JP2000038361A - New fluorine compound and method for producing the same - Google Patents
New fluorine compound and method for producing the sameInfo
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- JP2000038361A JP2000038361A JP10208076A JP20807698A JP2000038361A JP 2000038361 A JP2000038361 A JP 2000038361A JP 10208076 A JP10208076 A JP 10208076A JP 20807698 A JP20807698 A JP 20807698A JP 2000038361 A JP2000038361 A JP 2000038361A
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- producing
- group
- fluorinated
- same
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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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
(57)【要約】
【課題】新規な不飽和フッ素アルコールを得る。
【解決手段】一般式（２）
ＲｆＣＦ＝ＣＨ−ＣＨ2ＯＨ （２）
〔式中、Ｒｆは、パーフルオロアルキル基又はポリフル
オロアルキル基を示す。〕で表される化合物及び固体酸
触媒を用いたその製造法。(57) [Problem] To obtain a novel unsaturated fluorine alcohol. A general formula (2) RfCF = CH-CH 2 OH (2) wherein, Rf is selected from the group consisting illustrates a perfluoroalkyl group or a polyfluoroalkyl group. And a method for producing the same using a solid acid catalyst.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、１級の不飽和フッ
素アルコールの合成方法に関するものである。１級の不
飽和フッ素アルコールは、例えば各種撥剤等の原料であ
るフッ素アルコールとして利用できる。本発明は、固体
酸触媒を用いるため、反応物との分離も容易であり、工
業的実施も可能である。TECHNICAL FIELD The present invention relates to a method for synthesizing a primary unsaturated fluorine alcohol. Primary unsaturated fluoroalcohols can be used, for example, as fluoroalcohols as raw materials for various repellents. Since the present invention uses a solid acid catalyst, it can be easily separated from reactants, and can be industrially implemented.
【０００２】[0002]
【従来の技術及びその課題】炭化水素系オレフィンに固
体酸触媒を作用させ、水和によりアルコールを合成させ
る例は知られているが（特開昭６３−１５４６３６号公
報、特開昭６３−１５６７３６号公報、特開昭６３−１
５４６３３号公報、特開平９−１６９６８１号公報）、
フッ素化されたαオレフィンから、二重結合の位置が移
動したアリルアルコール型の不飽和フッ素アルコールを
得る方法は知られていない。2. Description of the Related Art There are known examples in which a solid acid catalyst is allowed to act on a hydrocarbon olefin to synthesize an alcohol by hydration (JP-A-63-154636, JP-A-63-156736). No., JP-A-63-1
54633, JP-A-9-169681),
There is no known method for obtaining an allylic alcohol type unsaturated fluoroalcohol in which the position of a double bond has been transferred from a fluorinated α-olefin.
【０００３】本発明は、不飽和フッ素アルコール、その
製造法及び不飽和フッ素アルコール製造用触媒を提供す
ることを目的とする。An object of the present invention is to provide an unsaturated fluoroalcohol, a method for producing the same, and a catalyst for producing an unsaturated fluoroalcohol.
【０００４】[0004]
【課題を解決するための手段】本発明は、以下の項１〜
項３を提供するものである。Means for Solving the Problems The present invention provides the following items 1 to
Item 3 is provided.
【０００５】項１． 一般式（１） ＲｆＣＦ2−ＣＨ＝ＣＨ2 （１） 〔式中、Ｒｆは、パーフルオロアルキル基又はポリフル
オロアルキル基を示す。〕で表されるフッ素化αオレフ
ィンを固体酸触媒の存在下に水と反応させることを特徴
とする一般式（２） ＲｆＣＦ＝ＣＨ−ＣＨ2ＯＨ （２） 〔式中、Ｒｆは、前記に定義された通りである。〕で表
される不飽和フッ素化アルコールの製造法。Item 1. Formula (1) RfCF 2 -CH = CH 2 (1) wherein, Rf is selected from the group consisting illustrates a perfluoroalkyl group or a polyfluoroalkyl group. Fluorinated α-olefin represented by] the general formula (2) RfCF = CH-CH 2 OH (2) wherein which comprises reacting with water in the presence of a solid acid catalyst, Rf is selected from the group consisting in the As defined. ] The method for producing an unsaturated fluorinated alcohol represented by the formula:
【０００６】項２． 固体酸触媒が、Ｓｉ−Ａｌ系複合
酸化物、Ｓｉ−Ａｌ−Ｐ系複合酸化物、あるいはそれら
がフッ素化されたものであることを特徴とする請求項１
記載の不飽和フッ素化アルコールの製造法 項３． 一般式（２） ＲｆＣＦ＝ＣＨ−ＣＨ2ＯＨ （２） 〔式中、Ｒｆは、パーフルオロアルキル基又はポリフル
オロアルキル基を示す。〕で表される化合物。Item 2. The solid acid catalyst is a Si-Al-based composite oxide, a Si-Al-P-based composite oxide, or a fluorinated compound thereof.
2. The method for producing the unsaturated fluorinated alcohol described in item 3. Formula (2) RfCF = CH-CH 2 OH (2) wherein, Rf is selected from the group consisting illustrates a perfluoroalkyl group or a polyfluoroalkyl group. ] The compound represented by these.
【０００７】[0007]
【発明の実施の形態】本明細書において、「固体酸」と
は、陽子供与体又は電子受容体として働く固体を意味
し、酸性白土のような粘土鉱物、シリカアルミナ、陽イ
オン交換樹脂、通常の酸を担体に付着させた固形化酸
（例えばシリカゲルやアルミナに硫酸、リン酸などを付
着させたもの）、酸化アルミニウム、酸化バナジウムな
どが例示される。BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, the term "solid acid" means a solid that acts as a proton donor or an electron acceptor, and includes clay minerals such as acid clay, silica alumina, and cation exchange resins. Solidified acids (for example, silica gel or alumina with sulfuric acid, phosphoric acid, or the like attached thereto), aluminum oxide, vanadium oxide, and the like.
【０００８】本発明の固体酸として、以下の１〜８が例
示される。[0008] Examples of the solid acid of the present invention include the following 1 to 8.
【０００９】１．単元系金属酸化物：アルミナ、シリ
カ、チタニア、ジルコニア、ニオブ酸等； ２．複合系金属酸化物：シリカ・アルミナ、シリカ・チ
タニア、シリカ・ジルコニア、アルミナ・バナジア、シ
リカ・マグネシア、チタニア・ジルコニア、ＡｌＰＯ4
等； ３．金属硫酸塩ないし金属燐酸塩：硫酸ニッケル、硫酸
鉄、燐酸鉄等； ４．固型化酸：燐酸／シリカ、ＳｂＦ5／シリカ、ＢＦ3
／Ｃ等； ５．天然鉱物および層状化合物：活性白土、天然ゼオラ
イト、モンモリロナイト等； ６．ヘテロポリ酸：Ｈ3ＰＷ12Ｏ40・５Ｈ2Ｏ、Ｈ3ＰＷ
12Ｏ40・６Ｈ2Ｏ ７．合成ゼオライト：ＺＳＭ−５、ＡｌＰＯ4ゼオライ
ト、ＳＡＰＯ（Ａｌ−Ｐ−Ｓｉ系合成ゼオライト）；お
よび ８．樹脂：ナフィオンＨなどの強酸性のカチオン交換樹
脂等。1. 1. Single metal oxide: alumina, silica, titania, zirconia, niobate, etc .; Complex metal oxides: silica / alumina, silica / titania, silica / zirconia, alumina / vanadia, silica / magnesia, titania / zirconia, AlPO 4
Etc .; 3. Metal sulfate or metal phosphate: nickel sulfate, iron sulfate, iron phosphate, etc .; Solid of acid: phosphoric acid / silica, SbF 5 / silica, BF 3
/ C etc .; 5. Natural minerals and layered compounds: activated clay, natural zeolites, montmorillonite, etc .; Heteropolyacids: H 3 PW 12 O 40 · 5H 2 O, H 3 PW
12 O 40 · 6H 2 O 7. Synthetic zeolites: ZSM-5, AlPO 4 zeolite, SAPO (Al-P-Si-based synthetic zeolite); and 8. Resin: Strongly acidic cation exchange resin such as Nafion H.
【００１０】前記固体酸は、一部がフッ素化されたもの
であってもよい。[0010] The solid acid may be partially fluorinated.
【００１１】Ｒｆで表されるパーフルオロアルキル基と
しては、ＣＦ3、ＣＦ3ＣＦ2、ＣＦ3（ＣＦ2ＣＦ2）
n（式中ｎは、１〜５の整数を示す。)、ＣＦ3ＣＦ（Ｃ
Ｆ3）、ＣＦ3ＣＦ2（ＣＦ2ＣＦ2）m（式中ｍは、１〜５
の整数を示す。)等の直鎖又は分枝を有する炭素数１〜
１２のパーフルオロアルキル基が挙げられる。The perfluoroalkyl group represented by Rf includes CF 3 , CF 3 CF 2 , CF 3 (CF 2 CF 2 )
n (n represents an integer of 1 to 5), CF 3 CF (C
F 3 ), CF 3 CF 2 (CF 2 CF 2 ) m (where m is 1 to 5)
Indicates an integer. )) Having 1 to 1 carbon atoms having a straight or branched chain
12 perfluoroalkyl groups.
【００１２】Ｒｆで表されるポリフルオロアルキル基と
しては、ＨＣＦ2、ＨＣＦ2ＣＦ2、ＨＣＦ2（ＣＦ2Ｃ
Ｆ2）n（式中ｎは１〜５の整数を示す)、ＨＣＦ2ＣＦ
（ＣＦ3）、ＨＣＦ2ＣＦ2（ＣＦ2ＣＦ2）m（式中ｍは、
１〜５の整数を示す。)等の直鎖又は分枝を有する炭素
数１〜１２のポリフルオロアルキル基が挙げられる。The polyfluoroalkyl group represented by Rf includes HCF 2 , HCF 2 CF 2 , HCF 2 (CF 2 C
F 2 ) n (n represents an integer of 1 to 5), HCF 2 CF
(CF 3 ), HCF 2 CF 2 (CF 2 CF 2 ) m (where m is
Shows an integer of 1 to 5. )) And a linear or branched polyfluoroalkyl group having 1 to 12 carbon atoms.
【００１３】本発明の酸触媒は、好ましくはＳｉ−Ａｌ
系複合酸化物である。該複合酸化物のＳｉＯ2／Ａｌ2Ｏ
3モル比は、５以上、好ましくは５〜４００、より好ま
しくは５〜１００である。[0013] The acid catalyst of the present invention is preferably Si-Al
This is a composite oxide. SiO 2 / Al 2 O of the composite oxide
The 3 molar ratio is 5 or more, preferably 5 to 400, more preferably 5 to 100.
【００１４】本発明の触媒（例えばＳｉＯ2／Ａｌ
2Ｏ3）は、一部がフッ素化されたものが望ましい。フッ
素化されたＳｉＯ2／Ａｌ2Ｏ3のフッ素含量は、０．１
〜２０重量％程度が好ましい。ゼオライト触媒のフッ素
化は、例えば文献(IntrazeoliteChemistry, ACS Symp.
Ser., 218 (1982) 41-58)に記載の方法に従い、ゼオラ
イトに対し希釈フッ素ガスを常温で約１０分間反応する
ことにより、行うことができる。The catalyst of the present invention (for example, SiO 2 / Al
2 O 3 ) is preferably partially fluorinated. The fluorine content of the fluorinated SiO 2 / Al 2 O 3 is 0.1
About 20% by weight is preferable. The fluorination of zeolite catalysts is described, for example, in the literature (Intrazeolite Chemistry, ACS Symp.
Ser., 218 (1982) 41-58) and reacting the zeolite with a diluted fluorine gas at room temperature for about 10 minutes.
【００１５】フッ素化されたゼオライトのフッ素含量
は、２〜１０重量％程度である。The fluorine content of the fluorinated zeolite is of the order of 2 to 10% by weight.
【００１６】本発明の方法によれば、一般式（１） ＲｆＣＦ2−ＣＨ＝ＣＨ2 （１） 〔式中、Ｒｆは、前記に同じ〕で表されるフッ素化αオ
レフィンを酸触媒の存在下に水と反応させることにより
を特徴とする一般式（２） ＲｆＣＦ＝ＣＨ−ＣＨ2ＯＨ （２） 〔式中、Ｒｆは、前記に同じ。〕で表される新規な１級
の不飽和フッ素アルコールが製造できる。反応温度は、
１２０〜４００℃程度が好ましい。According to the method of the present invention, the fluorinated α-olefin represented by the general formula (1) RfCF 2 —CH ＝ CH 2 (1) wherein Rf is the same as above is used in the presence of an acid catalyst. formula, wherein by reacting with water under (2) RfCF = CH-CH 2 OH (2) wherein, Rf is selected from the group consisting the same. And a novel primary unsaturated fluoroalcohol represented by the following formula: The reaction temperature is
About 120 to 400 ° C. is preferable.
【００１７】[0017]
【発明の効果】本発明によれば、工業的生産に適した方
法により、新規な不飽和フッ素アルコールを提供でき
る。According to the present invention, a novel unsaturated fluorine alcohol can be provided by a method suitable for industrial production.
【００１８】[0018]
【実施例】以下、本発明を実施例を用いてより詳細に説
明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail with reference to embodiments.
【００１９】実施例１（気相反応） 内径１０ｍｍ、長さ２５０ｍｍのステンレス製反応管に
市販の高シリカゼオライト（ＳｉＯ2／Ａｌ2Ｏ3＝４
０）触媒を１０ｇ充填し、ヒーターにて３００℃に昇温
した。本反応管にＣＦ3ＣＦ2（ＣＦ2ＣＦ2）2ＣＨ＝Ｃ
Ｈ2／水／窒素＝１／１７．５／２．５（モル比）のガ
スを供給し（ＣＦ3ＣＦ2（ＣＦ2ＣＦ2）2ＣＨ＝ＣＨ2の
供給速度は、９．７ｇ／ｈｒ）、触媒上で接触反応させ
た。反応管出口に取り付けた氷トラップ、およびドライ
アイス／メタノール・トラップにて反応物を回収しＧＣ
分析を行ったところ、転化率５％、選択率８０％でＣＦ
3ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ＝ＣＨＣＨ2（ＯＨ）が得ら
れた。Example 1 (gas phase reaction) A commercially available high silica zeolite (SiO 2 / Al 2 O 3 = 4) was placed in a stainless steel reaction tube having an inner diameter of 10 mm and a length of 250 mm.
0) 10 g of the catalyst was charged, and the temperature was raised to 300 ° C. by a heater. In this reaction tube, CF 3 CF 2 (CF 2 CF 2 ) 2 CH = C
A gas of H 2 /water/nitrogen=1/17.5/2.5 (molar ratio) is supplied (CF 3 CF 2 (CF 2 CF 2 ) 2 CH = CH 2 supply rate is 9.7 g / hr), a catalytic reaction was carried out on the catalyst. The reaction product was collected by an ice trap attached to the outlet of the reaction tube and a dry ice / methanol trap,
Analysis showed that the conversion rate was 5% and the selectivity was 80%.
3 CF 2 CF 2 CF 2 CF 2 CF = CHCH 2 (OH) was obtained.
【００２０】実施例２（気相反応） 内径１０ｍｍ、長さ２５０ｍｍのステンレス製反応管に
市販のＺＳＭ−５型ゼオライト（ＳｉＯ2／Ａｌ2Ｏ3＝
７０）触媒を１０ｇ充填し、ヒーターにて３００℃に昇
温した。本反応管にＣＦ3ＣＦ2（ＣＦ2ＣＦ2）2ＣＨ＝
ＣＨ2／水／窒素＝１／１７．５／２．５（モル比）の
ガスを供給し（ＣＦ3ＣＦ2（ＣＦ2ＣＦ2）2ＣＨ＝ＣＨ2
の供給速度は、９．７ｇ／ｈｒ）、触媒上で接触反応さ
せた。反応管出口に取り付けた氷トラップ、およびドラ
イアイス／メタノール・トラップにて反応物を回収しＧ
Ｃ分析を行ったところ、転化率６％、選択率７５％でＣ
Ｆ3ＣＦ2ＣＦ2ＣＦ2ＣＦ2ＣＦ＝ＣＨＣＨ2（ＯＨ）が得
られた。Example 2 (Vapor phase reaction) A commercially available ZSM-5 type zeolite (SiO 2 / Al 2 O 3 ) was placed in a stainless steel reaction tube having an inner diameter of 10 mm and a length of 250 mm.
70) 10 g of the catalyst was charged, and the temperature was raised to 300 ° C. by a heater. In this reaction tube, CF 3 CF 2 (CF 2 CF 2 ) 2 CH =
A gas of CH 2 /water/nitrogen=1/17.5/2.5 (molar ratio) is supplied (CF 3 CF 2 (CF 2 CF 2 ) 2 CH = CH 2
At a feed rate of 9.7 g / hr). The reaction product was collected by an ice trap attached to the outlet of the reaction tube and a dry ice / methanol trap, and
When C analysis was carried out, the conversion was 6% and the selectivity was 75%.
F 3 CF 2 CF 2 CF 2 CF 2 CF = CHCH 2 (OH) was obtained.
【００２１】実施例３（バッチ式反応） 冷却コンデンサー付きなす型フラスコ（５０ｃｃ）にＣ
Ｆ3ＣＦ2（ＣＦ2ＣＦ2）3ＣＨ＝ＣＨ2を５ｇ、実施例１
で用いた触媒を２ｇ仕込み、マントルヒーターにて加熱
した。還流下、９時間激しく撹拌しながら反応を行い、
冷却後、反応生成物をＧＣにて分析した。その結果、転
化率３％、選択率８３％でＣＦ3ＣＦ2（ＣＦ2ＣＦ2）2
ＣＦ2ＣＦ＝ＣＨＣＨ2（ＯＨ）が得られた。Example 3 (Batch type reaction) C was added to an eggplant type flask (50 cc) equipped with a cooling condenser.
5 g of F 3 CF 2 (CF 2 CF 2 ) 3 CH = CH 2 , Example 1
2 g of the catalyst used in the above was charged and heated with a mantle heater. The reaction was carried out under vigorous stirring for 9 hours under reflux.
After cooling, the reaction product was analyzed by GC. As a result, CF 3 CF 2 (CF 2 CF 2 ) 2 was obtained at a conversion of 3% and a selectivity of 83%.
CF 2 CF ＝ CHCH 2 (OH) was obtained.
【００２２】得られた化合物のデータを以下に示す。The data of the obtained compound are shown below.
【００２３】1Ｈ−ＮＭＲ（δ，ｐｐｍ）：５．８５
（ｄｔ、１Ｈ）、４．５５（ｍ、２Ｈ）19 Ｆ−ＮＭＲ（δ，ｐｐｍ）：−８１．６（３Ｆ０）、
−１１８．５（２Ｆ）、−１２２．７（４Ｆ）、−１２
３．４（４Ｆ）、−１２６．９（２Ｆ）、−１２８．６
（１Ｆ） ＭＳ（ｍ／ｅ）：４４３ 実施例４（バッチ式反応） 冷却コンデンサー付きなす型フラスコ（５０ｃｃ）にＣ
Ｆ3ＣＦ2（ＣＦ2ＣＦ2）3ＣＨ＝ＣＨ2を５ｇ、および文
献(Intrazeolite Chemistry, ACS Symp. Ser.,218 (198
2) 41-58)の方法によりフッ素化処理した実施例１の触
媒（フッ素化率１０％）２ｇを仕込み、マントルヒータ
ーにて加熱した。還流下、９時間激しく撹拌しながら反
応を行い、冷却後、反応生成物をＧＣにて分析した。そ
の結果、転化率１３％、選択率８０％でＣＦ3ＣＦ2（Ｃ
Ｆ2ＣＦ2）2ＣＦ2ＣＦ＝ＣＨＣＨ2（ＯＨ）が得られ
た。得られたアルコールの物性値は実施例３で得られた
ものと同一であった。 1 H-NMR (δ, ppm): 5.85
(Dt, 1H), 4.55 (m, 2H) 19 F-NMR (δ, ppm): -81.6 (3F0),
-118.5 (2F), -122.7 (4F), -12
3.4 (4F),-126.9 (2F), -128.6
(1F) MS (m / e): 443 Example 4 (Batch Reaction) C in an eggplant-shaped flask (50 cc) with a cooling condenser
5 g of F 3 CF 2 (CF 2 CF 2 ) 3 CHＣＨCH 2 and literature (Intrazeolite Chemistry, ACS Symp. Ser., 218 (198
2) 2 g of the catalyst of Example 1 (fluorination rate 10%) fluorinated by the method of 41-58) was charged, and heated with a mantle heater. The reaction was carried out under vigorous stirring for 9 hours under reflux, and after cooling, the reaction product was analyzed by GC. As a result, CF 3 CF 2 (C
F 2 CF 2 ) 2 CF 2 CF = CHCH 2 (OH) was obtained. The physical properties of the obtained alcohol were the same as those obtained in Example 3.
フロントページの続き Ｆターム(参考） 4H006 AA01 AA02 AB80 AC14 AC41 BA68 BE60 FC74 FE11 FE71 FE74 4H039 CA60 CF10 CG90 CJ10 Continued on the front page F term (reference) 4H006 AA01 AA02 AB80 AC14 AC41 BA68 BE60 FC74 FE11 FE71 FE74 4H039 CA60 CF10 CG90 CJ10
Claims (3)
オロアルキル基を示す。〕で表されるフッ素化αオレフ
ィンを固体酸触媒の存在下に水と反応させることを特徴
とする一般式（２） ＲｆＣＦ＝ＣＨ−ＣＨ2ＯＨ （２） 〔式中、Ｒｆは、前記に定義された通りである。〕で表
される不飽和フッ素化アルコールの製造法。(1) RfCF 2 —CH ＝ CH 2 (1) wherein Rf represents a perfluoroalkyl group or a polyfluoroalkyl group. Fluorinated α-olefin represented by] the general formula (2) RfCF = CH-CH 2 OH (2) wherein which comprises reacting with water in the presence of a solid acid catalyst, Rf is selected from the group consisting in the As defined. ] The method for producing an unsaturated fluorinated alcohol represented by the formula:
Ｓｉ−Ａｌ−Ｐ系複合酸化物、あるいはそれらがフッ素
化されたものであることを特徴とする請求項１記載の不
飽和フッ素化アルコールの製造法2. A solid acid catalyst comprising: a Si—Al-based composite oxide;
2. The method for producing an unsaturated fluorinated alcohol according to claim 1, wherein the compound is a Si-Al-P-based composite oxide or a fluorinated compound thereof.
オロアルキル基を示す。〕で表される化合物。3. A compound represented by the general formula (2): RfCFＣＦCH—CH 2 OH (2) wherein Rf represents a perfluoroalkyl group or a polyfluoroalkyl group. ] The compound represented by these.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10208076A JP2000038361A (en) | 1998-07-23 | 1998-07-23 | New fluorine compound and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
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| JP10208076A JP2000038361A (en) | 1998-07-23 | 1998-07-23 | New fluorine compound and method for producing the same |
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| JP2000038361A true JP2000038361A (en) | 2000-02-08 |
Family
ID=16550254
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| JP10208076A Pending JP2000038361A (en) | 1998-07-23 | 1998-07-23 | New fluorine compound and method for producing the same |
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| JP (1) | JP2000038361A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009093567A1 (en) * | 2008-01-24 | 2009-07-30 | Unimatec Co., Ltd. | Fluoroalkyl alcohol mixture and method for producing the same |
| WO2009093568A1 (en) * | 2008-01-24 | 2009-07-30 | Unimatec Co., Ltd. | Mixture of fluoroalkyl alcohol-unsaturated carboxylic acid derivatives, polymer of the derivatives, and water repellent oil repellent agent containing the polymer as active ingredient |
-
1998
- 1998-07-23 JP JP10208076A patent/JP2000038361A/en active Pending
Cited By (11)
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|---|---|---|---|---|
| WO2009093567A1 (en) * | 2008-01-24 | 2009-07-30 | Unimatec Co., Ltd. | Fluoroalkyl alcohol mixture and method for producing the same |
| WO2009093568A1 (en) * | 2008-01-24 | 2009-07-30 | Unimatec Co., Ltd. | Mixture of fluoroalkyl alcohol-unsaturated carboxylic acid derivatives, polymer of the derivatives, and water repellent oil repellent agent containing the polymer as active ingredient |
| JP2009173576A (en) * | 2008-01-24 | 2009-08-06 | Unimatec Co Ltd | Fluoroalkyl alcohol mixture and its production method |
| CN101925570A (en) * | 2008-01-24 | 2010-12-22 | 优迈特株式会社 | Fluoroalkyl alcohol unsaturated carboxylic acid derivative mixture, polymer thereof, and water-and oil-repellent agent containing the polymer as active ingredient |
| CN101925568A (en) * | 2008-01-24 | 2010-12-22 | 优迈特株式会社 | Fluoroalkyl alcohol mixture and method for producing the same |
| KR101129666B1 (en) | 2008-01-24 | 2012-03-28 | 유니마테크 가부시키가이샤 | Fluoroalkyl alcohol mixture and method for producing the same |
| KR101137286B1 (en) | 2008-01-24 | 2012-04-20 | 유니마테크 가부시키가이샤 | Mixture of fluoroalkyl alcohol-unsaturated carboxylic acid derivatives, polymer of the derivatives, and water repellent oil repellent agent containing the polymer as active ingredient |
| JP5003759B2 (en) * | 2008-01-24 | 2012-08-15 | ユニマテック株式会社 | Fluoroalkyl alcohol unsaturated carboxylic acid derivative mixture, these polymers, and water / oil repellent containing this polymer as an active ingredient |
| US8278361B2 (en) | 2008-01-24 | 2012-10-02 | Unimatec Co., Ltd. | Fluoroalkyl alcohol mixture and method for producing the same |
| CN101925570B (en) * | 2008-01-24 | 2013-06-19 | 优迈特株式会社 | Fluoroalkyl alcohol unsaturated carboxylic acid derivative mixture, their polymer, and water and oil repellent agent containing the polymer as an active ingredient |
| US8481660B2 (en) | 2008-01-24 | 2013-07-09 | Unimatec Co., Ltd. | Mixture of fluoroalkyl alcohol-unsaturated carboxylic acid derivatives, polymer of the mixture, and water-and oil-repellent containing the polymer as active ingredient |
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