JP4369614B2 - Perfluorodicarbonyl compounds - Google Patents
Perfluorodicarbonyl compounds Download PDFInfo
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- JP4369614B2 JP4369614B2 JP2000384155A JP2000384155A JP4369614B2 JP 4369614 B2 JP4369614 B2 JP 4369614B2 JP 2000384155 A JP2000384155 A JP 2000384155A JP 2000384155 A JP2000384155 A JP 2000384155A JP 4369614 B2 JP4369614 B2 JP 4369614B2
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- Prior art keywords
- perfluorodicarbonyl
- compounds
- compound
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- fluorine
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Description
【0001】
【発明の属する技術分野】
本発明は、新規なパーフルオロジカルボニル化合物に関する。
【0002】
【従来の技術】
パーフルオロジカルボニル化合物は、簡易に2価のアルコール、アミド、エステル等に誘導することができ、そうして得られる種々のパーフルオル化合物は界面活性剤、潤滑油、農薬、医薬品、防汚剤、離型剤などの含フッ素製品の成分として有用であり、また種々の含フッ素ポリマーの製造原料としても有用である。
【0003】
従来、こうした目的のためには、一般的にFOC-C6F12-COFなどのパーフルオロアルキレン基を骨格に有するパーフルオロ化合物が多く使用されてきた。しかし、このような化合物はフッ素が分子の中心部に直鎖パーフルオロアルキレン構造の形で存在するため通常固体状態にあり、また構造が剛直であるため得られる誘導体の物性も制限されるという問題があった。
【0004】
一方、柔軟な構造を持つパーフルオロアルキル基を導入しうるパーフルオロジカルボニル化合物の例としては米国特許998978号に示されるシュウ酸フロライドにヘキサフルオロプロピレンオキシドを付加させて得られる次のような化合物が知られている。
【0005】
【化3】
【0006】
この化合物は上記の式 FOC-C6F12-COFなどの化合物とは異なり、分子中に存在するエーテル結合により柔軟さを持つものの、原料となるシュウ酸フロライドは不安定で扱いにくく、合成過程において副生する不純物のために得られたパーフルオロジカルボニル化合物は精製が困難である。そのため、工程が煩雑になる上に収率も低く、高価にならざるを得ない。
以上のような背景から、本発明の目的は、柔軟な構造を有し、容易にかつ安価に製造することができ、純度の高いパーフルオロジカルボニル化合物を提供することにある。
【0007】
【課題を解決するための手段】
本発明者らは鋭意努力の結果、次式(8)、式(9)及び式(10):
【化1】
で示される3種のパーフルオロジカルボニル化合物の混合物が上記の課題を解決しうることを見出した。即ち、これらのパーフルオロジカルボニル化合物は、柔軟なエーテル結合を有し、トリフルオロメチル基(CF3−)により短い分子鎖でもより多くのフッ素原子を含み、なおかつ安価な原料から合成が可能である。
【0008】
【発明の実施の形態】
以下、本発明をさらに詳しく説明する。
本発明のパーフルオロジカルボニル化合物は上記一般式(1)で表されるものである。具体的には、次のものが例示される。
【0009】
【化5】
【0010】
これらのものは、例えば下記の反応経路に示されるように、一般式(2)に示されるような2価のアルコールを式:R-COClで表されるアセチルクロライド等のアシルクロライドでジエステル化して一般式(3)で表されるジエステルを得、その後、特許公報第2945693号に示されるような公知の液相フッ化法によりフッ化して一般式(4)で表されるパーフルオロジエステルとし、次にこれをKF等の触媒で処理することで得ることができる。
【0011】
〔反応経路〕
【0012】
【化6】
【0013】
【化7】
【0014】
(式中、Rf1、Rf2、Rf3およびRf4は、独立にフッ素原子もしくはトリフルオロメチル基であり、但しRf1とRf2とは異なり、Rf3とRf4とは異なる。Rは独立に炭素原子数1〜5のアルキル基であり、Rf5は独立にRがパーフルオロ化されて生成した炭素原子数1〜5のパーフルオロアルキル基である。)
一般式(2)の2価アルコール化合物は一種単独であってもよいし、二種以上の混合物で使用してもよい。この2価アルコール化合物の代表的な例としてはジプロピレングリコールがあげられる。ジプロピレングリコールは、下記の式(5)、(6)、(7):
【0015】
【化8】
で示され、第一級アルコール構造および/または第二級アルコール構造を有する構造異性体として存在し、これら3種の構造異性体の混合物として安価に市販されている。
【0016】
これら式(5)、(6)、(7)で表される化合物の混合物を前記反応経路において一般式(2)で表される2価アルコールと使用した場合には、混合状態のままエステル化、フッ素化、触媒処理の結果、一般式(1)のパーフルオロジカルボニル化合物は次の式(8)、(9)および(10)で示される3種の化合物の混合物として得られる。
【0017】
【化9】
【0018】
〔有用性〕
本発明のパーフルオロジカルボニル化合物は容易にアルコール、エステル、アミド等の様々な官能基を有するパーフルオロ化合物に誘導し合成するための中間体として有用である。また、このパーフルオロジカルボニル化合物やこうして誘導された化合物は界面活性剤、潤滑油、農薬、医薬品、防汚剤、離型剤などの含フッ素製品の成分として有用であり、さらに、種々の含フッ素ポリマーの製造原料として非常に有用である。
【0019】
【実施例】
(1) フラスコ内に、第一級アルコール構造と第二級アルコール構造の存在比(モル比)が38.5:61.5である、前記式(5)〜式(7)で表される3種の構造異性体からなるジプロピレングリコール混合物402g(6.0mol)を仕込み、窒素雰囲気下で攪拌した。これにアセチルクロライド620g(6.6mol)を4時間かけて滴下した。滴下終了後に、得られた反応混合物を50℃に加熱した後に、乾燥窒素で24時間バブリングした。この生成物を単蒸留して、定量収量で目的とするジプロピレングリコールジアセチルエステルが得られた。
【0020】
(2) 5.0リットルの1,1,2−トリクロロフルオロエタンを−7℃に保持した10リットルの攪拌タンク型反応槽に、窒素ガスを2000cc/min、フッ素ガスを500cc/minを流通させた。装置内の気体を完全に置換した後に、窒素−フッ素混合ガス流通下で、上記(1)のステップで得られたプロピレングリコールジアセチルエステル327g(1.50mol)を、1,1,2−トリクロロフルオロエタン320gと混合し24時間かけて計量しながら反応液にゆっくりと滴下した。滴下終了から30分後にフッ素ガスの流通を停止、窒素雰囲気下で得られた反応液を5時間攪拌した後に溶媒をエバポレータで蒸発させて濃縮を行った。濃縮後の反応液について成分を単蒸留したところ748gのパーフルオロエステルを得た。次に、得られたパーフルオロエステルについて窒素雰囲気下で、フッ化カリウム2gを加えて反応蒸留を行ったところ、bp65℃で420gの生成物が得られた。
得られた生成物を分析したところ、GC-MS分析からこの生成物の分子量は310と測定された。また、IR吸収スペクトルを測定したところ、1805cm-1にケトン構造を示す吸収ピークが、そして1844cm-1に酸フロライド構造のカルボニルを示す吸収ピークが観測できた。これらの測定結果から、得られた生成物は、前記式(8)〜式(10)で表される3種の構造異性体の混合物であるパーフルオロジカルボニル化合物であることがわかった。
【0021】
【発明の効果】
本発明によると、柔軟な構造を有し、容易にかつ安価に製造することができ、純度の高いを提供される。この化合物は種々の化合物を製造する中間体として、種々の含フッ素ポリマーの製造原料として有用である。また、この化合物は界面活性剤、潤滑油、農薬、医薬品、防汚剤、離型剤などの含フッ素製品の成分として有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel perfluorodicarbonyl compound.
[0002]
[Prior art]
Perfluorodicarbonyl compounds can be easily derived into dihydric alcohols, amides, esters, etc., and the various perfluoro compounds obtained in this way are surfactants, lubricants, agricultural chemicals, pharmaceuticals, antifouling agents, It is useful as a component of a fluorine-containing product such as a release agent, and is also useful as a raw material for producing various fluorine-containing polymers.
[0003]
Conventionally, perfluoro compounds having a perfluoroalkylene group such as FOC—C 6 F 12 —COF in the skeleton have been generally used for such purposes. However, such a compound is usually in a solid state because fluorine exists in the form of a linear perfluoroalkylene structure at the center of the molecule, and the physical properties of the resulting derivative are limited due to its rigid structure. was there.
[0004]
On the other hand, examples of perfluorodicarbonyl compounds into which a perfluoroalkyl group having a flexible structure can be introduced include the following compounds obtained by adding hexafluoropropylene oxide to oxalic acid fluoride shown in US Pat. No. 998978 It has been known.
[0005]
[Chemical 3]
[0006]
Unlike the compounds of formula FOC-C 6 F 12 -COF above, this compound has flexibility due to the ether bond present in the molecule, but the raw material oxalic acid fluoride is unstable and difficult to handle, and the synthesis process The perfluorodicarbonyl compound obtained due to impurities produced as a by-product in is difficult to purify. Therefore, the process becomes complicated, the yield is low, and it is unavoidable.
In view of the above background, an object of the present invention is to provide a perfluorodicarbonyl compound having a flexible structure, which can be easily and inexpensively manufactured, and has a high purity.
[0007]
[Means for Solving the Problems]
As a result of diligent efforts, the inventors of the present invention have the following formulas (8), (9) and (10):
[Chemical 1]
It has been found that a mixture of three perfluorodicarbonyl compounds represented by the above can solve the above problems. That is, perfluoro-dicarbonyl compounds of these has a flexible ether linkage, a trifluoromethyl group (CF 3 -) contain more fluorine atoms in a short molecular chain, the synthesis of yet inexpensive raw materials Is possible.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
The perfluorodicarbonyl compound of the present invention is represented by the above general formula (1). Specifically, the following are illustrated.
[0009]
[Chemical formula 5]
[0010]
For example, as shown in the following reaction route, these compounds are obtained by diesterifying a dihydric alcohol represented by the general formula (2) with an acyl chloride such as acetyl chloride represented by the formula: R-COCl. Obtaining a diester represented by the general formula (3), then fluorinated by a known liquid phase fluorination method as shown in Patent Publication No. 2945693 to obtain a perfluorodiester represented by the general formula (4), Next, this can be obtained by treating with a catalyst such as KF.
[0011]
[Reaction pathway]
[0012]
[Chemical 6]
[0013]
[Chemical 7]
[0014]
(In the formula, Rf 1 , Rf 2 , Rf 3 and Rf 4 are independently a fluorine atom or a trifluoromethyl group, except that Rf 1 and Rf 2 are different, and Rf 3 and Rf 4 are different. (Independently, it is an alkyl group having 1 to 5 carbon atoms, and Rf 5 is a perfluoroalkyl group having 1 to 5 carbon atoms, which is formed by R being perfluorinated independently.)
The dihydric alcohol compound of the general formula (2) may be used alone or in a mixture of two or more. A typical example of the dihydric alcohol compound is dipropylene glycol. Dipropylene glycol has the following formulas (5), (6), (7):
[0015]
[Chemical 8]
It exists as a structural isomer having a primary alcohol structure and / or a secondary alcohol structure, and is commercially available as a mixture of these three structural isomers at a low cost.
[0016]
When a mixture of the compounds represented by the formulas (5), (6), and (7) is used with the dihydric alcohol represented by the general formula (2) in the reaction pathway, esterification is performed in the mixed state. As a result of fluorination and catalyst treatment, the perfluorodicarbonyl compound of the general formula (1) is obtained as a mixture of three compounds represented by the following formulas (8), (9) and (10).
[0017]
[Chemical 9]
[0018]
〔Usefulness〕
The perfluorodicarbonyl compound of the present invention is useful as an intermediate for easily deriving and synthesizing perfluoro compounds having various functional groups such as alcohols, esters and amides. In addition, the perfluorodicarbonyl compound and the compound thus derived are useful as components of fluorine-containing products such as surfactants, lubricating oils, agricultural chemicals, pharmaceuticals, antifouling agents, mold release agents, etc. It is very useful as a raw material for producing a fluoropolymer.
[0019]
【Example】
(1) Three types of structures represented by the above formulas (5) to (7), wherein the abundance ratio (molar ratio) of primary alcohol structure to secondary alcohol structure is 38.5: 61.5 in the flask 402 g (6.0 mol) of a dipropylene glycol mixture consisting of isomers was charged and stirred under a nitrogen atmosphere. To this was added 620 g (6.6 mol) of acetyl chloride dropwise over 4 hours. After completion of the dropwise addition, the resulting reaction mixture was heated to 50 ° C. and then bubbled with dry nitrogen for 24 hours. The product was simply distilled to obtain the desired dipropylene glycol diacetyl ester in a quantitative yield.
[0020]
(2) 2000 cc / min of nitrogen gas and 500 cc / min of fluorine gas were circulated through a 10 liter stirred tank type reaction vessel in which 5.0 liters of 1,1,2-trichlorofluoroethane was maintained at -7 ° C. After completely replacing the gas in the apparatus, 327 g (1.50 mol) of the propylene glycol diacetyl ester obtained in the step (1) above was replaced with 1,1,2-trichlorofluoroethane under a nitrogen-fluorine mixed gas flow. The mixture was mixed with 320 g and slowly dropped into the reaction solution while weighing over 24 hours. After 30 minutes from the end of dropping, the flow of fluorine gas was stopped, and the reaction solution obtained in a nitrogen atmosphere was stirred for 5 hours, and then the solvent was evaporated by an evaporator and concentrated. The components of the concentrated reaction liquid were simply distilled to obtain 748 g of perfluoroester. Next, the obtained perfluoroester was subjected to reactive distillation by adding 2 g of potassium fluoride under a nitrogen atmosphere. As a result, 420 g of a product was obtained at bp 65 ° C.
When the obtained product was analyzed, the molecular weight of this product was determined to be 310 from GC-MS analysis. The measured IR absorption spectrum, the absorption peak showing a ketone structure 1805Cm -1 is and the absorption peak indicating the carbonyl of acid fluoride structure 1844Cm -1 could be observed. From these measurement results, it was found that the obtained product was a perfluorodicarbonyl compound which is a mixture of three kinds of structural isomers represented by the above formulas (8) to (10).
[0021]
【The invention's effect】
According to the present invention, it has a flexible structure, can be manufactured easily and inexpensively, and is provided with high purity. This compound is useful as an intermediate for producing various compounds and as a raw material for producing various fluoropolymers. Moreover, this compound is useful as a component of fluorine-containing products such as surfactants, lubricating oils, agricultural chemicals, pharmaceuticals, antifouling agents, and mold release agents.
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JP2000384155A JP4369614B2 (en) | 2000-12-18 | 2000-12-18 | Perfluorodicarbonyl compounds |
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JP2000384155A JP4369614B2 (en) | 2000-12-18 | 2000-12-18 | Perfluorodicarbonyl compounds |
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JP2002187865A JP2002187865A (en) | 2002-07-05 |
JP4369614B2 true JP4369614B2 (en) | 2009-11-25 |
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