JPH1072381A - Production of 1,1,1,3,3-pentafluoropropane - Google Patents
Production of 1,1,1,3,3-pentafluoropropaneInfo
- Publication number
- JPH1072381A JPH1072381A JP8226638A JP22663896A JPH1072381A JP H1072381 A JPH1072381 A JP H1072381A JP 8226638 A JP8226638 A JP 8226638A JP 22663896 A JP22663896 A JP 22663896A JP H1072381 A JPH1072381 A JP H1072381A
- Authority
- JP
- Japan
- Prior art keywords
- pentafluoropropane
- chloro
- hydrogen fluoride
- reaction
- catalyst
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリウレタンフォ−ム
等の発泡剤あるいは冷媒等として有用な１，１，１，
３，３−ペンタフルオロプロパンおよびその前駆体とな
る１，１，１，３−テトラフルオロ−３−クロロプロパ
ンの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to 1,1,1,1 useful as a foaming agent such as polyurethane foam or a refrigerant.
The present invention relates to a method for producing 3,3-pentafluoropropane and 1,1,1,3-tetrafluoro-3-chloropropane which is a precursor thereof.
【０００２】[0002]
【従来技術】１，１，１，３，３−ペンタフルオロプロ
パンの製造方法としては従来、ＣＦ3−ＣＣｌＸ−Ｃ
Ｆ2Ｃｌを接触水素化する方法（特開平６−２５６２３
５号公報）、１，１，３，３，３−ペンタフルオロ−
１−プロペンをＰｄ−Ａｌ2Ｏ3で水素化する方法（Ｉｚ
ｖｅｓｔ．Ａｋａｄ．Ｎａｕｋ Ｓ．Ｓ．Ｓ．Ｒ．，Ｏ
ｔｄｅｌ．Ｋｈｉｍ．Ｎａｕｋ．１９６０，１４１２−
１８；ＣＡ ５５，３４９ｆ）、１，２，２−トリク
ロロペンタフルオロプロパンを水素化する方法（ＵＳＰ
２９４２０３６号）、１，１，１，３，３−ペンタク
ロロプロパンを触媒の存在下液相フッ素化する方法（Ｗ
Ｏ９６／０１７９７）などが知られている。2. Description of the Related Art As a method for producing 1,1,1,3,3-pentafluoropropane, conventionally, CF 3 -CClX-C
Method for catalytic hydrogenation of F 2 Cl (JP-A-6-25623)
No. 5), 1,1,3,3,3-pentafluoro-
Method for hydrogenating 1-propene with Pd-Al 2 O 3 (Iz
vest. Akad. Nauk S.D. S. S. R. , O
tdel. Khim. Nauk. 1960, 1412-
18; CA 55,349f), a method for hydrogenating 1,2,2-trichloropentafluoropropane (USP
No. 294,036), a method of liquid-phase fluorination of 1,1,1,3,3-pentachloropropane in the presence of a catalyst (W
O96 / 01797) and the like.
【０００３】[0003]
【発明が解決しようとする課題】前記した特開平６−２
５６２３５号公報またはＵＳＰ２９４２０３６号公報な
どに記載された水素化による塩素原子の水素置換は反応
率および選択率に優れた方法ではあるが、触媒の劣化が
著しく、また、原料であるフッ素化塩素化物を予め調製
しなければならず、工業的に適用するには困難な点が多
い。一方、前記で示したオレフィンへの水素付加によ
る方法はすぐれた１，１，１，３，３−ペンタフルオロ
プロパンの製造方法であるが、原料となる１，１，３，
３，３−ペンタフルオロ−１−プロペンを入手すること
が困難であり工業的に採用するには問題がある。また、
ＷＯ９６／０１７９７の方法は１，１，１，３，３−ペ
ンタフルオロプロパンの選択率、収率がともに比較的低
い。SUMMARY OF THE INVENTION The above-mentioned JP-A-6-2
No. 56235 or US Pat. No. 2,942,036 discloses that hydrogen substitution of chlorine atoms by hydrogenation is a method excellent in the reaction rate and the selectivity. However, the deterioration of the catalyst is remarkable, It must be prepared in advance, and there are many difficulties for industrial application. On the other hand, the method by hydrogenation to an olefin described above is an excellent method for producing 1,1,1,3,3-pentafluoropropane.
It is difficult to obtain 3,3-pentafluoro-1-propene, and there is a problem in industrially employing it. Also,
The method of WO96 / 01797 has relatively low selectivity and yield of 1,1,1,3,3-pentafluoropropane.
【０００４】[0004]
【問題点を解決するための具体的手段】本発明者らはか
かる従来技術の問題点に鑑み、工業的規模での製造に適
した１，１，１，３，３−ペンタフルオロプロパンの製
造方法を確立するべく各種の製造プロセスについて鋭意
検討を加えたところ、対応する不飽和塩素化物にフッ化
水素を付加し、得られた塩素化フッ素化炭化水素を不均
化することでフッ素炭化水素を製造できることを見いだ
し、本発明を完成した。SUMMARY OF THE INVENTION In view of the above problems of the prior art, the present inventors have prepared 1,1,1,3,3-pentafluoropropane suitable for production on an industrial scale. After diligent studies on various manufacturing processes to establish a method, hydrogen fluoride was added to the corresponding unsaturated chlorinated product, and the resulting chlorinated fluorinated hydrocarbon was disproportionated to obtain a fluorine hydrocarbon. Have been found, and the present invention has been completed.
【０００５】すなわち、本発明は液相中において付加触
媒存在下、１−クロロ−３，３，３−トリフルオロプロ
ペンにフッ化水素を付加反応させた後、生成した１，
１，１，３−テトラフルオロ−３−クロロプロパンを不
均化触媒存在下不均化させることを特徴とする１，１，
１，３，３−ペンタフルオロプロパンの製造方法であ
る。That is, according to the present invention, 1-chloro-3,3,3-trifluoropropene is subjected to an addition reaction with hydrogen fluoride in the presence of an addition catalyst in a liquid phase, and the resulting 1,1 is formed.
1,1,3-tetrafluoro-3-chloropropane is disproportionated in the presence of a disproportionation catalyst,
This is a method for producing 1,3,3-pentafluoropropane.
【０００６】本発明に使用する１−クロロ−３，３，３
−トリフルオロプロペンは、１，１，１−トリフルオロ
プロパンを塩素化して得られた１，１，１−トリフルオ
ロ−３，３−ジクロロプロパンをアルコール性塩基性化
合物で脱塩化水素する方法（Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏ
ｃ．，１９４２，６４，１１５８．）、３，３，３−ト
リフルオロプロピンに塩化水素を付加反応させる方法
（Ｊ．Ｃｈｅｍ．Ｓｏｃ．，１９５２，３４９０．）ま
たは３−クロロ−１，１，１−トリフルオロ−３−ヨー
ドプロパンのエタノール性ＫＯＨによる脱ヨウ化水素反
応方法（Ｊ．Ｃｈｅｍ．Ｓｏｃ．，１９５３，１１９
９．）等で得ることができる。1-chloro-3,3,3 used in the present invention
-Trifluoropropene is a method of dehydrochlorinating 1,1,1-trifluoro-3,3-dichloropropane obtained by chlorinating 1,1,1-trifluoropropane with an alcoholic basic compound ( J. Am. Chem. So
c. , 1942, 64, 1158. ), 3,3,3-trifluoropropyne with addition of hydrogen chloride (J. Chem. Soc., 1952, 3490.) or 3-chloro-1,1,1-trifluoro-3-iodopropane Dehydroiodination reaction of ethanol with ethanolic KOH (J. Chem. Soc., 1953, 119)
9. ).
【０００７】また、本出願人は特願平８−５９７１号の
明細書に気相にてフッ素化触媒存在下、１，１，１，
３，３−ペンタクロロプロパンをフッ化水素によりフッ
素化して得る方法を開示している。Further, the present applicant has disclosed in the specification of Japanese Patent Application No. 8-5971 that 1,1,1,1 is used in the gas phase in the presence of a fluorination catalyst.
It discloses a method of fluorinating 3,3-pentachloropropane with hydrogen fluoride.
【０００８】本発明の付加反応ならびに不均化反応は、
回分式、または原料を連続的に反応領域に供給し、連続
的に抜き出す連続式のいずれも採り得るが、連続式が好
ましい。これらの反応形態において、当業者が容易に調
節しうる程度の反応条件の変更を妨げるものではない。[0008] The addition reaction and disproportionation reaction of the present invention include:
A batch system or a continuous system in which the raw materials are continuously supplied to the reaction zone and continuously withdrawn can be adopted, but a continuous system is preferable. In these reaction modes, it does not prevent the reaction conditions from being changed to a degree that can be easily adjusted by those skilled in the art.
【０００９】付加反応に用いる触媒は、アンチモンまた
はホウ素のハロゲン化物が好ましい。三フッ化ホウ素は
フッ化水素に配位し、Ｈ−Ｆ結合のイオン性を高め、オ
レフィンへの付加を助けるものと推測される（Ａ．Ｌ．
Ｈｅｎｎｅら、Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，１９４
８，７０，７５８）。本発明にかかるアンチモン化合物
を具体的に挙げると、五塩化アンチモン、五臭化アンチ
モン、五沃化アンチモン、五フッ化アンチモン、三塩化
アンチモン、三臭化アンチモン、三沃化アンチモンを例
示できるが、五塩化アンチモンまたは三塩化アンチモン
が最も好ましい。また、ホウ素の場合、三塩化ホウ素、
三臭化ホウ素、三沃化ホウ素、三フッ化ホウ素を例示で
きるが、三フッ化ホウ素が最も好ましい。The catalyst used in the addition reaction is preferably an antimony or boron halide. It is speculated that boron trifluoride coordinates to hydrogen fluoride, enhances the ionicity of the HF bond, and aids the addition to olefins (AL.
Henne et al. Am. Chem. Soc. , 194
8, 70, 758). Specific examples of the antimony compound according to the present invention include antimony pentachloride, antimony pentabromide, antimony pentaiodide, antimony pentafluoride, antimony trichloride, antimony tribromide, and antimony triiodide. Antimony pentachloride or antimony trichloride is most preferred. In the case of boron, boron trichloride,
Although boron tribromide, boron triiodide, and boron trifluoride can be exemplified, boron trifluoride is most preferred.
【００１０】不均化触媒に用いる触媒は、アンチモンま
たはアルミニウムのハロゲン化物が好ましく、前述のア
ンチモン化合物の他に、ハロゲン化アルミニウムとして
は、塩化アルミニウム、臭化アルミニウム、沃化アルミ
ニウムを例示できるが、塩化アルミニウムが最も好まし
い。The catalyst used for the disproportionation catalyst is preferably an antimony or aluminum halide. In addition to the above-mentioned antimony compound, examples of the aluminum halide include aluminum chloride, aluminum bromide and aluminum iodide. Aluminum chloride is most preferred.
【００１１】本発明の方法において、反応は次式に示す
ように１−クロロ−３，３，３−トリフルオロプロペン
とフッ化水素との付加反応ならびに１，１，１，３−テ
トラフルオロ−３−クロロプロパンの不均化反応の２段
反応で構成され、それぞれ個別に反応することができる
が、アンチモン触媒を用いる場合は１ポットの反応で目
的の１，１，１，３，３−ペンタフルオロプロパンが得
られるので、特に好ましい。 （１） ＣＦ3ＣＨ＝ＣＣｌＨ＋ＨＦ→ＣＦ3ＣＨ2ＣＣ
ｌＦＨ （２） ２ＣＦ3ＣＨ2ＣＣｌＦＨ→ＣＦ3ＣＨ2ＣＦ2Ｈ
＋ＣＦ3ＣＨ2ＣＣｌ2Ｈ １−クロロ−３，３，３−トリフルオロプロペンに対す
るフッ化水素のモル比は１〜２の範囲で十分であり、こ
の範囲未満では１−クロロ−３，３，３−トリフルオロ
プロペンへのフッ化水素の付加率は高くなく、この範囲
を越えても１−クロロ−３，３，３−トリフルオロプロ
ペン反応率の向上は認められず、未反応フッ化水素回収
の点からも経済的に有利でない。In the method of the present invention, the reaction is carried out by the addition reaction of 1-chloro-3,3,3-trifluoropropene with hydrogen fluoride and 1,1,1,3-tetrafluoro- It consists of a two-stage reaction of the disproportionation reaction of 3-chloropropane, which can react individually. However, when an antimony catalyst is used, the desired 1,1,1,3,3-pentane is reacted in a one-pot reaction. It is particularly preferred since fluoropropane is obtained. (1) CF 3 CH = CClH + HF → CF 3 CH 2 CC
IFH (2) 2CF 3 CH 2 CClFH → CF 3 CH 2 CF 2 H
The molar ratio of hydrogen fluoride to + CF 3 CH 2 CCl 2 H 1-chloro-3,3,3,3-trifluoropropene in the range of 1-2 is sufficient; below this range 1-chloro-3,3,3. The rate of addition of hydrogen fluoride to 3-trifluoropropene was not high, and even beyond this range, no improvement in the 1-chloro-3,3,3-trifluoropropene conversion was observed, and unreacted hydrogen fluoride was not observed. It is not economically advantageous in terms of recovery.
【００１２】付加反応に用いられる触媒濃度は１−クロ
ロ−３，３，３−トリフルオロプロペンに対し０．１〜
５０モル％が好ましく、２〜２０モル％がより好まし
い。０．１モル％以下では１−クロロ−３，３，３−ト
リフルオロプロペンへのフッ化水素の反応速度が小さ
く、また５０モル％以上では、高沸点化合物からなるタ
−ルの生成量の増加が著しいので好ましくない。The concentration of the catalyst used in the addition reaction is 0.1 to 0.1 to 1-chloro-3,3,3-trifluoropropene.
50 mol% is preferable, and 2 to 20 mol% is more preferable. At 0.1 mol% or less, the reaction rate of hydrogen fluoride to 1-chloro-3,3,3-trifluoropropene is low, and at 50 mol% or more, the amount of tar formed of a high-boiling compound is reduced. It is not preferable because the increase is remarkable.
【００１３】不均化反応に用いられる触媒濃度は、１，
１，１，３−テトラフルオロ−３−クロロプロパンに対
し０．１〜５０モル％が好ましく、１〜２０モル％がよ
り好ましい。０．１モル％以下では不均化反応速度が小
さく、また５０モル％以上では、触媒と１，１，１，３
−テトラフルオロ−３−クロロプロパンとの反応等によ
り触媒劣化が著しいので好ましくない。The catalyst concentration used in the disproportionation reaction is 1,
It is preferably 0.1 to 50 mol%, more preferably 1 to 20 mol%, based on 1,1,3-tetrafluoro-3-chloropropane. Below 0.1 mol%, the disproportionation reaction rate is low, and above 50 mol%, the catalyst and 1,1,1,3
-It is not preferable because the catalyst deteriorates remarkably due to reaction with tetrafluoro-3-chloropropane and the like.
【００１４】反応温度は０〜１５０℃が好ましく、３０
〜１００℃がより好ましい。０℃以下では１−クロロ−
３，３，３−トリフルオロプロペンの反応率、１，１，
１，３，３−ペンタフルオロプロパンの収率共低下し、
また１５０℃以上ではタ−ル生成量が増加し、触媒劣化
が著しい。The reaction temperature is preferably from 0 to 150.degree.
-100 ° C is more preferred. 1-chloro-
Conversion of 3,3,3-trifluoropropene, 1,1,
The yield of 1,3,3-pentafluoropropane decreases together,
If the temperature is higher than 150 ° C., the amount of tar generated increases and the catalyst deteriorates remarkably.
【００１５】本反応の方法では、反応の調節、触媒劣化
の防止を目的として反応系に溶媒を共存させることがで
きる。溶媒としては反応に不活性な飽和のフッ素化溶
剤、フッ素化塩素化溶媒またはパーフルオロ化合物等が
挙げられる。In the present reaction method, a solvent can be co-present in the reaction system for the purpose of controlling the reaction and preventing catalyst deterioration. Examples of the solvent include a saturated fluorinated solvent inert to the reaction, a fluorinated chlorinated solvent, a perfluoro compound, and the like.
【００１６】原料の反応器中への導入方法は、１−クロ
ロ−３，３，３−トリフルオロプロペン単独またはフッ
化水素と同時に行うことができる。これらの場合反応器
からの留出ガスを冷却する還流冷却器の温度を調節する
ことにより、生成有機物（モル）と原料有機物（モル）
のバランスをとることができる。The method of introducing the raw materials into the reactor can be carried out by using 1-chloro-3,3,3-trifluoropropene alone or simultaneously with hydrogen fluoride. In these cases, by adjusting the temperature of the reflux condenser for cooling the distillate gas from the reactor, the produced organic matter (mol) and the starting organic matter (mol) are controlled.
Can be balanced.
【００１７】反応に必要な圧力は反応温度にもよるが、
反応器内で反応混合物を液相の状態に保てれば良く、１
〜１００Ｋｇ／ｃｍ2Ｇが好ましく、１〜２０Ｋｇ／ｃ
ｍ2Ｇがより好ましい。The pressure required for the reaction depends on the reaction temperature.
What is necessary is just to keep the reaction mixture in a liquid phase in the reactor.
１００100 kg / cm 2 G is preferable, and 1-20 kg / c.
m 2 G is more preferred.
【００１８】本発明の方法に使用する反応器は、ハステ
ロイ、ステンレス鋼、モネル、ニッケルなど、あるいは
これらの金属または四フッ化エチレン樹脂、クロロトリ
フルオロエチレン樹脂、フッ化ビニリデン樹脂、ＰＦＡ
樹脂などを内部にライニングした材質で製作したものが
好ましい。The reactor used in the method of the present invention may be Hastelloy, stainless steel, Monel, nickel, or the like, or any of these metals, ethylene tetrafluoride resin, chlorotrifluoroethylene resin, vinylidene fluoride resin, PFA
It is preferable to use a resin or the like made of a material lined inside.
【００１９】本発明の方法で製造された１，１，１，
３，３−ペンタフルオロプロパンは、フッ素化反応生成
物について公知の方法、例えば、酸性分の除去、塩基性
水溶液または／および水での洗浄、乾燥、蒸留を適用し
て精製され、高純度の１，１，１，３，３−ペンタフル
オロプロパンが得られる。The 1,1,1, produced by the method of the present invention
The 3,3-pentafluoropropane is purified by applying known methods for the fluorination reaction product, for example, removal of acidic components, washing with a basic aqueous solution or / and water, drying, distillation, and high purity. 1,1,1,3,3-pentafluoropropane is obtained.
【００２０】[0020]
【実施例】以下、実施例により本発明を詳細に説明する
が、実施態様はこれらに限られない。EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments are not limited thereto.
【００２１】〔実施例１〕還流冷却器、調圧弁と攪拌機
を備えた１ｌのＳＵＳ３１６製オートクレーブに触媒と
して五塩化アンチモン０．０５モル（１５．０ｇ）およ
びフッ化水素０．６モル（１２ｇ）を加え、攪拌しなが
ら昇温した。五塩化アンチモンとフッ化水素との反応で
生ずる塩化水素を排出後、オートクレーブを氷冷し、１
−クロロ−３，３，３−トリフルオロプロペン０．５モ
ル（６４．１ｇ）を加え、攪拌しながら反応器内の温度
を８０℃に昇温し、ガス成分を還流冷却器を通して抜き
出しながら６ｋｇ／ｃｍ2Ｇで３時間保持した。反応中
および反応終了後圧力を常圧に戻した時に還流冷却器か
ら留出したガスを水層および濃硫酸層に通した後、ドラ
イアイス−メタノールで冷却されたトラップに捕集し
た。この捕集物とオートクレーブ中の内容物を塩酸で洗
浄し、さらに水で洗浄して得られた３７．２ｇの有機物
をガスクロマトグラフで分析し、生成物組成（面積％）
を求めた。その結果、１，１，１，３，３ーペンタフル
オロプロパンは５７．９％、１−クロロ−３，３，３−
トリフルオロプロペンは５．０％、１，１，１，３−テ
トラフルオロ−３−クロロプロパンは１０．７％、１，
１，１−トリフルオロ−３，３−ジクロロプロパンは２
６．４％であった。EXAMPLE 1 0.05 mol (15.0 g) of antimony pentachloride and 0.6 mol (12 g) of hydrogen fluoride were used as catalysts in a 1 l SUS316 autoclave equipped with a reflux condenser, a pressure regulating valve and a stirrer. Was added and the temperature was raised while stirring. After discharging hydrogen chloride produced by the reaction between antimony pentachloride and hydrogen fluoride, the autoclave was cooled on ice and
0.5 mol (64.1 g) of -chloro-3,3,3-trifluoropropene was added, the temperature in the reactor was increased to 80 ° C. while stirring, and 6 kg while extracting gas components through a reflux condenser. / Cm 2 G for 3 hours. During the reaction and after the completion of the reaction, when the pressure was returned to normal pressure, the gas distilled from the reflux condenser was passed through an aqueous layer and a concentrated sulfuric acid layer, and then collected in a trap cooled with dry ice-methanol. The collected substance and the contents in the autoclave were washed with hydrochloric acid, and further washed with water. 37.2 g of an organic substance obtained was analyzed by gas chromatography, and the product composition (area%) was obtained.
I asked. As a result, 57.9% of 1,1,1,3,3-pentafluoropropane and 1-chloro-3,3,3-
Trifluoropropene is 5.0%, 1,1,1,3-tetrafluoro-3-chloropropane is 10.7%,
1,1-trifluoro-3,3-dichloropropane is 2
6.4%.
【００２２】〔実施例２〕還流冷却器、調圧弁と攪拌機
を備えた１ｌのＳＵＳ３１６製オートクレーブに触媒と
して五塩化アンチモン０．１モル（２９．９ｇ）を導入
後、オートクレーブを氷冷し、１，１，１，３−テトラ
フルオロ−３−クロロプロパン１．０モル（１４９．７
ｇ）を加え、攪拌しながら反応器内の温度を８０℃に昇
温し、ガス成分を還流冷却器を通して抜き出しながら６
ｋｇ／ｃｍ2Ｇで３時間保持した。反応中および反応終
了後圧力を常圧に戻した時に還流冷却器から留出したガ
スを水層および濃硫酸層に通した後、ドライアイス−メ
タノールで冷却されたトラップに捕集した。この捕集物
とオートクレーブ中の内容物を塩酸で洗浄し、さらに水
で洗浄して得られた９４．５ｇの有機物をガスクロマト
グラフで分析し、生成物組成（面積％）を求めた。その
結果、１，１，１，３，３ーペンタフルオロプロパンは
５７．４％、１−クロロ−３，３，３−トリフルオロプ
ロペンは６．０％、１，１，１，３−テトラフルオロ−
３−クロロプロパンは１２．４％、１，１，１−トリフ
ルオロ−３，３−ジクロロプロパンは２３．２％であっ
た。Example 2 0.1 mol (29.9 g) of antimony pentachloride was introduced as a catalyst into a 1 liter SUS316 autoclave equipped with a reflux condenser, a pressure regulating valve and a stirrer, and the autoclave was cooled on ice. 1.0 mol of 1,1,1,3-tetrafluoro-3-chloropropane (149.7
g), the temperature inside the reactor was raised to 80 ° C. while stirring, and while extracting gas components through a reflux condenser, 6 g.
It was kept at kg / cm 2 G for 3 hours. During the reaction and after the completion of the reaction, when the pressure was returned to normal pressure, the gas distilled from the reflux condenser was passed through an aqueous layer and a concentrated sulfuric acid layer, and then collected in a trap cooled with dry ice-methanol. The collected substance and the contents in the autoclave were washed with hydrochloric acid, and then 94.5 g of an organic substance obtained by washing with water was analyzed by gas chromatography to obtain a product composition (area%). As a result, 57.4% of 1,1,1,3,3-pentafluoropropane, 6.0% of 1-chloro-3,3,3-trifluoropropene and 1,1,1,3-tetrapropene Fluoro-
3-chloropropane was 12.4% and 1,1,1-trifluoro-3,3-dichloropropane was 23.2%.
【００２３】〔実施例３〕触媒として塩化アルミニウム
０．０５モル（６．７ｇ）を用いた以外は実施例２と同
様にして反応を行い、回収して得られた１０３．１ｇの
有機物をガスクロマトグラフで分析し、生成物組成（面
積％）を求めた。その結果、１，１，１，３，３ーペン
タフルオロプロパンの組成は４２．４％、１−クロロ−
３，３，３−トリフルオロプロペンは３７．２％、１，
１，１，３−テトラフルオロ−３−クロロプロパンは
３．２％、１，１，１−トリフルオロ−３，３−ジクロ
ロプロパンは１７．２％であった。Example 3 A reaction was carried out in the same manner as in Example 2 except that 0.05 mol (6.7 g) of aluminum chloride was used as a catalyst, and 103.1 g of an organic substance obtained by recovery was subjected to gas chromatography. The product composition (area%) was determined by chromatography. As a result, the composition of 1,1,1,3,3-pentafluoropropane was 42.4% and 1-chloro-
3,3,3-trifluoropropene is 37.2%,
1,1,3-Tetrafluoro-3-chloropropane was 3.2% and 1,1,1-trifluoro-3,3-dichloropropane was 17.2%.
【００２４】〔実施例４〕還流冷却器、調圧弁と攪拌機
を備えた１ｌのＳＵＳ３１６製オートクレーブに触媒と
して三臭化ホウ素０．０５モル（１２．５ｇ）およびフ
ッ化水素０．６５モル（１３ｇ）を加え、攪拌しながら
昇温した。三臭化ホウ素とフッ化水素との反応で生じた
臭化水素を排出後、オートクレーブを氷冷し、１−クロ
ロ−３，３，３−トリフルオロプロペン０．５モル（６
４．１ｇ）を加え、攪拌しながら反応器内の温度を８０
℃に昇温し、ガス成分を還流冷却器を通して抜き出しな
がら６ｋｇ／ｃｍ2Ｇで６時間保持した。反応中および
反応終了後圧力を常圧に戻した時に還流冷却器から留出
したガスを水層および濃硫酸層に通した後、ドライアイ
ス−メタノールで冷却されたトラップに捕集した。この
捕集物とオートクレーブ中の内容物を塩酸で洗浄し、さ
らに水で洗浄して得られた６３．９ｇの有機物をガスク
ロマトグラフで分析し、生成物組成（面積％）を求める
と、１，１，１，３−テトラフルオロ−３−クロロプロ
パンの組成は９０．７％、１−クロロ−３，３，３−ト
リフルオロプロペンは９．３％であった。Example 4 In a 1-liter SUS316 autoclave equipped with a reflux condenser, a pressure regulating valve and a stirrer, 0.05 mol (12.5 g) of boron tribromide and 0.65 mol (13 g) of hydrogen fluoride were used as catalysts. ) Was added and the temperature was raised while stirring. After discharging the hydrogen bromide generated by the reaction between boron tribromide and hydrogen fluoride, the autoclave was cooled with ice, and 0.5 mol of 1-chloro-3,3,3-trifluoropropene (6 mol
4.1 g), and the temperature in the reactor was increased to 80 with stirring.
The temperature was raised to 0 ° C, and the gas component was kept at 6 kg / cm 2 G for 6 hours while being extracted through a reflux condenser. During the reaction and after the completion of the reaction, when the pressure was returned to normal pressure, the gas distilled from the reflux condenser was passed through an aqueous layer and a concentrated sulfuric acid layer, and then collected in a trap cooled with dry ice-methanol. The collected substance and the contents in the autoclave were washed with hydrochloric acid, and then 63.9 g of an organic substance obtained by washing with water was analyzed by gas chromatography to determine the product composition (area%). The composition of 1,1,3-tetrafluoro-3-chloropropane was 90.7%, and the composition of 1-chloro-3,3,3-trifluoropropene was 9.3%.
【００２５】[0025]
【発明の効果】本発明の製造方法は、１−クロロ−３，
３，３−トリフルオロプロペンへのフッ化水素の付加
と、その際得られる１，１，１，３−テトラフルオロ−
３−クロロプロパンの不均化反応による１，１，１，
３，３−ペンタフルオロプロパンの生成が何れも高い選
択率と収率で起こるので、工業的製造方法として有用で
ある。According to the production method of the present invention, 1-chloro-3,
Addition of hydrogen fluoride to 3,3-trifluoropropene and 1,1,1,3-tetrafluoro-
1,1,1,1 by disproportionation reaction of 3-chloropropane
Since the formation of 3,3-pentafluoropropane occurs in all cases with high selectivity and yield, it is useful as an industrial production method.
Claims (6)
ロペンに付加触媒存在下フッ化水素を付加して１，１，
１，３−テトラフルオロ−３−クロロプロパンを得、次
いで該１，１，１，３−テトラフルオロ−３−クロロプ
ロパンを不均化触媒存在下不均化することを特徴とする
１，１，１，３，３−ペンタフルオロプロパンの製造方
法。1. A method according to claim 1, wherein hydrogen fluoride is added to 1-chloro-3,3,3-trifluoropropene in the presence of an addition catalyst to form 1,1,1.
1,1,1 characterized by obtaining 1,3-tetrafluoro-3-chloropropane and then disproportionating the 1,1,1,3-tetrafluoro-3-chloropropane in the presence of a disproportionation catalyst. For producing 3,3,3-pentafluoropropane.
ロゲン化ホウ素（ハロゲンは、塩素、臭素、沃素、フッ
素をいう。）から選ばれる少なくとも１種類の化合物で
ある請求項１記載の１，１，１，３，３−ペンタフルオ
ロプロパンの製造方法。2. The 1,1 compound according to claim 1, wherein the addition catalyst is at least one compound selected from antimony pentahalide and boron trihalide (halogen means chlorine, bromine, iodine and fluorine). For producing 1,1,3,3-pentafluoropropane.
ロゲン化アルミニウム（ハロゲンは、塩素、臭素、沃
素、フッ素をいう。）から選ばれる少なくとも１種類の
化合物である請求項１記載の１，１，１，３，３−ペン
タフルオロプロパンの製造方法。3. The method according to claim 1, wherein the disproportionation catalyst is at least one compound selected from antimony pentahalide and aluminum halide (halogen means chlorine, bromine, iodine and fluorine). A method for producing 1,1,3,3-pentafluoropropane.
リフルオロプロペン１モルに対し、約１〜２モル用いる
請求項１記載の１，１，１，３，３−ペンタフルオロプ
ロパンの製造方法。4. The 1,1,1,3,3-pentafluorohydrogen according to claim 1, wherein hydrogen fluoride is used in an amount of about 1 to 2 mol per 1 mol of 1-chloro-3,3,3-trifluoropropene. Propane manufacturing method.
ロペンに付加触媒存在下フッ化水素を付加することから
なる１，１，１，３−テトラフルオロ−３−クロロプロ
パンの製造方法。5. A process for producing 1,1,1,3-tetrafluoro-3-chloropropane, comprising adding hydrogen fluoride to 1-chloro-3,3,3-trifluoropropene in the presence of an addition catalyst.
ロロプロパンを不均化触媒存在下不均化することからな
る１，１，１，３，３−ペンタフルオロプロパンの製造
方法。6. A process for producing 1,1,1,3,3-pentafluoropropane, comprising disproportionating 1,1,1,3-tetrafluoro-3-chloropropane in the presence of a disproportionation catalyst.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22663896A JP3164288B2 (en) | 1996-08-28 | 1996-08-28 | Method for producing 1,1,1,3,3-pentafluoropropane |
| US08/752,879 US6235951B1 (en) | 1996-01-17 | 1996-11-20 | Method for producing 1,1,1,3,3-pentafluoropropane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22663896A JP3164288B2 (en) | 1996-08-28 | 1996-08-28 | Method for producing 1,1,1,3,3-pentafluoropropane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1072381A true JPH1072381A (en) | 1998-03-17 |
| JP3164288B2 JP3164288B2 (en) | 2001-05-08 |
Family
ID=16848325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22663896A Expired - Fee Related JP3164288B2 (en) | 1996-01-17 | 1996-08-28 | Method for producing 1,1,1,3,3-pentafluoropropane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3164288B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010090086A1 (en) * | 2009-02-03 | 2010-08-12 | セントラル硝子株式会社 | Method of purifying (z)-1-chloro-3,3,3-trifluoropropene |
-
1996
- 1996-08-28 JP JP22663896A patent/JP3164288B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010090086A1 (en) * | 2009-02-03 | 2010-08-12 | セントラル硝子株式会社 | Method of purifying (z)-1-chloro-3,3,3-trifluoropropene |
| JP2010202640A (en) * | 2009-02-03 | 2010-09-16 | Central Glass Co Ltd | Method for purifying (z)-1-chloro-3,3,3-trifluoropropene |
| US8524956B2 (en) | 2009-02-03 | 2013-09-03 | Central Glass Company, Limited | Method of purifying (Z)-1-chloro-3,3,3-trifluoropropene |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3164288B2 (en) | 2001-05-08 |
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