JP4864714B2 - フルオロプロペンを製造する方法 - Google Patents
フルオロプロペンを製造する方法 Download PDFInfo
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- JP4864714B2 JP4864714B2 JP2006538129A JP2006538129A JP4864714B2 JP 4864714 B2 JP4864714 B2 JP 4864714B2 JP 2006538129 A JP2006538129 A JP 2006538129A JP 2006538129 A JP2006538129 A JP 2006538129A JP 4864714 B2 JP4864714 B2 JP 4864714B2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
本発明は、市販の容易に入手可能な出発原料を使用して、工業的規模で且つ好収率でフルオロプロペンを製造する方法に関する。更に詳しくは、本発明は、非アルコール溶媒中における実質的に相溶性のアルカリ金属水酸化物若しくはアルカリ土類金属水酸化物の溶液と反応させることによって、又は、熱分解によって、ハロプロパンを脱ハロゲン化水素してフルオロプロペンを製造する方法に関する。
本発明は、フルオロプロペンを、高い収率及び選択性で商業的に製造できる2つの新規な脱ハロゲン化水素法を提供する。本発明の一つの面にしたがって、次式CF3CY=CXNHP(式中、X及びYは、独立に、水素であるか、又はフッ素、塩素、臭素及び沃素から選択されるハロゲンであり、そしてN及びPは、独立に、(N+P)=2という条件下で0,1又は2に等しい整数である)で表されるフルオロプロペンを調製する脱ハロゲン化水素法を提供する。前記方法では、下式:
本発明は、次式CF3CY=CXNHP(式中、X及びYは、独立に、水素であるか、又はフッ素、塩素、臭素及び沃素から選択されるハロゲンであり;そしてN及びPは、独立に、(N+P)=2という条件下で0,1又は2に等しい整数である)で表されるフルオロプロペンを調製する方法として一般的に説明できる。
脱ハロゲン化水素は、ハロプロパンが脱ハロゲン化水素する温度範囲で行う。この方法の一つの面にしたがって、アルカリ金属水酸化物又はアルカリ土類金属水酸化物のペレットを、周囲条件下で、撹拌しながら溶媒中に溶かす。次いで、アルカリ金属水酸化物又はアルカリ土類金属水酸化物の溶液の温度を加熱によって徐々に上げながら、その溶液中にハロプロパンを泡立てる。脱ハロゲン化水素反応の開始が観察されるまで段階的な加熱を継続し、その後で、プロセスが完了するまで、脱ハロゲン化水素反応が開始した温度に保つ。
真空下での反応も許容できる。真空圧は、約5トル〜約760トルであることができる。
実施例1
三つ口丸底フラスコ(5L)、機械式撹拌装置、還流冷却器、及び低温コールドトラップから成る反応構成に、3000mlのアセトニトリル及び9.9モル(504g)のKOHペレットを加えた。混合した後、5.1モル(684g)のHFC−245faをディップ管から加えた。試薬は、激しく撹拌しながらゆっくりと加熱した。反応は、60℃で観察された。粗生成物は、コールドフィンガーで捕集した。粗製物質をGCで分析すると、好収率のHFC−1234zeから成っていた。
5モル(752g)のHCFC 244faをディップ管からアセトニトリル/苛性アルカリ溶液に加える以外は、実施例1を繰り返す。試薬は、激しく撹拌しながらゆっくりと加熱した。反応は、実施例1での温度に比べてわずかに低い温度で観察される。粗生成物は、コールドフィンガーで捕集した。粗製物質をGCで分析すると、好収率のHFC−1234zeから成っていた。
フルオロポリマーで裏張りされた50ガロンの反応器に、75ポンドの液体SbCl5フッ素化触媒を入れた。その反応器に、構造化されたパッキングと還流冷却器とを含む直径6インチ x 長さ8フィートの触媒ストリッパを取り付けた。まず最初に、充分量のフッ化水素(HF)を加えることによって、触媒をフッ素化した。その反応器を、80〜95℃まで加熱し、そして150〜180psigの圧力にした。気体HFをスパージャから23〜28ポンド/時の流量で連続的に反応器に供給し、また、液体1,1,1,3,3−ペンタクロロプロパン(HCC−240fa)を40〜50ポンド/時の流量で連続的に供給した。Cl2を反応混合物に連続的に1.5〜2.0ポンド/時で加えて、触媒活性を保った。還流冷却器から出る気体を、KOH溶液を含むスクラバーを通過させて、過剰のHF及び反応中に発生するHClを除去した。スクラバー後に数千ポンドの粗生成物が捕集され、そしてそれをGCで分析した。以下の表は、GC面積%での粗生成物の主成分に関する分析である。材料をKOH溶液を含むスクラバーを通過させた後でのHFC1234zeの存在に注目されたい。
約132g(約1.33g/ccのかさ密度)の酸化クロム(III)触媒を、直径1インチのMonel管の反応器に入れた。触媒は、使用前に、乾燥させ、HFで前処理した。無水HFを反応器に供給しながら、反応器を約300℃の反応温度まで予熱した。
反応器が所望の温度及び圧力に達したら、有機供給原料(HCC−240)の供給を開始した。次に、HF及び有機供給原料を、所望の割合に調整した。HCFC244fa及びHFC−245faが、他の部分的にフッ素化された種、例えば1233zd、1234ze及び243faと一緒に、反応器流出生成物中に見出された。
典型的実験において、2.54cm x 81cmのMonel(登録商標)反応器を使用する。活性炭上に担持されたFeCl3触媒を約500ml反応器中に充填した。1リットル/時の窒素流下で反応器を150℃に加熱して、触媒を4時間乾燥させた。次いで、反応器の温度を、同じ窒素流下で250℃に加熱し、そして244faを1g/分で反応器に供給し、それと同時に窒素流を止めた。HFC−1234zeは、反応器の放出口におけるインラインGCの使用によって、98%の選択性及び95%のシングルパス転化率(single pass conversion)であることが分かった。
245faを供給原料として使用する以外は、実施例5に記載した同じ実験を繰り返す。反応器の出口では、1234zeが、95%の選択率及び85%のシングルパス転化率で見出される。
Claims (1)
- 1,3,3,3−テトラフルオロプロペン(HFO−1234ze)を調製するための方法であって、
1)気相又は液相での、1,1,1,3,3−ペンタクロロプロパン(HCC−240fa)とフッ化水素との反応によって、1−クロロ−1,3,3,3−テトラフルオロプロパン(HCFC−244fa)を含むハロプロパン反応物質を調製し、
2)HCFC−244faを含む前記ハロプロパン反応物質と、該ハロプロパン反応物質と相溶性である、アルカリ金属水酸化物又はアルカリ土類金属水酸化物のための非水非アルコール溶媒中で、少なくとも1種のアルカリ金属水酸化物又はアルカリ土類金属水酸化物の苛性溶液とを、触媒を使用せずに反応させることによって、HCFC−244faを含む前記ハロプロパン反応物質を分解し、HFO−1234zeを含む反応生成物を形成することを含み、ここで、該反応は、HCFC−244faの脱塩化水素が起こり、HFO−1234zeが形成する温度範囲内で行われ、前記非水非アルコール溶媒は、ニトリル、エーテル、エステル、アミド、ケトン、スルホキシド、ホスフェート、カルボキシレート、及びこれらの2つ以上の組み合わせからなる群から選択される、前記方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/694,272 US7230146B2 (en) | 2003-10-27 | 2003-10-27 | Process for producing fluoropropenes |
US10/694,272 | 2003-10-27 | ||
PCT/US2004/035131 WO2005042451A2 (en) | 2003-10-27 | 2004-10-25 | Process for producing fluoropropenes |
Related Child Applications (1)
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JP2010142786A Division JP5554643B2 (ja) | 2003-10-27 | 2010-06-23 | フルオロプロペンを製造する方法 |
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JP2007509942A JP2007509942A (ja) | 2007-04-19 |
JP4864714B2 true JP4864714B2 (ja) | 2012-02-01 |
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JP2006538129A Expired - Fee Related JP4864714B2 (ja) | 2003-10-27 | 2004-10-25 | フルオロプロペンを製造する方法 |
JP2010142786A Expired - Fee Related JP5554643B2 (ja) | 2003-10-27 | 2010-06-23 | フルオロプロペンを製造する方法 |
JP2013258584A Pending JP2014111601A (ja) | 2003-10-27 | 2013-12-13 | フルオロプロペンを製造する方法 |
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JP2010142786A Expired - Fee Related JP5554643B2 (ja) | 2003-10-27 | 2010-06-23 | フルオロプロペンを製造する方法 |
JP2013258584A Pending JP2014111601A (ja) | 2003-10-27 | 2013-12-13 | フルオロプロペンを製造する方法 |
Country Status (8)
Country | Link |
---|---|
US (5) | US7230146B2 (ja) |
EP (2) | EP1678106B1 (ja) |
JP (3) | JP4864714B2 (ja) |
CN (1) | CN1902152B (ja) |
DE (1) | DE04817444T1 (ja) |
ES (1) | ES2273620T3 (ja) |
TW (1) | TW200613245A (ja) |
WO (1) | WO2005042451A2 (ja) |
Cited By (1)
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EP4219607A1 (en) | 2022-01-28 | 2023-08-02 | Ricoh Company, Ltd. | Foam sheet |
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US8247624B2 (en) | 2012-08-21 |
JP2007509942A (ja) | 2007-04-19 |
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DE04817444T1 (de) | 2007-02-22 |
JP5554643B2 (ja) | 2014-07-23 |
US20120053370A1 (en) | 2012-03-01 |
JP2010215659A (ja) | 2010-09-30 |
EP1678106A2 (en) | 2006-07-12 |
US20080194888A1 (en) | 2008-08-14 |
EP1678106B1 (en) | 2012-01-04 |
EP2284143A2 (en) | 2011-02-16 |
US7803973B2 (en) | 2010-09-28 |
ES2273620T3 (es) | 2012-03-28 |
JP2014111601A (ja) | 2014-06-19 |
CN1902152B (zh) | 2010-10-13 |
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