには
、金属亜鉛を希塩酸で処理した後、水洗、乾燥すればよ
い。Although a commercially available metal zinc can be used as it is, it is preferable to remove the metal oxide on the surface before using it in the reaction. In order to remove oxides on the surface of metal zinc, it is sufficient to treat the metal zinc with dilute hydrochloric acid, then wash with water and dry.
フルオロアルキルクロライドと金属亜鉛との反応に際し
て用いられるエーテル結合含有炭化水素溶媒としては、
ジオキサン、テトラヒドロフラン、エチレングリコール
ジメチルエーテル、ジエチレングリコールジメチルエー
テル、などが用いられる。このうらジオキサン、テトラ
ヒドロフランが好ましく、特にジオキサンが好ましい。The ether bond-containing hydrocarbon solvent used in the reaction between fluoroalkyl chloride and metallic zinc includes:
Dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc. are used. Dioxane and tetrahydrofuran are preferred, and dioxane is particularly preferred.
なお溶媒として活性水素を有するアルコール類などの化
合物を用いると、中間体として生成する有機含フッ素亜
鉛化合物が溶媒によって分解される恐れがあるため好ま
しくない。Note that it is not preferable to use a compound such as an alcohol having active hydrogen as a solvent because the organic fluorine-containing zinc compound produced as an intermediate may be decomposed by the solvent.
このようなエーテル結合含有炭化水素溶媒は、原料であ
るフルオロアルキルクロライド１容量に対して、５容量
以上のけで用いられることが好ましい。また反応に用い
る前に、エーテル結合含有炭化水素溶媒を脱水しておく
ことが好ましい。Such an ether bond-containing hydrocarbon solvent is preferably used in an amount of 5 or more volumes per 1 volume of the raw material fluoroalkyl chloride. Further, it is preferable to dehydrate the ether bond-containing hydrocarbon solvent before using it in the reaction.
フルオロアルキルクロライドと金属亜鉛との反応は、１
００〜３００℃好ましくは１８０〜２５０’Ｃ程度の温
度で行なわれる。反応温度が低すぎると、中間体として
生成するＸＲｒＣＦ２ＣＦ２−Ｚ ｎ ＣＩまたは（Ｘ
ＲｆＣＦ２ＣＦ２ ＞２ Ｚｎで表わされる有機含フッ
素亜鉛化合物の熱分解が起こりにくいため好ましくなく
、一方反応温度が高すぎると、上記有機含フッ素亜鉛イ
し合物の熱分解によりＸＲｆ ＣＦ２ＣＦ２で表わされ
る含フッ素オレフィン以外の化合物が生成し、含フッ素
オレフィンの選択率が低下するため好ましくない。The reaction between fluoroalkyl chloride and metal zinc is 1
It is carried out at a temperature of about 00 to 300°C, preferably about 180 to 250'C. If the reaction temperature is too low, XRrCF2CF2-Z n CI or (X
RfCF2CF2 >2 This is not preferable because thermal decomposition of the organic fluorine-containing zinc compound represented by Zn is difficult to occur.On the other hand, if the reaction temperature is too high, the fluorine-containing compound represented by XRfCF2CF2 is This is not preferable because compounds other than olefins are produced and the selectivity of fluorine-containing olefins is reduced.
上記の反応時間は、反応温度によって大きく変化するが
、通常５〜２０時間程度である。The above reaction time varies greatly depending on the reaction temperature, but is usually about 5 to 20 hours.
上記のような反応は常圧下または加圧下で行なうことが
できるが、加圧下で行なうことが好ましい。また反応は
窒素などの不活性雰囲気下で行なうことが好ましい。Although the above reaction can be carried out under normal pressure or under increased pressure, it is preferable to carry out under increased pressure. Further, the reaction is preferably carried out under an inert atmosphere such as nitrogen.
次に本発明に係る第２の含フッ素オレフィンの製造方法
について説明すると、反応原料としてのフルオロアルキ
ルクロライドと金属亜鉛とを、エーテル結合含有炭化水
素溶媒の存在下に反応させるまでは、第１含フッ素オレ
フインの製造方法と同様である。第２の含フッ素オレフ
ィンの製造方法では、フルオロアルキルクロライドと金
属亜鉛とを反応させた後、一般式［ＩＩ１］ＸＲｊ Ｃ
Ｆ２ＣＦ２・ＺｎＣｌ・Ａおよび／または一般式［ＩＶ
］ （ＸＲｆＣＦ２ＣＦ２ ）２ ・Ｚｎ−Ａ（式中、
Ｘ、Ｒｆは上記と同様であり、Ａはエーテル結合含有炭
化水素溶媒である）で表わされる有機含フッ素亜鉛化合
物を反応液から分離し、この有機含フッ素亜鉛化合物を
熱分解させて、一般式［ＩＩ］ＸＲｆＣＦ＝ＣＦ２で表
わされる含フッ素オレフィンを製造している。Next, the second method for producing a fluorine-containing olefin according to the present invention will be explained. The method is similar to the method for producing fluorine olefin. In the second method for producing a fluorine-containing olefin, after reacting a fluoroalkyl chloride and metal zinc, the general formula [II1]XRj C
F2CF2・ZnCl・A and/or general formula [IV
] (XRfCF2CF2)2 ・Zn-A (in the formula,
X and Rf are the same as above, A is an ether bond-containing hydrocarbon solvent) is separated from the reaction solution, and this organic fluorine-containing zinc compound is thermally decomposed to give the general formula [II] A fluorine-containing olefin represented by XRfCF=CF2 is produced.
ここで一般式［Ｉ１１］ ＸＲ「ＣＦ２ ＣＦ２ ・Ｚ
ｎＣＩ −Ａあ６（、Ｎは一般式［ＩＶ］ （ＸＲｙ
ＣＦ２ＣＦ２＞２・Ｚｎ−Ａとして表わされる有機含フ
ッ素亜鉛化合物は、従来知られていない新規な化合物で
ある。この新規な有機含フッ素亜鉛化合物の構造は、元
素分析、熱重量分析、ＩＲ，ＮＭＲなどにより確認され
る。Here, the general formula [I11] XR "CF2 CF2 ・Z
nCI-Aa6(, N is the general formula [IV] (XRy
The organic fluorine-containing zinc compound represented by CF2CF2>2.Zn-A is a novel compound that has not been previously known. The structure of this novel organic fluorine-containing zinc compound is confirmed by elemental analysis, thermogravimetric analysis, IR, NMR, etc.
わされる有機含フッ素亜鉛化合物は、元素分析すると理
論値とよく一致した値を示す。また熱重母分析によると
、下記の反応が起っていることがわかる。Elemental analysis of the organic fluorine-containing zinc compound shown in Table 1 shows values in good agreement with the theoretical values. Furthermore, according to thermal deuterium analysis, it is found that the following reactions occur.
メタノールに溶かし、ガスクロマトグラフにより分析す
ると、亜鉛１モルに対してジオキサンが１モル検出され
、この有機含フッ素亜鉛化合物は亜剣）１モルに対して
ジオキサン１モルが付加していることがわかる。When dissolved in methanol and analyzed by gas chromatography, 1 mol of dioxane was detected per 1 mol of zinc, indicating that 1 mol of dioxane was added to 1 mol of this organic fluorine-containing zinc compound.
上記のような有機含フッ素亜鉛化合物の熱分解は、１０
０〜３００℃好ましくは１８０〜２５０℃の温度で行な
われる。また上記有機含フッ素亜鉛化合物の熱分解は、
活性水素を有しない化合物溶媒たとえばジオキサン、テ
トラヒドロフランなどのエーテル結合含有炭化水素溶媒
中で行なうことが好ましいが、必ずしも溶媒の存在下に
行なわなくともよい。Thermal decomposition of the organic fluorine-containing zinc compound as described above takes place at 10
It is carried out at a temperature of 0 to 300°C, preferably 180 to 250°C. In addition, the thermal decomposition of the above organic fluorine-containing zinc compound is
Although it is preferable to carry out the reaction in a compound solvent having no active hydrogen, such as an ether bond-containing hydrocarbon solvent such as dioxane or tetrahydrofuran, the reaction does not necessarily have to be carried out in the presence of a solvent.
有機含フッ素亜鉛化合物の熱分解を行なうに際して、新
たに金属亜鉛を反応系に添加すると、含フッ素オレフィ
ンの収率が向上するので好ましい。When thermally decomposing an organic fluorine-containing zinc compound, it is preferable to newly add metallic zinc to the reaction system because the yield of the fluorine-containing olefin improves.
なお本発明により得られた含フッ素オレフィンは、たと
えば界面活性剤用原料、エポキシ樹脂硬化剤、農薬、医
薬の中間体などとして用いられうる。The fluorine-containing olefin obtained according to the present invention can be used, for example, as a raw material for surfactants, an epoxy resin curing agent, agricultural chemicals, and intermediates for medicines.
発明の効果
本発明に係る含フッ素オレフィンの製造方法によれば、
テトラフルオロエチレンの製造時に副生じ、反応性がな
いため従来廃棄処分されていた末端に塩素を有する一般
式［Ｉ］ＸＲｆＣＦ２ＣＦ２Ｃｌで表わされるフルオロ
アルキルクロライドから、種々の用途に用いられうる含
フッ素オレフィンを高収率かつ高選択率で製造すること
ができる。Effects of the Invention According to the method for producing a fluorine-containing olefin according to the present invention,
From the fluoroalkyl chloride represented by the general formula [I] It can be produced with high yield and high selectivity.
以下本発明を実施例により説明するが、本発明はこれら
実施例に限定されるものではない。EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.
Ｘ匹叢ユ
電ｖｉ１ｍ拌装置を備えた５００ｒｎｉオートクレーブ
（材質５ＵＳ−３１６＞、Ｈ（ＣＦ２）８Ｃ１４５ｄ（
７８，６５？、０．１８０ｍｏｌ）と、モレキュラシー
ブで脱水したジオキサン２２５ｄと、金属亜鉛粉末５０
ｇ（０，７６５ｍｏｆ）とを窒素雰囲気下に仕込んだ。500rni autoclave (material 5US-316>, H (CF2) 8C145d (
78,65? , 0.180 mol), 225 d of dioxane dehydrated with a molecular sieve, and 50 mol of metallic zinc powder.
g (0,765 mof) was charged under a nitrogen atmosphere.
この金属亜鉛は表面の酸化被膜を除くため、水中に懸濁
させた亜鉛粉末に濃塩酸をＺｎ／ＨＣｌ ＝ １０／１
（ｍｏｌ比）となルヨウニ、窒素雰囲気下で攪拌下に
滴下し、濾過水洗した後加熱下に減圧乾燥することによ
って、調製した。In order to remove the oxide film on the surface of this metallic zinc, concentrated hydrochloric acid was added to the zinc powder suspended in water at a ratio of Zn/HCl = 10/1.
(molar ratio) was added dropwise under stirring under a nitrogen atmosphere, filtered and washed with water, and then dried under reduced pressure while heating.
次に窒素によりオートクレーブを２０Ｋｇ／ｃＩｉに加
圧した後、オイルバスに浸して２００℃に加熱し、攪拌
下に６時間反応させた。Next, the autoclave was pressurized to 20 kg/cIi with nitrogen, then immersed in an oil bath, heated to 200° C., and reacted for 6 hours with stirring.
オートクレーブを冷却し、未反応亜鉛を濾別した後、濾
液の一部を採りガスクロマトグラフで分析定量したとこ
ろ、Ｈ（ＣＦ２）９ ＣＩの反応率は７０％であり、Ｈ
（ＣＦ２）６０Ｆ＝ＣＦ２ｈ〜７７％の選択率で生成し
ていることがわかった。After cooling the autoclave and filtering off unreacted zinc, a portion of the filtrate was taken and analyzed and quantified using a gas chromatograph.The reaction rate of H(CF2)9CI was 70%, and the reaction rate of H(CF2)9CI was 70%.
It was found that (CF2)60F=CF2h was produced with a selectivity of 77%.
残りの濾液を、２０段のオルダシヨー型蒸留塔（３０７
１１＃１φ）を用いて、常圧下に還流比１０〜２０で精
留した。塔頂温度９５〜９９．５℃で留出した留分をガ
スクロマトグラフで分析したところ、この留分はほとん
どがジオキサンとＨ（ＣＦ２ ＞５ ＣＦ＝ＣＦ２とか
ら成っており、その組成比はほぼ７：３であった。この
留出物を１０倍容■の蒸留水中に投入し、下層に分離し
たオイルを分液し、再度同様の水洗操作を行なったとこ
ろ、ジオキサンは完全に除去され、ＩＩＴ！度９９．１
％の ）−１（ＣＦ２ ）６ ＣＦ＝ＣＦ２３４．０ｇ
が無色透明液体として得られた。The remaining filtrate was passed through a 20-stage Oldasillo distillation column (307
11#1φ) at a reflux ratio of 10 to 20 under normal pressure. A gas chromatograph analysis of the fraction distilled at a top temperature of 95 to 99.5°C revealed that this fraction was mostly composed of dioxane and H (CF2 > 5 CF=CF2, and the composition ratio was approximately The ratio was 7:3. When this distillate was poured into 10 times the volume of distilled water, the oil separated into the lower layer was separated, and the same water washing operation was performed again, dioxane was completely removed. IIT! Degree 99.1
%)-1(CF2)6 CF=CF234.0g
was obtained as a colorless transparent liquid.
Ｘ塵■２
反応温度を変化させた以外は、実施例１と同様にして反
応を行なった。結果を表１に示す。X dust 2 The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed. The results are shown in Table 1.
よ適医旦
金属亜鉛とＨ（ＣＦ２＞８ｃ＋の仕込みモル比を変化ざ
けた以外は、実施例１と同様にして反応を行なった。結
果を表２に示す。The reaction was carried out in the same manner as in Example 1, except that the molar ratio of metallic zinc and H (CF2>8c+) was varied. The results are shown in Table 2.
夫直叢Ａ
Ｈ（ＣＦ２）８Ｃ１および金属亜鉛粉末の伍を１／２に
減らし、Ｈ（ＣＦ２）ｇ ＣＩ／ジオキサン（ｖｏｌ比
）を変化させた以外は、実施例１と同様にして反応を行
なった。結果を表３に示づ。The reaction was carried out in the same manner as in Example 1, except that the concentrations of H(CF2)8C1 and metal zinc powder were reduced to 1/2 and the H(CF2)g CI/dioxane (vol ratio) was changed. I did it. The results are shown in Table 3.
実施例５
金属亜鉛の種類を変えた以外は、実施例１と同様にして
反応を行なった。結果を表４に示す。Example 5 A reaction was carried out in the same manner as in Example 1 except that the type of metal zinc was changed. The results are shown in Table 4.
実施例６
ジオキサンを他の溶媒に変えた以外は、実施例１と同様
にして反応を行なった。結果を表５に示す。Example 6 A reaction was carried out in the same manner as in Example 1, except that dioxane was replaced with another solvent. The results are shown in Table 5.
止較邸ニ
ジオキサンを全く用いなかった以外は、実施例４と同様
にして反応を行なった。ガスクロマトグラフで分析定徂
したところ、Ｈ（ＣＦ２＞８ＣＩは全く反応していなか
った。The reaction was carried out in the same manner as in Example 4, except that no dioxane was used. Analysis by gas chromatography revealed that H (CF2>8CI) had not reacted at all.
±に血ｌ
溶媒としてジオキサンの代わりにエタノールを用いた以
外は、実施例６と同様にして反応を行なった。ガスクロ
マトグラフで分析したところ、１−１ （ＣＦ２ ）３
ＣＩの反応率は９５％であったが、Ｈ（ＣＦ ）
ＣＦ＝ＣＦ２は全く生成しておらず、Ｈ（ＣＦ２）
８８が８９％の選択率で生成していた。The reaction was carried out in the same manner as in Example 6, except that ethanol was used instead of dioxane as the solvent. When analyzed by gas chromatography, 1-1 (CF2)3
The reaction rate of CI was 95%, but H(CF)
CF=CF2 is not generated at all, H(CF2)
88 was produced with a selectivity of 89%.
大血叢ユ
反応温度を１６５℃とし、反応時間を８時間とした以外
は１．実施例１と同様にして反応を行なった。未反応亜
鉛を濾別した後、濾液の一部を採ってガスクロマトグラ
フで分析したところ、Ｈ（ＣＦ２＞８ＣＩの反応率は４
３％Ｈ（ＣＦ２ ）。1. Except that the macroplexus reaction temperature was 165°C and the reaction time was 8 hours. The reaction was carried out in the same manner as in Example 1. After filtering off unreacted zinc, a portion of the filtrate was analyzed using a gas chromatograph, and the reaction rate of H(CF2>8CI) was 4.
3% H(CF2).
ＣＦ＝ＣＦ２の選択率は１１％であった。The selectivity of CF=CF2 was 11%.
残りの濾液を減圧下に濃縮（５Ｉｒｔ！ｎＨｇ、１００
℃）したところ、全体が固化し、褐色固体が得られた。The remaining filtrate was concentrated under reduced pressure (5 Irt! nHg, 100
℃), the whole solidified and a brown solid was obtained.
この固化物を次のようにｆｆｉ理した。まず、ジオキチ
ン／ヘキサン＝１／２（ｖｏｌ比）を加えてスラリーと
し、不溶物を濾別した。この不溶物は分析の結果ＺｎＣ
ｌ２で必った。濾液を濃縮固化した後、ジオキサン／ヘ
キサン＝３／８で再結晶し、黄褐色結晶を得、さらにこ
の結晶をジオキサン／ヘキサン＝２／３で再結晶後、室
温で３時間減圧乾燥することにより、白色結晶１０．４
ｙを（ワだ（結晶■）。This solidified product was subjected to ffi treatment as follows. First, diochitin/hexane=1/2 (vol ratio) was added to form a slurry, and insoluble matter was filtered off. As a result of analysis, this insoluble material was found to be ZnC.
I needed it in l2. After concentrating and solidifying the filtrate, it was recrystallized with dioxane/hexane = 3/8 to obtain yellowish brown crystals, which was further recrystallized with dioxane/hexane = 2/3, and then dried under reduced pressure at room temperature for 3 hours. , white crystal 10.4
y (Wada (crystal ■).
１回目の再結晶母液を濃縮固化させた後、ＣＦ３−ＣＨ
Ｃ１２を加えてスラリーとし、不溶物を濾別することに
よって得られた白色固体を、ジオキサン／ヘキサン＝２
／３から再結晶し、室温で３時間減圧乾燥することによ
り、白色結晶５．２ｇを（ｑた（結晶■）、。After concentrating and solidifying the first recrystallization mother liquor, CF3-CH
The white solid obtained by adding C12 to make a slurry and filtering out insoluble matter was dioxane/hexane=2
By recrystallizing from /3 and drying under reduced pressure at room temperature for 3 hours, 5.2 g of white crystals were obtained (crystals ■).
このようにして得られた結晶は、■、■いずれも強い潮
解性を示した。結晶■および結晶■の元素分析結果を表
６に示す。The crystals obtained in this way both exhibited strong deliquescent properties. Table 6 shows the elemental analysis results of crystals ■ and crystals ■.
表に
れらの結晶をメタノールに溶かし、ガスクロマトグラフ
により分析したところ、いずれの結晶も亜鉛１モルに対
し１モルのジオキナンを含有していることがわかった。When these crystals were dissolved in methanol and analyzed by gas chromatography, it was found that each crystal contained 1 mole of dioquinane per 1 mole of zinc.
る。また結晶■の熱重■分析を行なったところ、重量減
少が７８．２％（理論値７９．７％）であり、その残渣
を分析すると残渣中には、Ｆ：１６．２％（１５，８％
）、Ｃ１：２８．７％結晶■の熱重量分析における重旧
減少率は８６．６％（理論値８９．２％）であり、その
残渣中にはＦ：３８．１％（３６，８％）が含まれてお
り、Ｃ１は検出されなかったことから、の反応が起きて
いることがわかった。Ru. In addition, when the crystal (2) was subjected to thermogravimetric analysis, the weight loss was 78.2% (theoretical value 79.7%), and the residue was analyzed and found to contain F: 16.2% (15, 8%
), C1:28.7% crystal ■ in thermogravimetric analysis showed a reduction rate of 86.6% (theoretical value: 89.2%), and the residue contained F:38.1% (36.8%). %), and C1 was not detected, indicating that the reaction occurred.
Ｘ亙叢旦
反応温度を１７０℃とし、反応時間を１０時間とし、Ｃ
ｕＣｌ２ ａ即した亜鉛を用いた以外は、実施例１と同
様にして反応を行なった。未反応亜鉛を濾別した後、濾
液の一部を採ってガスクロマトグラフで分析したところ
、この濾液中にはト１（ＣＦ２ ＞ ８ ｃ＋
が ２．４５’ｌミ」％、 ト１ （ＯＦ２ ）６０
Ｆ＝ＣＦ２が３．９６重量％含まれており、Ｈ（ＣＦ２
）３Ｃ１の反応率は９０．２％であり、Ｈ（ＣＦ２）６
ＣＦ＝ＣＦ２の選択率は１９．８％であった。The reaction temperature was 170°C, the reaction time was 10 hours, and the
The reaction was carried out in the same manner as in Example 1, except that zinc containing uCl2a was used. After filtering off unreacted zinc, a portion of the filtrate was taken and analyzed by gas chromatography.
is 2.45'l%, 1 (OF2) 60
Contains 3.96% by weight of F=CF2, H(CF2
)3C1 reaction rate was 90.2%, H(CF2)6
The selectivity of CF=CF2 was 19.8%.
次に、５０ｄオートクレーブ（材質５ＵＳ−３０４）に
、上記の濾液５ｄ、亜鉛粉末１Ｊおよび回転子を窒素雰
囲気下に仕込み、窒素で２０に３／ｃｍに加圧した後、
オイルバスに浸し２００℃で所定時間処理した。その後
、室温まで冷却し、ガスクロマトグラフにより分析した
。結果を、亜鉛を添加しない場合の結果とともに表７に
示した。Next, 5 d of the above filtrate, 1 J of zinc powder, and a rotor were placed in a 50 d autoclave (material 5US-304) under a nitrogen atmosphere, and after pressurizing with nitrogen to 20 to 3/cm,
It was immersed in an oil bath and treated at 200°C for a predetermined time. Thereafter, it was cooled to room temperature and analyzed by gas chromatography. The results are shown in Table 7 along with the results when zinc was not added.
Claims (1)
中、Ｘは水素原子またはフッ素原子を示し、Ｒ＿ｆは分
枝状または直鎖状のパーフルオロアルキレン基を示す）
で表わされるパーフルオロアルキルクロライドを、亜鉛
金属およびエーテル結合含有炭化水素溶媒の存在下に反
応させて、 一般式［II］ＸＲ＿ｆＣＦ＝ＣＦ＿２（式中、Ｘおよび
Ｒ＿ｆは上記と同様である）で表わされる含フッ素オレ
フィンを製造することを特徴とする含フッ素オレフィン
の製造方法。 ２）一般式ＸＲ＿ｆＣＦ＿２ＣＦ＿２Ｃｌ（式中、Ｘは
水素原子またはフッ素原子を示し、Ｒ＿ｆは分枝状また
は直鎖状のパーフルオロアルキレン基を示す）で表わさ
れるパーフルオロアルキルクロライドを、亜鉛金属およ
びエーテル結合含有炭化水素溶媒の存在下に反応させて
、 一般式［III］ＸＲ＿ｆＣＦ＿２ＣＦ＿２・ＺｎＣｌ・
Ａおよび／または一般式［IV］（ＸＲ＿ｆＣＦ＿２ＣＦ
＿２）＿２・Ｚｎ・Ａ（式中、Ｘ、Ｒ＿ｆは上記と同様
であり、Ａは溶媒分子を示す）で表わされる有機含フッ
素亜鉛化合物とし、次いでこの有機含フッ素亜鉛化合物
を反応液から分離した後熱分解させて、一般式［II］Ｘ
Ｒ＿ｆＣＦ＝ＣＦ＿２（式中、ＸおよびＲ＿ｆは上記と
同様である）で表わされる含フッ素オレフィンを製造す
ることを特徴とする含フッ素オレフィンの製造方法。 ３）一般式［III］ ＸＲ＿ｆＣＦ＿２ＣＦ＿２・ＺｎＣｌ・Ａ （式中、Ｘは水素原子またはフッ素原子を示し、Ｒ＿ｆ
は分枝状または直鎖状のパーフルオロアルキレン基を示
し、Ａは溶媒分子を示す。）で表わされる有機含フッ素
亜鉛化合物。 ４）一般式［IV］ （ＸＲ＿ｆＣＦ＿２ＣＦ＿２）＿２・Ｚｎ・Ａ（式中、
Ｘは水素原子またはフッ素原子を示し、Ｒ＿ｆは分枝状
または直鎖状のパーフルオロアルキレン基を示し、Ａは
溶媒分子を示す。）で表わされる有機含フッ素亜鉛化合
物。[Claims] 1) General formula [I]XR_fCF_2CF_2Cl (wherein, X represents a hydrogen atom or a fluorine atom, and R_f represents a branched or linear perfluoroalkylene group)
A perfluoroalkyl chloride represented by is reacted in the presence of zinc metal and an ether bond-containing hydrocarbon solvent to form a compound represented by the general formula [II] XR_fCF=CF_2 (wherein X and R_f are the same as above) A method for producing a fluorine-containing olefin, the method comprising producing a fluorine-containing olefin. 2) A perfluoroalkyl chloride represented by the general formula XR_fCF_2CF_2Cl (wherein, By reacting in the presence of a containing hydrocarbon solvent, the general formula [III]XR_fCF_2CF_2・ZnCl・
A and/or general formula [IV] (XR_fCF_2CF
_2) _2.Zn.A (in the formula, X and R_f are the same as above, and A represents a solvent molecule) is an organic fluorine-containing zinc compound, and then this organic fluorine-containing zinc compound is separated from the reaction solution. After that, it is thermally decomposed to give the general formula [II]
A method for producing a fluorine-containing olefin, comprising producing a fluorine-containing olefin represented by R_fCF=CF_2 (wherein X and R_f are the same as above). 3) General formula [III] XR_fCF_2CF_2・ZnCl・A (wherein, X represents a hydrogen atom or a fluorine atom, and R_f
represents a branched or linear perfluoroalkylene group, and A represents a solvent molecule. ) is an organic fluorine-containing zinc compound represented by 4) General formula [IV] (XR_fCF_2CF_2)_2・Zn・A (in the formula,
X represents a hydrogen atom or a fluorine atom, R_f represents a branched or linear perfluoroalkylene group, and A represents a solvent molecule. ) is an organic fluorine-containing zinc compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31064886A JPS63162633A (en) | 1986-12-26 | 1986-12-26 | Production of fluorine-containing olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31064886A JPS63162633A (en) | 1986-12-26 | 1986-12-26 | Production of fluorine-containing olefin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63162633A true JPS63162633A (en) | 1988-07-06 |
Family
ID=18007776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31064886A Pending JPS63162633A (en) | 1986-12-26 | 1986-12-26 | Production of fluorine-containing olefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63162633A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001192347A (en) * | 1999-10-26 | 2001-07-17 | Kanto Denka Kogyo Co Ltd | Method for producing perfluoroalkadiene |
| JP2001192346A (en) * | 1999-10-26 | 2001-07-17 | Kanto Denka Kogyo Co Ltd | Method for producing perfluoroalkadiene |
| JP2006312637A (en) * | 2005-05-05 | 2006-11-16 | Solvay Solexis Spa | Method of dehalogenation |
| JP2006312636A (en) * | 2005-05-05 | 2006-11-16 | Solvay Solexis Spa | Method of dehalogenation |
| JP2008056690A (en) * | 2001-12-04 | 2008-03-13 | Mitsubishi Tanabe Pharma Corp | Method for producing grignard reagent |
| JP2011157287A (en) * | 2010-01-29 | 2011-08-18 | Tokyo Institute Of Technology | Perfluoroalkyl (organic zinc)-lithium complex and method for producing perfluoroalkyl group-containing alcohols using the same |
| WO2019230456A1 (en) * | 2018-05-28 | 2019-12-05 | Ａｇｃ株式会社 | Method for producing fluorine-containing propene |
-
1986
- 1986-12-26 JP JP31064886A patent/JPS63162633A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001192347A (en) * | 1999-10-26 | 2001-07-17 | Kanto Denka Kogyo Co Ltd | Method for producing perfluoroalkadiene |
| JP2001192346A (en) * | 1999-10-26 | 2001-07-17 | Kanto Denka Kogyo Co Ltd | Method for producing perfluoroalkadiene |
| JP4684401B2 (en) * | 1999-10-26 | 2011-05-18 | 関東電化工業株式会社 | Method for producing perfluoroalkadiene |
| JP2008056690A (en) * | 2001-12-04 | 2008-03-13 | Mitsubishi Tanabe Pharma Corp | Method for producing grignard reagent |
| JP2006312637A (en) * | 2005-05-05 | 2006-11-16 | Solvay Solexis Spa | Method of dehalogenation |
| JP2006312636A (en) * | 2005-05-05 | 2006-11-16 | Solvay Solexis Spa | Method of dehalogenation |
| JP2011157287A (en) * | 2010-01-29 | 2011-08-18 | Tokyo Institute Of Technology | Perfluoroalkyl (organic zinc)-lithium complex and method for producing perfluoroalkyl group-containing alcohols using the same |
| WO2019230456A1 (en) * | 2018-05-28 | 2019-12-05 | Ａｇｃ株式会社 | Method for producing fluorine-containing propene |
| JPWO2019230456A1 (en) * | 2018-05-28 | 2021-06-17 | Ａｇｃ株式会社 | Fluorine-containing propene manufacturing method |
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