JP2001031684A - Production of fluorine-containing organosilicon compound - Google Patents

Production of fluorine-containing organosilicon compound

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Publication number
JP2001031684A
JP2001031684A JP11200344A JP20034499A JP2001031684A JP 2001031684 A JP2001031684 A JP 2001031684A JP 11200344 A JP11200344 A JP 11200344A JP 20034499 A JP20034499 A JP 20034499A JP 2001031684 A JP2001031684 A JP 2001031684A
Authority
JP
Japan
Prior art keywords
fluorine
organosilicon compound
compound
mol
aliphatic hydrocarbon
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
Application number
JP11200344A
Other languages
Japanese (ja)
Inventor
Yoichi Tonomura
洋一 殿村
Toru Kubota
透 久保田
Mikio Endo
幹夫 遠藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin Etsu Chemical Co Ltd
Original Assignee
Shin Etsu Chemical Co Ltd
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Filing date
Publication date
Application filed by Shin Etsu Chemical Co Ltd filed Critical Shin Etsu Chemical Co Ltd
Priority to JP11200344A priority Critical patent/JP2001031684A/en
Publication of JP2001031684A publication Critical patent/JP2001031684A/en
Pending legal-status Critical Current

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    • 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

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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a fluorine-containing organosilicon compound in high yield by reacting a fluorine-containing olefin compound with an organosilicon compound having silicon-hydrogen bond in the presence of a platinum catalyst in an aliphatic hydrocarbon-based solvent. SOLUTION: (A) a fluorine-containing olefin compound of the formula CF3(CF2)nCH=CH2 [(n) is 3-9] (e.g. 3,3,4,4,5,5,6,6,6nonafluorohexene) is reacted with (B) an organosilicon compound of the formula: HSi(CH3)aClb [(a) is 0 or 1; (b) is 2 or 3 and (a+b)=3] (e.g. trichlorosilane or methyldichlorosilane) in the presence of (C) a platinum catalyst (e.g. chloroplatinic acid) in (D) an aliphatic hydrocarbon-based solvent (e.g. pentane, 2-methylbutane or nonane). In the above reaction, it is preferable that these components B and C are each compounded in amounts of 0.5-2.0 mol and 0.000001-0.01 mol based on 1 mol component A and the component D is used in an amount of 0.01-5 pts.wt. based on 1 pt.wt. component A.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、含フッ素オレフィ
ン化合物と、ケイ素−水素結合を有する有機ケイ素化合
物とを白金触媒存在下に反応させて、安全に、かつ高反
応性、高収率で含フッ素有機ケイ素化合物を製造するこ
とができる含フッ素有機ケイ素化合物の製造法に関す
る。BACKGROUND OF THE INVENTION The present invention relates to a process for reacting a fluorine-containing olefin compound with an organosilicon compound having a silicon-hydrogen bond in the presence of a platinum catalyst to provide a safe, highly reactive and high yield compound. The present invention relates to a method for producing a fluorinated organosilicon compound capable of producing a fluorinated organosilicon compound.

【０００２】[0002]

【従来の技術及び発明が解決しようとする課題】含フッ
素有機ケイ素化合物は、表面張力が小さく、撥水性、撥
油性、耐薬品性に優れているため、各種基材の表面処理
剤として利用されている。2. Description of the Related Art Fluorine-containing organosilicon compounds have low surface tension and are excellent in water repellency, oil repellency and chemical resistance, and are therefore used as surface treatment agents for various substrates. ing.

【０００３】このような含フッ素有機ケイ素化合物の製
造法としては、含フッ素オレフィン化合物とケイ素−水
素結合を有する有機ケイ素化合物とを白金触媒存在下に
付加させる方法（特開平８−１５７６４３号公報、Ｊ．
Ｃｏｌｌｏｉｄ Ｉｎｔｅｒｆａｃｅ Ｓｃｉ．，１５
９，２３８（１９９３）、Ｂｕｌｌ．Ｃｈｅｍ．Ｓｏ
ｃ．Ｊｐｎ．，６６，４７２（１９９３）、Ｂｕｌｌ．
Ｃｈｅｍ．Ｓｏｃ．Ｊｐｎ．，６６，１７５４（１９９
３））が提案されている。[0003] As a method for producing such a fluorine-containing organosilicon compound, a method of adding a fluorine-containing olefin compound and an organosilicon compound having a silicon-hydrogen bond in the presence of a platinum catalyst (JP-A-8-157463, J.
Colloid Interface Sci. , 15
9, 238 (1993), Bull. Chem. So
c. Jpn. , 66, 472 (1993), Bull.
Chem. Soc. Jpn. , 66, 1754 (199
3)) has been proposed.

【０００４】しかし、これらの方法はいずれも耐圧ガラ
ス、もしくはステンレス製オートクレーブを使用し、加
圧下で反応を行う必要があるため、工業的規模で行うに
は安全性の点で問題があった。However, these methods all require the use of pressure-resistant glass or a stainless steel autoclave and the reaction to be carried out under pressure, and thus have a problem in terms of safety when carried out on an industrial scale.

【０００５】一方、これらの反応は常圧下で行うと反応
性に乏しいため、満足な収量が得られるまでに長時間を
必要とするか、もしくは反応が途中で進行しなくなるこ
とから、常圧下での反応は工業的規模で行うには有利で
ない。On the other hand, these reactions are poor in reactivity when carried out under normal pressure, so that a long time is required until a satisfactory yield is obtained, or the reaction does not progress on the way. Is not advantageous to be carried out on an industrial scale.

【０００６】本発明は、上記事情に鑑みなされたもの
で、含フッ素オレフィン化合物と有機ケイ素化合物とを
白金触媒存在下で反応させ、安全に、かつ高反応性、高
収率で含フッ素有機ケイ素化合物を製造することができ
る含フッ素有機ケイ素化合物の製造法を提供することを
目的とする。The present invention has been made in view of the above circumstances, and is intended to allow a fluorine-containing olefin compound and an organosilicon compound to react in the presence of a platinum catalyst, and to provide a safe, high-reactivity, high-yield fluorine-containing organosilicon compound. An object of the present invention is to provide a method for producing a fluorine-containing organosilicon compound capable of producing a compound.

【０００７】[0007]

【課題を解決するための手段及び発明の実施の形態】本
発明者は、上記目的を達成するために鋭意検討を重ねた
結果、下記一般式（１）で示される含フッ素オレフィン
化合物と、下記一般式（２）で示されるケイ素−水素結
合を有する有機ケイ素化合物とを白金触媒存在下で反応
させ、下記一般式（３）で示される含フッ素有機ケイ素
化合物を製造する際、溶媒として脂肪族炭化水素系溶媒
を用いることにより、意外にもニトリル系化合物やテト
ラヒドロフランなどの極性溶媒、芳香族炭化水素系溶媒
を用いた場合に比較して、反応性が極めて向上して、常
圧下で反応させても反応が速やか、かつ持続的に進行
し、比較的短時間で満足な収量の目的化合物が得られる
こと、それ故、安全に、かつ高反応性、高収率で工業的
に有利に一般式（３）の含フッ素有機ケイ素化合物を製
造することができることを知見し、本発明を完成するに
至った。Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that a fluorine-containing olefin compound represented by the following general formula (1): When the organosilicon compound having a silicon-hydrogen bond represented by the general formula (2) is reacted in the presence of a platinum catalyst to produce a fluorinated organosilicon compound represented by the following general formula (3), an aliphatic solvent is used as a solvent. By using a hydrocarbon-based solvent, it is surprisingly much more reactive than when a polar solvent such as a nitrile-based compound or tetrahydrofuran or an aromatic hydrocarbon-based solvent is used, and is reacted under normal pressure. However, the reaction proceeds quickly and continuously, and a desired yield of the target compound can be obtained in a relatively short time. Therefore, it is generally safe, highly reactive, and highly industrially advantageous with a high yield. Equation (3 And it found that it is possible to produce a fluorine-containing organic silicon compound, and have completed the present invention.

【０００８】従って、本発明は、下記一般式（１） ＣＦ3（ＣＦ2）nＣＨ＝ＣＨ2 （１） （式中、ｎは３〜９の整数である。）で示される含フッ
素オレフィン化合物と、下記一般式（２） ＨＳｉ（ＣＨ3）aＣｌb （２） （式中、ａは０又は１、ｂは２又は３であり、ａ＋ｂ＝
３である。）で示される有機ケイ素化合物とを白金触媒
存在下、少なくとも１種類の脂肪族炭化水素系溶媒中で
反応させ、下記一般式（３） ＣＦ3（ＣＦ2）nＣＨ2ＣＨ2Ｓｉ（ＣＨ3）aＣｌb （３） （式中、ａ，ｂ，ｎは前記と同様である。）で表される
含フッ素有機ケイ素化合物を得ることを特徴とする含フ
ッ素有機ケイ素化合物の製造法を提供する。Accordingly, the present invention provides a fluorine-containing olefin represented by the following general formula (1): CF 3 (CF 2 ) n CHＣＨCH 2 (1), wherein n is an integer of 3 to 9. Compound and the following general formula (2) HSi (CH 3 ) a Cl b (2) (where a is 0 or 1, b is 2 or 3, and a + b =
3. With an organosilicon compound represented by the following general formula (3): CF 3 (CF 2 ) n CH 2 CH 2 Si (CH 3 ) in the presence of a platinum catalyst in at least one kind of aliphatic hydrocarbon solvent. ) a Cl b (3) (wherein, a, b, n are a manufacturing method of the and is the same.) to obtain a fluorine-containing organic silicon compound represented by the wherein the fluorine-containing organic silicon compound I do.

【０００９】以下、本発明につき更に詳しく説明する
と、本発明の含フッ素有機ケイ素化合物の製造法におい
て原料として用いられる含フッ素オレフィン化合物は、
下記一般式（１）で示されるものである。 ＣＦ3（ＣＦ2）nＣＨ＝ＣＨ2 （１）Hereinafter, the present invention will be described in more detail. The fluorine-containing olefin compound used as a raw material in the process for producing a fluorine-containing organosilicon compound of the present invention is as follows:
It is represented by the following general formula (1). CF 3 (CF 2 ) n CH = CH 2 (1)

【００１０】上記式中、ｎは３〜９の整数である。式
（１）の含フッ素オレフィン化合物として具体的には、
３，３，４，４，５，５，６，６，６−ノナフルオロヘ
キセン、３，３，４，４，５，５，６，６，７，７，７
−ウンデカフルオロヘプテン、３，３，４，４，５，
５，６，６，７，７，８，８，８−トリデカフルオロオ
クテン、３，３，４，４，５，５，６，６，７，７，
８，８，９，９，９−ペンタデカフルオロノネン、３，
３，４，４，５，５，６，６，７，７，８，８，９，
９，１０，１０，１０−ヘプタデカフルオロデセン、
３，３，４，４，５，５，６，６，７，７，８，８，
９，９，１０，１０，１１，１１，１１−ノナデカフル
オロウンデセン、３，３，４，４，５，５，６，６，
７，７，８，８，９，９，１０，１０，１１，１１，１
２，１２−ヘニコサフルオロドデセン等が挙げられる。In the above formula, n is an integer of 3 to 9. Specifically, as the fluorine-containing olefin compound of the formula (1),
3,3,4,4,5,5,6,6,6-nonafluorohexene, 3,3,4,4,5,5,6,6,7,7,7
-Undecafluoroheptene, 3,3,4,4,5
5,6,6,7,7,8,8,8-tridecafluorooctene, 3,3,4,4,5,5,6,6,7,7,
8,8,9,9,9-pentadecafluorononene, 3,
3,4,4,5,5,6,6,7,7,8,8,9,
9,10,10,10-heptadecafluorodecene,
3,3,4,4,5,5,6,6,7,7,8,8,
9,9,10,10,11,11,11-nonadecafluoroundecene, 3,3,4,4,5,5,6,6
7, 7, 8, 8, 9, 9, 10, 10, 11, 11, 1
2,12-henicosafluorododecene and the like.

【００１１】また、ケイ素−水素結合を有する有機ケイ
素化合物は、下記一般式（２）で示されるものである。 ＨＳｉ（ＣＨ3）aＣｌb （２）The organic silicon compound having a silicon-hydrogen bond is represented by the following general formula (2). HSi (CH 3 ) a Cl b (2)

【００１２】上記式中、ａは０又は１、ｂは２又は３で
あり、ａ＋ｂ＝３である。一般式（２）の有機ケイ素化
合物としては、具体的にトリクロロシラン、メチルジク
ロロシランが例示される。In the above formula, a is 0 or 1, b is 2 or 3, and a + b = 3. Specific examples of the organosilicon compound of the general formula (2) include trichlorosilane and methyldichlorosilane.

【００１３】含フッ素オレフィン化合物とケイ素−水素
結合を有する有機ケイ素化合物との配合割合は、含フッ
素オレフィン化合物１ｍｏｌに対し、ケイ素−水素結合
を有する有機ケイ素化合物を０．５〜２．０ｍｏｌ、特
に０．８〜１．２ｍｏｌの範囲とすることが、反応性、
生産性の点から好ましい。有機ケイ素化合物の配合量が
少なすぎると反応性に劣る場合があり、多すぎると生産
性に劣る場合がある。The mixing ratio of the fluorinated olefin compound and the organosilicon compound having a silicon-hydrogen bond is such that the organosilicon compound having a silicon-hydrogen bond is 0.5 to 2.0 mol, preferably 1 mol of the fluorinated olefin compound. To be in the range of 0.8 to 1.2 mol, reactivity,
It is preferable from the viewpoint of productivity. If the amount of the organosilicon compound is too small, the reactivity may be poor. If the amount is too large, the productivity may be poor.

【００１４】本発明で用いる白金触媒としては、例えば
塩化白金酸、塩化白金酸のアルコール溶液、白金とジビ
ニルテトラメチルジシロキサン等の白金錯体、白金−炭
素、白金−シリカ等の担持触媒などが挙げられる。これ
ら白金触媒は、各種アルコール等の有機溶媒に添加する
などして通常の方法で用いることができる。Examples of the platinum catalyst used in the present invention include chloroplatinic acid, an alcohol solution of chloroplatinic acid, platinum complexes such as platinum and divinyltetramethyldisiloxane, and supported catalysts such as platinum-carbon and platinum-silica. Can be These platinum catalysts can be used in a usual manner, for example, by adding them to organic solvents such as various alcohols.

【００１５】白金触媒の配合量は、上記含フッ素オレフ
ィン化合物１ｍｏｌに対して、白金金属で０．００００
０１〜０．０１ｍｏｌ、特に０．００００１〜０．００
１ｍｏｌの範囲とすることが好ましい。The platinum catalyst is used in an amount of 0.0000 platinum metal with respect to 1 mol of the fluorine-containing olefin compound.
01-0.01 mol, especially 0.00001-0.00
It is preferred to be in the range of 1 mol.

【００１６】本発明においては、溶媒として脂肪族炭化
水素系溶媒を用いるもので、脂肪族炭化水素系溶媒とし
ては、炭素数が５〜１５、特に５〜１０のものが好適に
用いられる。炭素数が少なすぎるものは常温で気体であ
るため好ましくなく、多すぎると目的物である含フッ素
有機ケイ素化合物との蒸留による分離が困難となる場合
があり、好ましくない。In the present invention, an aliphatic hydrocarbon solvent is used as the solvent. As the aliphatic hydrocarbon solvent, those having 5 to 15 carbon atoms, particularly those having 5 to 10 carbon atoms, are suitably used. If the number of carbon atoms is too small, it is unfavorable because it is a gas at normal temperature, and if it is too large, it may be difficult to separate from the target fluorine-containing organosilicon compound by distillation, which is not preferable.

【００１７】脂肪族炭化水素系溶媒として具体的には、
ペンタン、２−メチルブタン、２，２−ジメチルプロパ
ン、ヘキサン、２−メチルペンタン、２，２−ジメチル
ブタン、２，３−ジメチルブタン、シクロヘキサン、ヘ
プタン、オクタン、２，２，３−トリメチルペンタン、
イソオクタン、ノナン、デカン、ウンデカン、ドデカン
などが挙げられる。Specific examples of the aliphatic hydrocarbon solvent include:
Pentane, 2-methylbutane, 2,2-dimethylpropane, hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, heptane, octane, 2,2,3-trimethylpentane,
Isooctane, nonane, decane, undecane, dodecane and the like.

【００１８】脂肪族炭化水素系溶媒の使用量は特に限定
されないが、反応性、生産性の点から、上記式（１）の
含フッ素オレフィン化合物１重量部に対し０．０１〜５
重量部、特に０．１〜２重量部の範囲が好ましい。脂肪
族炭化水素系溶媒の使用量が少なすぎると反応性に劣る
場合があり、多すぎると生産性において劣る場合があ
る。The amount of the aliphatic hydrocarbon solvent used is not particularly limited, but from the viewpoint of reactivity and productivity, 0.01 to 5 parts by weight per 1 part by weight of the fluorine-containing olefin compound of the above formula (1).
It is preferably in the range of 0.1 to 2 parts by weight. If the amount of the aliphatic hydrocarbon solvent is too small, the reactivity may be poor, and if it is too large, the productivity may be poor.

【００１９】上記脂肪族炭化水素系溶媒は、それ単独で
用いてもよいが、他の溶媒と混合して用いてもよい。こ
の場合、他の溶媒としては、例えばベンゼン、トルエ
ン、キシレン等の芳香族炭化水素系溶媒、ジエチルエー
テル、テトラヒドロフラン、ジオキサン等のエーテル系
溶媒、酢酸エチル、酢酸ブチル等のエステル系溶媒、ア
セトニトリル等の非プロトン性極性溶媒、ジクロロメタ
ン、クロロホルム等の塩素化炭化水素溶媒等が使用でき
る。他の溶媒の配合割合は、本発明の目的を損なわない
限り任意である。The above aliphatic hydrocarbon-based solvent may be used alone, or may be used as a mixture with another solvent. In this case, as other solvents, for example, benzene, toluene, xylene and other aromatic hydrocarbon solvents, diethyl ether, tetrahydrofuran, dioxane and other ether solvents, ethyl acetate, butyl acetate and other ester solvents, acetonitrile and the like An aprotic polar solvent, a chlorinated hydrocarbon solvent such as dichloromethane, chloroform and the like can be used. The mixing ratio of the other solvent is arbitrary as long as the object of the present invention is not impaired.

【００２０】上記の反応は、含フッ素オレフィン化合
物、白金触媒、脂肪族炭化水素系溶媒の混合液にケイ素
−水素結合を有する有機ケイ素化合物を加える方法、ケ
イ素−水素結合を有する有機ケイ素化合物、白金触媒、
脂肪族炭化水素系溶媒の混合液に含フッ素オレフィン化
合物を加える方法、白金触媒、脂肪族炭化水素系溶媒の
混合液にケイ素−水素結合を有する有機ケイ素化合物、
含フッ素オレフィン化合物の両方を滴下する方法のいず
れの方法を採用してもよく、また、滴下物を脂肪族炭化
水素系溶媒で希釈して加えてもよい。反応終了後は、通
常の方法で目的物を回収することができる。The above reaction is carried out by adding an organosilicon compound having a silicon-hydrogen bond to a mixture of a fluorine-containing olefin compound, a platinum catalyst and an aliphatic hydrocarbon solvent, an organosilicon compound having a silicon-hydrogen bond, platinum catalyst,
A method of adding a fluorinated olefin compound to a mixture of aliphatic hydrocarbon solvents, a platinum catalyst, an organosilicon compound having a silicon-hydrogen bond in a mixture of aliphatic hydrocarbon solvents,
Any of the methods of dropping both of the fluorine-containing olefin compounds may be employed, and the dropped product may be diluted with an aliphatic hydrocarbon-based solvent and added. After completion of the reaction, the target substance can be recovered by a usual method.

【００２１】上記反応は、常圧下もしくは加圧下のどち
らの条件でも行うことができるが、安全性の点から常圧
下で行うことが好ましい。なお、上記の反応の反応温度
は特に限定されないが、反応性、選択性の点から、０〜
１５０℃、特に常温〜１００℃が好ましく、反応時間は
１〜１０時間とすることができる。The above reaction can be carried out under normal pressure or under elevated pressure, but it is preferable to carry out the reaction under normal pressure from the viewpoint of safety. In addition, the reaction temperature of the above reaction is not particularly limited, but from the viewpoint of reactivity and selectivity, 0 to
The temperature is preferably 150 ° C., particularly normal temperature to 100 ° C., and the reaction time can be 1 to 10 hours.

【００２２】このような本発明の製造法では、下記一般
式（３）で示される含フッ素有機ケイ素化合物を高収率
で得ることができる。 ＣＦ3（ＣＦ2）nＣＨ2ＣＨ2Ｓｉ（ＣＨ3）aＣｌb （３） （式中、ｎ，ａ，ｂはそれぞれ上記と同様である。）According to the production method of the present invention, a fluorine-containing organosilicon compound represented by the following general formula (3) can be obtained in a high yield. CF 3 (CF 2 ) n CH 2 CH 2 Si (CH 3 ) a Cl b (3) (where n, a and b are the same as above)

【００２３】式（３）で示される含フッ素有機ケイ素化
合物として具体的には、３，３，４，４，５，５，６，
６，６−ノナフルオロヘキシルトリクロロシラン、３，
３，４，４，５，５，６，６，６−ノナフルオロヘキシ
ルメチルジクロロシラン、３，３，４，４，５，５，
６，６，７，７，７−ウンデカフルオロヘプチルトリク
ロロシラン、３，３，４，４，５，５，６，６，７，
７，７−ウンデカフルオロヘプチルメチルジクロロシラ
ン、３，３，４，４，５，５，６，６，７，７，８，
８，８−トリデカフルオロオクチルトリクロロシラン、
３，３，４，４，５，５，６，６，７，７，８，８，８
−トリデカフルオロオクチルメチルジクロロシラン、
３，３，４，４，５，５，６，６，７，７，８，８，
９，９，９−ペンタデカフルオロノニルトリクロロシラ
ン、３，３，４，４，５，５，６，６，７，７，８，
８，９，９，９−ペンタデカフルオロノニルメチルジク
ロロシラン、３，３，４，４，５，５，６，６，７，
７，８，８，９，９，１０，１０，１０−ヘプタデカフ
ルオロデシルトリクロロシラン、３，３，４，４，５，
５，６，６，７，７，８，８，９，９，１０，１０，１
０−ヘプタデカフルオロデシルメチルジクロロシラン、
３，３，４，４，５，５，６，６，７，７，８，８，
９，９，１０，１０，１１，１１，１１−ノナデカフル
オロウンデセニルトリクロロシラン、３，３，４，４，
５，５，６，６，７，７，８，８，９，９，１０，１
０，１１，１１，１１−ノナデカフルオロウンデセニル
メチルジクロロシラン、３，３，４，４，５，５，６，
６，７，７，８，８，９，９，１０，１０，１１，１
１，１２，１２−ヘニコサフルオロドデシルトリクロロ
シラン、３，３，４，４，５，５，６，６，７，７，
８，８，９，９，１０，１０，１１，１１，１２，１２
−ヘニコサフルオロドデシルメチルジクロロシランなど
が例示される。As the fluorine-containing organosilicon compound represented by the formula (3), specifically, 3,3,4,4,5,5,6
6,6-nonafluorohexyltrichlorosilane, 3,
3,4,4,5,5,6,6,6-nonafluorohexylmethyldichlorosilane, 3,3,4,4,5,5
6,6,7,7,7-undecafluoroheptyltrichlorosilane, 3,3,4,4,5,5,6,6,7,
7,7-undecafluoroheptylmethyldichlorosilane, 3,3,4,4,5,5,6,6,7,7,8,
8,8-tridecafluorooctyltrichlorosilane,
3,3,4,4,5,5,6,6,7,7,8,8,8
-Tridecafluorooctylmethyldichlorosilane,
3,3,4,4,5,5,6,6,7,7,8,8,
9,9,9-pentadecafluorononyltrichlorosilane, 3,3,4,4,5,5,6,6,7,7,8,
8,9,9,9-pentadecafluorononylmethyldichlorosilane, 3,3,4,4,5,5,6,6,7,
7,8,8,9,9,10,10,10-heptadecafluorodecyltrichlorosilane, 3,3,4,4,5
5,6,6,7,7,8,8,9,9,10,10,1
0-heptadecafluorodecylmethyldichlorosilane,
3,3,4,4,5,5,6,6,7,7,8,8,
9,9,10,10,11,11,11-nonadecafluoroundecenyltrichlorosilane, 3,3,4,4
5,5,6,6,7,7,8,8,9,9,10,1
0,11,11,11-nonadecafluoroundecenylmethyldichlorosilane, 3,3,4,4,5,5,6
6,7,7,8,8,9,9,10,10,11,1
1,12,12-henicosafluorododecyltrichlorosilane, 3,3,4,4,5,5,6,6,7,7,7,
8, 8, 9, 9, 10, 10, 11, 11, 12, 12
-Henikosafluorododecylmethyldichlorosilane and the like.

【００２４】[0024]

【実施例】以下、実施例及び比較例を示して本発明を具
体的に説明するが、本発明は下記の実施例に制限される
ものではない。EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

【００２５】［実施例１］撹拌機、還流器、滴下ロート
及び温度計を備えたフラスコに３，３，４，４，５，
５，６，６，７，７，８，８，９，９，１０，１０，１
０−ヘプタデカフルオロデセン８９．２ｇ（０．２０ｍ
ｏｌ）、２０重量％塩化白金酸−イソプロパノール溶液
０．０８ｇ、イソオクタン１７．８ｇを仕込み、８０℃
に加熱した。内温が安定した後、メチルジクロロシラン
２５．３ｇ（０．２２ｍｏｌ）を２時間かけて滴下し、
滴下終了後、反応液を８０℃で２時間撹拌したところ、
３，３，４，４，５，５，６，６，７，７，８，８，
９，９，１０，１０，１０−ヘプタデカフルオロデシル
メチルジクロロシランが得られた。ガスクロマトグラフ
ィーで反応率を求めたところ、８８．４％であった（ガ
スクロマトグラフィーの面積％にて。以下同様）。Example 1 A flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 3, 3, 4, 4, 5,
5,6,6,7,7,8,8,9,9,10,10,1
89.2 g of 0-heptadecafluorodecene (0.20 m
ol), 0.08 g of a 20% by weight chloroplatinic acid-isopropanol solution, and 17.8 g of isooctane were charged, and 80 ° C.
Heated. After the internal temperature was stabilized, 25.3 g (0.22 mol) of methyldichlorosilane was added dropwise over 2 hours.
After completion of the dropwise addition, the reaction solution was stirred at 80 ° C. for 2 hours.
3,3,4,4,5,5,6,6,7,7,8,8,
9,9,10,10,10-Heptadecafluorodecylmethyldichlorosilane was obtained. The reaction rate was determined by gas chromatography to be 88.4% (in terms of gas chromatography area%; the same applies hereinafter).

【００２６】［実施例２］撹拌機、還流器、滴下ロート
及び温度計を備えたフラスコに３，３，４，４，５，
５，６，６，７，７，８，８，８−トリデカフルオロオ
クテン６９．２ｇ（０．２０ｍｏｌ）、２０重量％塩化
白金酸−イソプロパノール溶液０．０８ｇ、イソオクタ
ン１３．８ｇを仕込み、８０℃に加熱した。内温が安定
した後、メチルジクロロシラン２５．３ｇ（０．２２ｍ
ｏｌ）を２時間かけて滴下し、滴下終了後、反応液を８
０℃で２時間撹拌したところ、３，３，４，４，５，
５，６，６，７，７，８，８，８−トリデカフルオロオ
クチルメチルジクロロシランが得られた。ガスクロマト
グラフィーで反応率を求めたところ、８６．９％であっ
た。Example 2 In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 3,3,4,4,5,
6,9.2 g (0.20 mol) of 5,6,6,7,7,8,8,8-tridecafluorooctene, 0.08 g of a 20 wt% chloroplatinic acid-isopropanol solution, and 13.8 g of isooctane were charged. Heated to ° C. After the internal temperature was stabilized, 25.3 g of methyldichlorosilane (0.22 m
ol) was added dropwise over 2 hours.
After stirring at 0 ° C for 2 hours, 3,3,4,4,5
5,6,6,7,7,8,8,8-Tridecafluorooctylmethyldichlorosilane was obtained. The conversion was determined by gas chromatography to be 86.9%.

【００２７】［実施例３］撹拌機、還流器、滴下ロート
及び温度計を備えたフラスコに３，３，４，４，５，
５，６，６，７，７，８，８，９，９，１０，１０，１
０−ヘプタデカフルオロデセン８９．２ｇ（０．２０ｍ
ｏｌ）、２０重量％塩化白金酸−イソプロパノール溶液
０．０８ｇ、イソオクタン１７．８ｇを仕込み、８０℃
に加熱した。内温が安定した後、トリクロロシラン２
９．８ｇ（０．２２ｍｏｌ）を２時間かけて滴下し、滴
下終了後、反応液を８０℃で２時間撹拌したところ、
３，３，４，４，５，５，６，６，７，７，８，８，
９，９，１０，１０，１０−ヘプタデカフルオロデシル
トリクロロシランが得られた。ガスクロマトグラフィー
で反応率を求めたところ、９６．８％であった。Example 3 In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 3,3,4,4,5,
5,6,6,7,7,8,8,9,9,10,10,1
89.2 g of 0-heptadecafluorodecene (0.20 m
ol), 0.08 g of a 20% by weight chloroplatinic acid-isopropanol solution, and 17.8 g of isooctane were charged, and 80 ° C.
Heated. After the internal temperature is stabilized, trichlorosilane 2
9.8 g (0.22 mol) was added dropwise over 2 hours, and after completion of the addition, the reaction solution was stirred at 80 ° C. for 2 hours.
3,3,4,4,5,5,6,6,7,7,8,8,
9,9,10,10,10-Heptadecafluorodecyltrichlorosilane was obtained. The conversion was determined by gas chromatography to be 96.8%.

【００２８】［比較例１］イソオクタンを用いなかった
以外は、実施例１と同様に反応を行い、８０℃で２時間
撹拌したところ、反応率は１０．３％であり、８時間撹
拌後でも反応率は１５．０％であった。[Comparative Example 1] A reaction was carried out in the same manner as in Example 1 except that isooctane was not used. When the mixture was stirred at 80 ° C for 2 hours, the reaction rate was 10.3%, and even after stirring for 8 hours. The conversion was 15.0%.

【００２９】［比較例２］溶媒としてイソオクタンの代
わりにテトラヒドロフランを用いた以外は、実施例１と
同様に反応を行い、８０℃で２時間撹拌したところ、反
応率は３．４％であり、８時間撹拌後でも変化はなかっ
た。Comparative Example 2 A reaction was carried out in the same manner as in Example 1 except that tetrahydrofuran was used instead of isooctane as a solvent, and the mixture was stirred at 80 ° C. for 2 hours. As a result, the reaction rate was 3.4%. There was no change after stirring for 8 hours.

【００３０】［比較例３］溶媒としてイソオクタンの代
わりにアセトニトリルを用いた以外は、実施例１と同様
に反応させ、８０℃で２時間撹拌したが、反応は全く進
行しておらず、８時間撹拌後でもやはり反応は進行して
いなかった。Comparative Example 3 The reaction was carried out in the same manner as in Example 1 except that acetonitrile was used instead of isooctane as the solvent, and the mixture was stirred at 80 ° C. for 2 hours. Even after stirring, the reaction did not proceed.

【００３１】［比較例４］溶媒としてイソオクタンの代
わりにトルエンを用いた以外は、実施例３と同様に反応
させ、８０℃で２時間撹拌した後、反応率は２６．４％
であり、８時間撹拌後でも反応率は６６．９％であっ
た。Comparative Example 4 A reaction was carried out in the same manner as in Example 3 except that toluene was used instead of isooctane as a solvent. After stirring at 80 ° C. for 2 hours, the reaction rate was 26.4%.
The reaction rate was 66.9% even after stirring for 8 hours.

【００３２】[0032]

【発明の効果】本発明の含フッ素有機ケイ素化合物の製
造法は、高反応性で、常圧下でも反応が速やかかつ持続
的に進行し、比較的短時間で高収率で目的とする上記式
（３）の含フッ素有機ケイ素化合物を製造することがで
きる。この製造法によれば、安全に、かつ効率的に工業
的規模で含フッ素有機ケイ素化合物を製造することがで
きる。The process for producing a fluorine-containing organosilicon compound according to the present invention is highly reactive, the reaction proceeds rapidly and continuously even under normal pressure, and the desired compound of the formula The fluorine-containing organosilicon compound of (3) can be produced. According to this production method, a fluorine-containing organosilicon compound can be produced safely and efficiently on an industrial scale.

フロントページの続き (72)発明者 遠藤 幹夫 新潟県中頸城郡頸城村大字西福島28−１ 信越化学工業株式会社合成技術研究所内 Ｆターム(参考） 4H049 VN01 VQ12 VS12 VT17 VT25 VT42 VT43 VT45 VU21 VU28 VV02 VW02 VW32 Continued on the front page (72) Inventor Mikio Endo 28-1 Nishifukushima, Nishifukushima, Nakakushijo-gun, Niigata Pref. Shin-Etsu Chemical Co., Ltd. Synthetic Research Laboratory F-term (reference) 4H049 VN01 VQ12 VS12 VT17 VT25 VT42 VT43 VT45 VU21 VU28 VV02 VW02 VW32

Claims (1)

【特許請求の範囲】[Claims] 【請求項１】 下記一般式（１） ＣＦ3（ＣＦ2）nＣＨ＝ＣＨ2 （１） （式中、ｎは３〜９の整数である。）で示される含フッ
素オレフィン化合物と、下記一般式（２） ＨＳｉ（ＣＨ3）aＣｌb （２） （式中、ａは０又は１、ｂは２又は３であり、ａ＋ｂ＝
３である。）で示される有機ケイ素化合物とを白金触媒
存在下、少なくとも１種類の脂肪族炭化水素系溶媒中で
反応させ、下記一般式（３） ＣＦ3（ＣＦ2）nＣＨ2ＣＨ2Ｓｉ（ＣＨ3）aＣｌb （３） （式中、ａ，ｂ，ｎは前記と同様である。）で表される
含フッ素有機ケイ素化合物を得ることを特徴とする含フ
ッ素有機ケイ素化合物の製造法。1. A fluorine-containing olefin compound represented by the following general formula (1) CF 3 (CF 2 ) n CHＣＨCH 2 (1) (wherein n is an integer of 3 to 9); General formula (2) HSi (CH 3 ) a Cl b (2) (where a is 0 or 1, b is 2 or 3, and a + b =
3. With an organosilicon compound represented by the following general formula (3): CF 3 (CF 2 ) n CH 2 CH 2 Si (CH 3 ) in the presence of a platinum catalyst in at least one kind of aliphatic hydrocarbon solvent. ) a Cl b (3) (wherein, a, b, n the preparation of fluorine-containing organosilicon compound, characterized by obtaining the the same as is.) fluorine-containing organic silicon compound represented by the.
JP11200344A 1999-07-14 1999-07-14 Production of fluorine-containing organosilicon compound Pending JP2001031684A (en)

Priority Applications (1)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007514708A (en) * 2003-12-19 2007-06-07 デグサ ゲーエムベーハー Prescribed method for producing a silicon compound having a fluoroalkyl group by hydrosilylation
US8163391B2 (en) 2006-12-20 2012-04-24 Nippon Steel Corporation Surface treated steel sheet

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007514708A (en) * 2003-12-19 2007-06-07 デグサ ゲーエムベーハー Prescribed method for producing a silicon compound having a fluoroalkyl group by hydrosilylation
US8163391B2 (en) 2006-12-20 2012-04-24 Nippon Steel Corporation Surface treated steel sheet

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