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KR20050016881A - Fluorine-containing alcohols and process for production thereof - Google Patents

Fluorine-containing alcohols and process for production thereof

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Publication number
KR20050016881A
KR20050016881A KR10-2004-7021125A KR20047021125A KR20050016881A KR 20050016881 A KR20050016881 A KR 20050016881A KR 20047021125 A KR20047021125 A KR 20047021125A KR 20050016881 A KR20050016881 A KR 20050016881A
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fluorine
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후루카와유타카
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아사히 가라스 가부시키가이샤
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/13—Saturated ethers containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

신규인 불소함유 알코올 및 그 제조방법을 제공한다.A novel fluorine-containing alcohol and a method of manufacturing the same are provided.

R1CY1HCY2Y3OQ1OH 또는 HOQ2OCZ1 Z2CZ3HR2CZ4HCZ5Z6OQ2OH 로 나타내는 불소함유 알코올 (단, R1 은 1가 불소함유 유기기 등, R2는 2가 불소함유 유기기 등, Y1∼Y 3, Z1∼Z6 은 불소원자, Q1, Q2 는 알킬렌기 등). 또한, -CX1 = CX2X3 으로 나타내는 기를 갖는 화합물과 HOQOH 로 나타내는 디올을 알칼리 금속 화합물의 존재 하에 반응시키는, -CX1HCX2X3OQOH 으로 나타내는 기를 갖는 불소함유 알코올의 제조방법 (단, X1, X2, X3 은 불소원자, Q 는 알킬렌기 등).Fluorine-containing alcohols represented by R 1 CY 1 HCY 2 Y 3 OQ 1 OH or HOQ 2 OCZ 1 Z 2 CZ 3 HR 2 CZ 4 HCZ 5 Z 6 OQ 2 OH (wherein R 1 is a monovalent fluorine-containing organic group, R 2 is a divalent fluorine-containing organic group such as Y 1 to Y 3 , Z 1 to Z 6 are fluorine atoms, Q 1 and Q 2 are alkylene groups. A method for producing a fluorine-containing alcohol having a group represented by -CX 1 HCX 2 X 3 OQOH, wherein the compound having a group represented by -CX 1 = CX 2 X 3 and the diol represented by HOQOH are reacted in the presence of an alkali metal compound. , X 1 , X 2 , X 3 are fluorine atoms, Q is alkylene group and the like.

Description

불소함유 알코올 및 그 제조방법{FLUORINE-CONTAINING ALCOHOLS AND PROCESS FOR PRODUCTION THEREOF}Fluorine-containing alcohol and its manufacturing method {FLUORINE-CONTAINING ALCOHOLS AND PROCESS FOR PRODUCTION THEREOF}

본 발명은 신규인 불소함유 알코올 및 그 제조방법에 관한 것이다.The present invention relates to a novel fluorine-containing alcohol and a method for producing the same.

말단 부분에 수산기를 갖는 불소함유 화합물로는 Rf(CF2CF2)nCH 2CH2OH (Rf 는 폴리플루오로알킬기를 나타낸다) 가 있고, 그 불소함유 화합물의 제조방법에는 이하의 방법이 있다.Examples of the fluorine-containing compound having a hydroxyl group at the terminal portion include R f (CF 2 CF 2 ) n CH 2 CH 2 OH (R f represents a polyfluoroalkyl group). There is this.

RfI 와 CF2 = CF2 를 텔로메리제이션 반응에 의해 Rf(CF2 CF2)nI (n 은 1 이상의 정수) 로 한 것을 에틸렌에 부가하여 Rf(CF2CF2)nCH2 CH2I 로 하고, 다시 알칼리 금속을 담지한 고체 산촉매를 사용하여 Rf(CF2CF2)nCH2CH 2OH 로 하는 방법 (일본 공개특허공보 2000-79345호).R f I and CF 2 = a CF 2 by telomerase Mary hybridization reaction R f (CF 2 CF 2) n I , in addition to ethylene it was the (n is an integer of 1 or more) R f (CF 2 CF 2 ) n CH A method of converting 2 CH 2 I to R f (CF 2 CF 2 ) n CH 2 CH 2 OH using a solid acid catalyst carrying an alkali metal (JP-A-2000-79345).

그러나, 텔로메리제이션 반응에 의해 Rf(CF2CF2)nI 를 제조하면 탄소수 (즉, 상기 화학식에서의 n) 에 분포를 갖는 화합물이 생성되기 때문에, 그 화합물에서 유도된 Rf(CF2CF2)nCH2CH2OH 도 탄소수에 분포를 갖는 불소함유 화합물이 된다. 따라서, 말단 부분에 수산기가 있고 또 특정한 탄소수를 갖는 불소함유 화합물을 얻기 위해서는, 반응 후에 분리할 필요가 있다.However, the preparation of R f (CF 2 CF 2 ) n I by the telomerization reaction produces a compound having a distribution in carbon number (ie, n in the formula), and therefore R f (CF derived from the compound 2 CF 2 ) n CH 2 CH 2 OH is also a fluorine-containing compound having a distribution in carbon number. Therefore, in order to obtain the fluorine-containing compound which has a hydroxyl group in a terminal part and has a specific carbon number, it is necessary to isolate | separate after reaction.

본 발명자들은 상기 텔로메리제이션 반응에서의 탄소수 분포의 난점을 해소하기 위해서는 반응원료에 디올을 사용하는 것이 중요하고, 그것에 기초하여 말단 부분에 수산기를 갖는 신규 화합물을 찾아내었다. 즉 본 발명은, 신규인 불소함유 알코올 및 그 제조방법을 제공하는 것을 목적으로 한다.The present inventors found that it is important to use diols in the reaction raw materials in order to solve the difficulty of the carbon number distribution in the telomerization reaction, and based on them, a new compound having a hydroxyl group at the terminal portion was found. That is, an object of the present invention is to provide a novel fluorine-containing alcohol and a production method thereof.

발명의 개시Disclosure of the Invention

본 발명은, 아래 식 1 (화합물 1) 또는 아래 식 2 (화합물 2) 로 나타내는 불소함유 알코올을 제공한다.The present invention provides a fluorine-containing alcohol represented by the following formula 1 (compound 1) or the following formula 2 (compound 2).

R1CY1HCY2Y3OQ1OH ···식 1R 1 CY 1 HCY 2 Y 3 OQ 1 OH

HOQ2OCZ1Z2CZ3HR2CZ4HCZ5Z 6OQ3OH ···식 2HOQ 2 OCZ 1 Z 2 CZ 3 HR 2 CZ 4 HCZ 5 Z 6 OQ 3 OH

단, 식 1, 식 2 에서의 기호는 이하의 의미를 나타낸다.However, the symbol in Formula 1 and Formula 2 represents the following meaning.

R1 : 1가 유기기, 할로겐원자 또는 수소원자.R 1 : monovalent organic group, halogen atom or hydrogen atom.

R2 : 2가 유기기.R 2 : divalent organic group.

Y1, Y2, Y3 : 각각 독립하여 수소원자 또는 불소원자이고, R1 이 불소원자가 아닌 경우는 Y1, Y2, Y3 중 적어도 하나는 불소원자이다.Y 1 , Y 2 , Y 3 are each independently a hydrogen atom or a fluorine atom, and when R 1 is not a fluorine atom, at least one of Y 1 , Y 2 and Y 3 is a fluorine atom.

Z1, Z2, Z3, Z4, Z5, Z6 : 각각 독립하여 수소원자 또는 불소원자이고, Z1, Z2, Z3 중 적어도 하나는 불소원자이며, 또한 Z4, Z5, Z6 중 적어도 하나는 불소원자이다.Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 : are each independently a hydrogen atom or a fluorine atom, at least one of Z 1 , Z 2 , Z 3 is a fluorine atom, and Z 4 , Z 5 At least one of Z 6 is a fluorine atom.

Q1, Q2, Q3 : 각각 독립하여 2가 유기기.Q 1 , Q 2 , Q 3 : each independently a divalent organic group.

또, 본 발명은 아래 식 3 으로 나타내는 기를 갖는 화합물 (화합물 3) 과 아래 식 4 로 나타내는 디올 (화합물 4) 을 알칼리 금속 화합물의 존재 하에 반응시키는 것을 특징으로 하는, 아래 식 5 로 나타내는 기를 갖는 불소함유 알코올 (화합물 5) 의 제조방법을 제공한다.Moreover, this invention reacts the compound (compound 3) which has a group represented by following formula (3), and the diol (compound 4) represented by following formula 4 in presence of an alkali metal compound, The fluorine which has a group represented by following formula (5) A method for producing a containing alcohol (Compound 5) is provided.

-CX1 = CX2X3 ···식 3CX 1 = CX 2 X 3 Equation 3

HOQOH ···식 4HOQOH ...

-CX1HCX2X3OQOH ···식 5-CX 1 HCX 2 X 3 OQOH ...

단, 식 3, 식 4, 식 5 에서의 기호는 이하의 의미를 나타낸다.However, the symbol in Formula 3, Formula 4, and Formula 5 shows the following meaning.

X1, X2, X3 : 각각 독립하여 수소원자 또는 불소원자이고,X 1 , X 2 , X 3 : each independently represent a hydrogen atom or a fluorine atom,

X1, X2, X3 중 적어도 하나는 불소원자이다.At least one of X 1 , X 2 and X 3 is a fluorine atom.

Q : 2가 유기기.Q: A divalent organic group.

발명을 실시하기 위한 최선의 형태Best Mode for Carrying Out the Invention

화합물 1 에 있어서, R1 은 1가 유기기, 할로겐원자 또는 수소원자이다. R1 로는, 1가 탄화수소기 또는 1가 할로겐화 탄화수소기가 바람직하고, 특히 에테르성 산소원자를 함유하는 1가 할로겐화 탄화수소기가 바람직하다. R1 은 직쇄 구조일 수도 있고, 분기 구조를 갖고 있을 수도 있으며, 고리 구조를 갖고 있을 수도 있다.In compound 1, R 1 is a monovalent organic group, a halogen atom or a hydrogen atom. As R 1 , a monovalent hydrocarbon group or a monovalent halogenated hydrocarbon group is preferable, and a monovalent halogenated hydrocarbon group containing an etheric oxygen atom is particularly preferable. R 1 may have a linear structure, may have a branched structure, or may have a ring structure.

그 중에서도 R1 은 불소화 탄화수소기가 바람직하고, 특히 탄화수소기의 모든 수소원자가 불소원자로 치환된 퍼플루오로 탄화수소기가 바람직하고, 특히 에테르성 산소원자를 함유하는 퍼플루오로 탄화수소기가 바람직하다. 에테르성 산소원자가 함유되는 경우는, 그 에테르성 산소원자는 말단 부분에 존재하는 것이 바람직하다.Among them, R 1 is preferably a fluorinated hydrocarbon group, particularly a perfluoro hydrocarbon group in which all hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms, and particularly preferably a perfluoro hydrocarbon group containing etheric oxygen atoms. When an ether oxygen atom is contained, it is preferable that the ether oxygen atom exists in a terminal part.

화합물 1 에 있어서, Y1, Y2, Y3 으로는 불소원자가 바람직하고, 전부가 불소원자인 것이 바람직하다. 또한, Q1 은 2가 탄화수소기가 바람직하고, 특히 알킬렌기가 바람직하다. 또한 Q1 로는 -(CH2)t- (t 는 1 이상의 정수) 로 나타내는 기가 바람직하고, 특히 t 가 2∼12 인 기가 바람직하며, 특히 t 가 2∼6 인 기가 바람직하다.In the compound 1, Y 1, Y 2, Y 3 is a fluorine atom is preferred, and it is preferable that all of the fluorine atoms. In addition, Q 1 is preferably a divalent hydrocarbon group, and particularly preferably an alkylene group. Roneun also Q 1 - (CH 2) t - is preferably a group, particularly preferably represents a t (t is an integer of 1 or more) groups and 2 to 12, especially preferred is the t is 2 to 6.

화합물 1 로는, 합성이 용이하기 때문에 R'CFHCF2O(CH2)mOH (단, R' 는 탄소수 1∼16 의 에테르성 산소원자를 함유하는 1가 불소함유 유기기, m 은 2∼12 의 정수를 나타낸다) 로 나타내는 화합물 (화합물 6) 이 바람직하다. 화합물 6 에 있어서, R' 는 직쇄 구조일 수도 있고, 분기 구조를 갖고 있을 수도 있다. 분기 구조를 갖는 경우에는 분기 부분이 말단에 존재하는 것이 바람직하고, 그 분기 부분은 (CF3)2CF- 가 바람직하다.Roneun Compound 1, because the synthesis is easy R'CFHCF 2 O (CH 2) m OH ( However, R 'is a first oil containing ethereal oxygen atoms with a carbon number of 1 to 16 fluorine unit, m is 2 to 12 Preference is given to compounds (compound 6) represented by the following formulae. In compound 6, R 'may be a linear structure, and may have a branched structure. If having a branched structure is preferable to a branched part present at the terminal, and the branch portion is the (CF 3) 2 CF- preferred.

그 중에서도 R' 로는 불소화 탄화수소기가 바람직하고, 특히 탄화수소기의 모든 수소원자가 불소원자로 치환된 퍼플루오로 탄화수소기가 바람직하고, 특히 에테르성 산소원자를 함유하는 퍼플루오로 탄화수소기가 바람직하다. 에테르성 산소원자가 함유되는 경우는 그 에테르성 산소원자는 말단 부분에 존재하는 것이 바람직하다.Among them, R 'is preferably a fluorinated hydrocarbon group, particularly a perfluoro hydrocarbon group in which all hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms, and particularly preferably a perfluoro hydrocarbon group containing an etheric oxygen atom. When an ether oxygen atom is contained, it is preferable that the ether oxygen atom exists in a terminal part.

화합물 1 의 구체예로는 이하의 화합물을 들 수 있다.Specific examples of the compound 1 include the following compounds.

H(CF2)2O(CH2)2OH,H (CF 2 ) 2 O (CH 2 ) 2 OH,

H(CF2)2O(CH2)3OH,H (CF 2 ) 2 O (CH 2 ) 3 OH,

H(CF2)2O(CH2)4OH,H (CF 2 ) 2 O (CH 2 ) 4 OH,

H(CF2)2O(CH2)6OH,H (CF 2 ) 2 O (CH 2 ) 6 OH,

CF3CFHCF2O(CH2)2OH,CF 3 CFHCF 2 O (CH 2 ) 2 OH,

CF3CFHCF2O(CH2)3OH,CF 3 CFHCF 2 O (CH 2 ) 3 OH,

CF3CFHCF2O(CH2)4OH,CF 3 CFHCF 2 O (CH 2 ) 4 OH,

CF3CFHCF2O(CH2)6OH,CF 3 CFHCF 2 O (CH 2 ) 6 OH,

C2F5CFHCF2O(CH2)2OH,C 2 F 5 CFHCF 2 O (CH 2 ) 2 OH,

C2F5CFHCF2O(CH2)3OH,C 2 F 5 CFHCF 2 O (CH 2 ) 3 OH,

C2F5CFHCF2O(CH2)4OH,C 2 F 5 CFHCF 2 O (CH 2 ) 4 OH,

C2F5CFHCF2O(CH2)6OH,C 2 F 5 CFHCF 2 O (CH 2 ) 6 OH,

C3F7CFHCF2O(CH2)2OH,C 3 F 7 CFHCF 2 O (CH 2 ) 2 OH,

C3F7CFHCF2O(CH2)3OH,C 3 F 7 CFHCF 2 O (CH 2 ) 3 OH,

C3F7CFHCF2O(CH2)4OH,C 3 F 7 CFHCF 2 O (CH 2 ) 4 OH,

C3F7CFHCF2O(CH2)6OH,C 3 F 7 CFHCF 2 O (CH 2 ) 6 OH,

C5F11CFHCF2O(CH2)2OH,C 5 F 11 CFHCF 2 O (CH 2 ) 2 OH,

C5F11CFHCF2O(CH2)3OH,C 5 F 11 CFHCF 2 O (CH 2 ) 3 OH,

C5F11CFHCF2O(CH2)4OH,C 5 F 11 CFHCF 2 O (CH 2 ) 4 OH,

C5F11CFHCF2O(CH2)6OH,C 5 F 11 CFHCF 2 O (CH 2 ) 6 OH,

C7F15CFHCF2O(CH2)2OH,C 7 F 15 CFHCF 2 O (CH 2 ) 2 OH,

C7F15CFHCF2O(CH2)3OH,C 7 F 15 CFHCF 2 O (CH 2 ) 3 OH,

C7F15CFHCF2O(CH2)4OH,C 7 F 15 CFHCF 2 O (CH 2 ) 4 OH,

C7F15CFHCF2O(CH2)6OH,C 7 F 15 CFHCF 2 O (CH 2 ) 6 OH,

C3F7OCFHCF2O(CH2)2OH,C 3 F 7 OCFHCF 2 O (CH 2 ) 2 OH,

C3F7OCFHCF2O(CH2)3OH,C 3 F 7 OCFHCF 2 O (CH 2 ) 3 OH,

C3F7OCFHCF2O(CH2)4OH,C 3 F 7 OCFHCF 2 O (CH 2 ) 4 OH,

C3F7OCFHCF2O(CH2)6OH,C 3 F 7 OCFHCF 2 O (CH 2 ) 6 OH,

C4F9OCFHCF2OCH2CH2OH,C 4 F 9 OCFHCF 2 OCH 2 CH 2 OH,

C4F9OCFHCF2O(CH2)3OH,C 4 F 9 OCFHCF 2 O (CH 2 ) 3 OH,

C4F9OCFHCF2O(CH2)4OH,C 4 F 9 OCFHCF 2 O (CH 2 ) 4 OH,

C4F9OCFHCF2O(CH2)6OH,C 4 F 9 OCFHCF 2 O (CH 2 ) 6 OH,

C5F11OCFHCF2O(CH2)2OH,C 5 F 11 OCFHCF 2 O (CH 2 ) 2 OH,

C5F11OCFHCF2O(CH2)3OH,C 5 F 11 OCFHCF 2 O (CH 2 ) 3 OH,

C5F11OCFHCF2O(CH2)4OH,C 5 F 11 OCFHCF 2 O (CH 2 ) 4 OH,

C5F11OCFHCF2O(CH2)6OH,C 5 F 11 OCFHCF 2 O (CH 2 ) 6 OH,

C6F13OCFHCF2O(CH2)2OH,C 6 F 13 OCFHCF 2 O (CH 2 ) 2 OH,

C6F13OCFHCF2O(CH2)3OH,C 6 F 13 OCFHCF 2 O (CH 2 ) 3 OH,

C6F13OCFHCF2O(CH2)4OH,C 6 F 13 OCFHCF 2 O (CH 2 ) 4 OH,

C6F13OCFHCF2O(CH2)6OH,C 6 F 13 OCFHCF 2 O (CH 2 ) 6 OH,

(CF3)2CFCF2CFHCF2O(CH2)2OH,(CF 3 ) 2 CFCF 2 CFHCF 2 O (CH 2 ) 2 OH,

(CF3)2CFCF2CFHCF2O(CH2)3OH,(CF 3 ) 2 CFCF 2 CFHCF 2 O (CH 2 ) 3 OH,

(CF3)2CFCF2CFHCF2O(CH2)4OH,(CF 3 ) 2 CFCF 2 CFHCF 2 O (CH 2 ) 4 OH,

(CF3)2CFCF2CFHCF2O(CH2)6OH,(CF 3 ) 2 CFCF 2 CFHCF 2 O (CH 2 ) 6 OH,

F[CF(CF3)CF2O]CFHCF2O(CH2)2OH,F [CF (CF 3 ) CF 2 O] CFHCF 2 O (CH 2 ) 2 OH,

F[CF(CF3)CF2O]CFHCF2O(CH2)4OH,F [CF (CF 3 ) CF 2 O] CFHCF 2 O (CH 2 ) 4 OH,

F[CF(CF3)CF2O]2CFHCF2O(CH2)2OH,F [CF (CF 3 ) CF 2 O] 2 CFHCF 2 O (CH 2 ) 2 OH,

F[CF(CF3)CF2O]2CFHCF2O(CH2)4OH,F [CF (CF 3 ) CF 2 O] 2 CFHCF 2 O (CH 2 ) 4 OH,

F[CF(CF3)CF2O]3CFHCF2O(CH2)2OH,F [CF (CF 3 ) CF 2 O] 3 CFHCF 2 O (CH 2 ) 2 OH,

F[CF(CF3)CF2O]3CFHCF2O(CH2)4OH.F [CF (CF 3 ) CF 2 O] 3 CFHCF 2 O (CH 2 ) 4 OH.

화합물 2 에 있어서, R2 로는 2가 탄화수소기 또는 2가 할로겐화 탄화수소기가 바람직하고, 특히 에테르성 산소원자를 함유하는 2가 할로겐화 탄화수소기가 바람직하다. R2 는 직쇄 구조일 수도 있고, 분기 구조를 갖고 있을 수도 있고, 고리 구조를 갖고 있을 수도 있다.In the compound 2, R 2 roneun is preferably a divalent hydrocarbon group or a divalent halogenated hydrocarbon group is preferable and, in particular, the second containing ethereal oxygen atom halogenated hydrocarbon. R 2 may have a linear structure, may have a branched structure, or may have a ring structure.

그 중에서도 R2 는 불소화 탄화수소기가 바람직하고, 특히 탄화수소기의 모든 수소원자가 불소원자로 치환된 퍼플루오로 탄화수소기가 바람직하고, 특히 에테르성 산소원자를 함유하는 퍼플루오로 탄화수소기가 바람직하다. 에테르성 산소원자가 함유되는 경우는, 그 에테르성 산소원자는 말단 부분에 존재하는 것이 바람직하다.Among them, R 2 is preferably a fluorinated hydrocarbon group, particularly a perfluoro hydrocarbon group in which all hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms, and particularly preferably a perfluoro hydrocarbon group containing an etheric oxygen atom. When an ether oxygen atom is contained, it is preferable that the ether oxygen atom exists in a terminal part.

화합물 2 에 있어서, Z1, Z2, Z3, Z4, Z5, Z6 으로는 불소원자가 바람직하고, 전부가 불소원자인 것이 바람직하다. 또한, Q2, Q3 은 상기 화합물 1 에서의 Q 1 과 동일한 양태가 바람직하다.In compound 2, Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , and Z 6 are preferably fluorine atoms, and all of them are preferably fluorine atoms. In addition, the same aspect as Q <1> in the said compound 1 is preferable for Q <2> , Q <3> .

화합물 2 로는, 합성이 용이하기 때문에 R"[CFHCF2O(CH2)qOH]2 (단, R" 는 탄소수 1∼16 의 에테르성 산소원자를 함유하는 2가 불소함유 유기기, q 는 2∼12 의 정수를 나타낸다) 로 나타내는 화합물 (화합물 7) 이 바람직하다. 화합물 7 에 있어서, R" 는 직쇄 구조일 수도 있고, 분기 구조를 갖고 있을 수도 있다. 분기 구조를 갖는 경우에는 분기 부분이 말단에 존재하는 것이 바람직하고, 그 분기 부분은 (CF3)2CF- 가 바람직하다.As compound 2, since it is easy to synthesize | combine, R "[CFHCF 2 O (CH 2 ) q OH] 2 (wherein R" is a divalent fluorine-containing organic group containing an ether oxygen atom of 1 to 16 carbon atoms, q is Preference is given to compounds represented by the integers of 2 to 12 (compound 7). In the compound 7, R "may be a straight chain structure, there may be have a branch structure. When having a branched structure is preferred to a branched part present at the terminal, and the branch section (CF 3) 2 CF- Is preferred.

그 중에서도 R" 로는 불소화 탄화수소기가 바람직하고, 특히 탄화수소기의 모든 수소원자가 불소원자로 치환된 퍼플루오로 탄화수소기가 바람직하고, 특히 에테르성 산소원자를 함유하는 퍼플루오로 탄화수소기가 바람직하다. 에테르성 산소원자가 함유되는 경우는, 그 에테르성 산소원자는 말단 부분에 존재하는 것이 바람직하다.Among them, R ″ is preferably a fluorinated hydrocarbon group, particularly a perfluoro hydrocarbon group in which all hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms, and particularly preferably a perfluoro hydrocarbon group containing an ether oxygen atom. When contained, the etheric oxygen atom is preferably present at the terminal portion.

화합물 2 의 구체예로는 이하의 화합물을 들 수 있다.Specific examples of the compound 2 include the following compounds.

HO(CH2)2OCF2CFH(CF2)2CFHCF2O(CH2 )2OH,HO (CH 2 ) 2 OCF 2 CFH (CF 2 ) 2 CFHCF 2 O (CH 2 ) 2 OH,

HO(CH2)3OCF2CFH(CF2)2CFHCF2O(CH2 )3OH,HO (CH 2 ) 3 OCF 2 CFH (CF 2 ) 2 CFHCF 2 O (CH 2 ) 3 OH,

HO(CH2)4OCF2CFH(CF2)2CFHCF2O(CH2 )4OH,HO (CH 2 ) 4 OCF 2 CFH (CF 2 ) 2 CFHCF 2 O (CH 2 ) 4 OH,

HO(CH2)6OCF2CFH(CF2)2CFHCF2O(CH2 )6OH,HO (CH 2 ) 6 OCF 2 CFH (CF 2 ) 2 CFHCF 2 O (CH 2 ) 6 OH,

HOCH2CH2OCF2CFH(CF2)3CFHCF2OCH2 CH2OH,HOCH 2 CH 2 OCF 2 CFH (CF 2 ) 3 CFHCF 2 OCH 2 CH 2 OH,

HO(CH2C)3OCF2CFH(CF2)3CFHCF2O(CH2 )3OH,HO (CH 2 C) 3 OCF 2 CFH (CF 2 ) 3 CFHCF 2 O (CH 2 ) 3 OH,

HO(CH2)4OCF2CFH(CF2)3CFHCF2O(CH2 )4OH,HO (CH 2 ) 4 OCF 2 CFH (CF 2 ) 3 CFHCF 2 O (CH 2 ) 4 OH,

HO(CH2)6OCF2CFH(CF2)3CFHCF2O(CH2 )6OH,HO (CH 2 ) 6 OCF 2 CFH (CF 2 ) 3 CFHCF 2 O (CH 2 ) 6 OH,

HO(CH2)2OCF2CFHO(CF2)2OCFHCF2O(CH 2)2OH,HO (CH 2 ) 2 OCF 2 CFHO (CF 2 ) 2 OCFHCF 2 O (CH 2 ) 2 OH,

HO(CH2)3OCF2CFHO(CF2)2OCFHCF2O(CH 2)3OH,HO (CH 2 ) 3 OCF 2 CFHO (CF 2 ) 2 OCFHCF 2 O (CH 2 ) 3 OH,

HO(CH2)4OCF2CFHO(CF2)2OCFHCF2O(CH 2)4OH,HO (CH 2 ) 4 OCF 2 CFHO (CF 2 ) 2 OCFHCF 2 O (CH 2 ) 4 OH,

HO(CH2)6OCF2CFHO(CF2)2OCFHCF2O(CH 2)6OH,HO (CH 2 ) 6 OCF 2 CFHO (CF 2 ) 2 OCFHCF 2 O (CH 2 ) 6 OH,

HO(CH2)2OCF2CFHO(CF2)3OCFHCF2O(CH 2)2OH,HO (CH 2 ) 2 OCF 2 CFHO (CF 2 ) 3 OCFHCF 2 O (CH 2 ) 2 OH,

HO(CH2)3OCF2CFHO(CF2)3OCFHCF2O(CH 2)3OH,HO (CH 2 ) 3 OCF 2 CFHO (CF 2 ) 3 OCFHCF 2 O (CH 2 ) 3 OH,

HO(CH2)4OCF2CFHO(CF2)3OCFHCF2O(CH 2)4OH,HO (CH 2 ) 4 OCF 2 CFHO (CF 2 ) 3 OCFHCF 2 O (CH 2 ) 4 OH,

HO(CH2)6OCF2CFHO(CF2)3OCFHCF2O(CH 2)6OH,HO (CH 2 ) 6 OCF 2 CFHO (CF 2 ) 3 OCFHCF 2 O (CH 2 ) 6 OH,

HO(CH2)2OCF2CFH[OCF2CF(CF3)]OCF2(CF 2)4CF2O[CF(CF3)CF2O]CFHCF2O(CH2 )2OH,HO (CH 2 ) 2 OCF 2 CFH [OCF 2 CF (CF 3 )] OCF 2 (CF 2 ) 4 CF 2 O [CF (CF 3 ) CF 2 O] CFHCF 2 O (CH 2 ) 2 OH,

HO(CH2)3OCF2CFH[OCF2CF(CF3)]OCF2(CF 2)4CF2O[CF(CF3)CF2O]CFHCF2O(CH2 )3OH,HO (CH 2 ) 3 OCF 2 CFH [OCF 2 CF (CF 3 )] OCF 2 (CF 2 ) 4 CF 2 O [CF (CF 3 ) CF 2 O] CFHCF 2 O (CH 2 ) 3 OH,

HO(CH2)4OCF2CFH[OCF2CF(CF3)]OCF2(CF 2)4CF2O[CF(CF3)CF2O]CFHCF2O(CH2 )4OH,HO (CH 2 ) 4 OCF 2 CFH [OCF 2 CF (CF 3 )] OCF 2 (CF 2 ) 4 CF 2 O [CF (CF 3 ) CF 2 O] CFHCF 2 O (CH 2 ) 4 OH,

HO(CH2)6OCF2CFH[OCF2CF(CF3)]OCF2(CF 2)4CF2O[CF(CF3)CF2O]CFHCF2O(CH2 )6OH.HO (CH 2 ) 6 OCF 2 CFH [OCF 2 CF (CF 3 )] OCF 2 (CF 2 ) 4 CF 2 O [CF (CF 3 ) CF 2 O] CFHCF 2 O (CH 2 ) 6 OH.

화합물 3 에 있어서, X1, X2, X3 은 불소원자가 바람직하고, 전부가 불소원자인 것이 바람직하다. 화합물 3 은 J. Am. Chem. Soc, 75, 4525 (1953) 등에 기재되는 제조방법에 의해 합성할 수 있다.In compound 3, X 1 , X 2 and X 3 are preferably fluorine atoms, and all of them are preferably fluorine atoms. Compound 3 is J. Am. Chem. It can synthesize | combine by the manufacturing method described in Soc, 75, 4525 (1953).

화합물 3 으로는 아래 식 8 로 나타내는 화합물 (화합물 8) 이 바람직하다.As compound 3, the compound (compound 8) represented by following formula 8 is preferable.

R[CX1 = CX2X3]p ···식 8R [CX 1 = CX 2 X 3 ] p ...

R : p가 유기기. R: p is an organic group.

p : 1∼4 의 정수.p: integer of 1-4.

X1, X2, X3 : 각각 독립하여 수소원자 또는 불소원자이고, X1, X2, X3 중 적어도 하나는 불소원자이다.X 1 , X 2 and X 3 are each independently a hydrogen atom or a fluorine atom, and at least one of X 1 , X 2 and X 3 is a fluorine atom.

화합물 8 에 있어서, R 로는 상기 화합물 1 에서의 R1 또는 상기 화합물 2 에서의 R2 와 동일한 양태가 바람직하다. X1, X2, X3 으로는 불소원자가 바람직하고, 전부가 불소원자인 것이 바람직하다. p 로는 1 또는 2 가 바람직하다.In compound 8, R roneun the same aspects and R 2 in the R 1 or 2 wherein the compound in the compound 1 is preferable. As X <1> , X <2> , X <3> , a fluorine atom is preferable and it is preferable that all are fluorine atoms. As p, 1 or 2 is preferable.

화합물 3 의 구체예로는 이하의 화합물을 들 수 있다.As specific examples of the compound 3, the following compounds may be mentioned.

CF2 = CF2, CF3CF = CF2, C2F5CF = CF 2,CF 2 = CF 2 , CF 3 CF = CF 2 , C 2 F 5 CF = CF 2 ,

C3F7CF = CF2, C5F11CF = CF2,C 3 F 7 CF = CF 2 , C 5 F 11 CF = CF 2 ,

C7F15CF = CF2, C3F7OCF = CF2,C 7 F 15 CF = CF 2 , C 3 F 7 OCF = CF 2 ,

C4F9OCF = CF2, C5F11OCF = CF2,C 4 F 9 OCF = CF 2 , C 5 F 11 OCF = CF 2 ,

C6F13OCF = CF2, (CF3)2CFCF2CF = CF 2,C 6 F 13 OCF = CF 2 , (CF 3 ) 2 CFCF 2 CF = CF 2 ,

F[CF(CF3)CF2O]CF = CF2,F [CF (CF 3 ) CF 2 O] CF = CF 2 ,

F[CF(CF3)CF2O]2CF = CF2,F [CF (CF 3 ) CF 2 O] 2 CF = CF 2 ,

F[CF(CF3)CF2O]3CF = CF2, F [CF (CF 3 ) CF 2 O] 3 CF = CF 2,

CF2 = CF(CF2)2CF = CF2,CF 2 = CF (CF 2 ) 2 CF = CF 2 ,

CF2 = CF(CF2)3CF = CF2,CF 2 = CF (CF 2 ) 3 CF = CF 2 ,

CF2 = CFO(CF2)2OCF = CF2,CF 2 = CFO (CF 2 ) 2 OCF = CF 2 ,

CF2 = CFO(CF2)3OCF = CF2,CF 2 = CFO (CF 2 ) 3 OCF = CF 2 ,

CF2 = CF[OCF2CF(CF3)]OCF2(CF2)4CF 2O[CF(CF3)CF2O]CF = CF2.CF 2 = CF [OCF 2 CF (CF 3 )] OCF 2 (CF 2 ) 4 CF 2 O [CF (CF 3 ) CF 2 O] CF = CF 2 .

화합물 4 에 있어서, Q 는 상기 화합물 1 에서의 Q1 과 동일한 양태가 바람직하다.In compound 4, Q is preferably the same as Q 1 in compound 1.

화합물 4 의 구체예로는, HO(CH2)2OH, HO(CH2)3OH, HO(CH2 )4OH, HO(CH2)6OH 등을 바람직하게 들 수 있다.Concrete examples of the compound 4, HO (CH 2) there may be mentioned 2 OH, HO (CH 2) 3 OH, HO (CH 2) 4 OH, HO (CH 2) 6 OH , etc. Preferably.

화합물 5 에 있어서, X1, X2, X3, Q 는 상기 화합물 3 또는 화합물 4 에서와 동일한 양태가 바람직하다.In the compound 5, X 1 , X 2 , X 3 and Q are preferably the same as those in the compound 3 or the compound 4.

화합물 5 로는, 아래 식 9 로 나타내는 화합물 (화합물 9) 이 바람직하다.As compound 5, the compound (compound 9) represented by following formula 9 is preferable.

R[CX1HCX2X3OQOH]p ···식 9R [CX 1 HCX 2 X 3 OQOH] p ...

R : p가 유기기.R: p is an organic group.

X1, X2, X3 : 각각 독립하여 수소원자 또는 불소원자이고, X1, X2, X3 중 적어도 하나는 불소원자이다.X 1 , X 2 and X 3 are each independently a hydrogen atom or a fluorine atom, and at least one of X 1 , X 2 and X 3 is a fluorine atom.

Q : 2가 유기기. Q: A divalent organic group.

p : 1∼4 의 정수.p: integer of 1-4.

화합물 9 에 있어서, R, X1, X2, X3, Q, p 로는 상기 화합물 4 또는 상기 화합물 8 에서와 동일한 양태가 바람직하다. 화합물 5 로는, 상기 화합물 1 또는 상기 화합물 2 를 바람직하게 들 수 있다.In the compound 9, R, X 1, X 2, X 3, Q, p roneun the same aspect as in the compound 4 or the compound 8 is preferred. As compound 5, the said compound 1 or the said compound 2 is mentioned preferably.

화합물 3 과 화합물 4 의 반응에서 사용되는 알칼리 금속 화합물로는, 알칼리 금속, 알칼리 금속 수소화물, 알칼리 금속 수산화물, 알칼리 금속 아미드 등을 바람직하게 들 수 있다. 구체적으로는 Na, K, Cs 등의 알칼리 금속, NaOH, KOH 등의 알칼리 금속 수산화물, NaH, KH 등의 알칼리 금속 수소화물, NaNH2, KNH2 등의 알칼리 금속 아미드를 바람직하게 들 수 있다.As an alkali metal compound used by reaction of the compound 3 and the compound 4, an alkali metal, an alkali metal hydride, an alkali metal hydroxide, an alkali metal amide, etc. are mentioned preferably. Specific examples thereof include alkali metal hydrides such as alkali metals such as Na, K and Cs, alkali metal hydroxides such as NaOH and KOH, alkali metal hydrides such as NaH and KH, and alkali metal amides such as NaNH 2 and KNH 2 .

상기 반응에 있어서, 알칼리 금속 화합물의 사용량은 특별히 한정되지 않지만, 화합물 3 의 1몰에 대하여 0.01∼1.0배몰을 사용하는 것이 바람직하고, 특히 반응속도를 고려하면 0.05∼0.5배몰을 사용하는 것이 바람직하다. 그 범위에서 사용하면, 부생성물의 생성이 적고 적절한 반응속도에서 반응이 진행하기 때문에 바람직하다.In the above reaction, the amount of the alkali metal compound to be used is not particularly limited, but it is preferable to use 0.01 to 1.0 times mole with respect to 1 mole of the compound 3, and particularly preferably 0.05 to 0.5 times mole in consideration of the reaction rate. . It is preferable to use in this range because the formation of by-products is small and the reaction proceeds at an appropriate reaction rate.

상기 반응에 있어서, 식 5 로 나타내는 기를 1개 갖는 화합물, 즉 화합물 1 을 제조하는 경우에는, 화합물 4 의 사용량은 화합물 3 의 1몰에 대하여 1∼5배몰이 바람직하고, 특히 2∼4배몰이 바람직하다. 또, 식 5 로 나타내는 기를 2개 갖는 화합물, 즉 화합물 2 를 제조하는 경우에는, 화합물 4 의 사용량은 화합물 3 의 1몰에 대하여 2∼10배몰이 바람직하고, 특히 4∼8배몰이 바람직하다. 그 범위에서 반응시키면 화합물 4 의 한쪽 수산기하고만 화합물 3 이 반응한 생성물이 생성되기 쉬우므로 바람직하다.In the above reaction, in the case of producing a compound having one group represented by the formula (5), that is, compound 1, the amount of compound 4 is preferably 1 to 5 times mole, more preferably 2 to 4 times mole relative to 1 mole of compound 3. desirable. Moreover, when manufacturing the compound which has two groups represented by Formula 5, ie, the compound 2, 2-10 times mole is preferable with respect to 1 mol of compounds 3, and, as for the usage-amount of compound 4, 4-8 times mole is especially preferable. When it reacts in the range, since the product which compound 3 reacted only with one hydroxyl group of compound 4 is easy to produce | generate, it is preferable.

또, 상기 반응의 온도는 0∼150℃ 가 바람직하고, 특히 40∼120℃ 가 바람직하다. 그 범위에서 반응시키면 적절한 반응속도로 반응이 진행되어 화합물 3 만의 중합반응이 실시되지 않기 때문에 바람직하다.Moreover, 0-150 degreeC is preferable and, as for the temperature of the said reaction, 40-120 degreeC is especially preferable. It is preferable to react in this range because the reaction proceeds at an appropriate reaction rate and the polymerization reaction of only compound 3 is not carried out.

또 그 반응에서는 용매를 사용할 수도 있고 사용하지 않을 수도 있지만, 용매는 사용하는 것이 바람직하다. 그 용매로는, 화합물 4 를 용해하는 용매, 화합물 5 를 용해하는 용매, 상기 반응에서 실질적으로 불활성인 용매가 바람직하다. 그 용매로는 에테르, 니트릴 화합물 등이 바람직하고, 구체적으로는 디에틸에테르, 글라임, 디옥산, 테트라히드로푸란, 아세토니트릴, 프로피오니트릴이 바람직하며, 특히 디옥산, 테트라히드로푸란 또는 아세토니트릴이 바람직하다.Moreover, although the solvent may be used or may not be used in the reaction, it is preferable to use a solvent. As this solvent, the solvent which melt | dissolves compound 4, the solvent which melt | dissolves compound 5, and the solvent which is substantially inert in the said reaction are preferable. The solvent is preferably an ether, a nitrile compound, or the like, and specifically, diethyl ether, glyme, dioxane, tetrahydrofuran, acetonitrile or propionitrile are preferable, in particular dioxane, tetrahydrofuran or acetonitrile This is preferable.

용매의 사용량은 특별히 한정되지 않지만, 반응속도, 생산성을 고려하면 생성물인 화합물 5 가 1∼60질량% 가 되는 양을 사용하는 것이 바람직하고, 특히 3∼50질량% 가 되는 양을 사용하는 것이 바람직하다.Although the usage-amount of a solvent is not specifically limited, When considering reaction rate and productivity, it is preferable to use the quantity which the compound 5 which is a product becomes 1-60 mass%, and it is especially preferable to use the quantity which becomes 3-50 mass%. Do.

또, 화합물 3 은 높은 압력에서 중합반응이 일어나기 쉽기 때문에, 그 중합반응을 방지하기 위해 상기 반응에서는 중합금지제를 사용하는 것이 바람직하다. 그 중합금지제는 원료보다도 전에 반응계에 넣어 두어도 되고, 원료와 함께 반응계에 넣어도 된다. 그 중합금지제로는 특별히 한정없이 사용할 수 있지만, 예를 들어 리모넨, 피넨, 시멘, 테르피넨 등을 바람직하게 들 수 있다.Moreover, since compound 3 tends to produce a polymerization reaction at high pressure, it is preferable to use a polymerization inhibitor in the said reaction in order to prevent the polymerization reaction. The polymerization inhibitor may be put in the reaction system before the raw material, or may be put in the reaction system together with the raw material. Although it can use without a restriction | limiting in particular as this polymerization inhibitor, For example, limonene, pinene, cymene, terpinene etc. are mentioned preferably.

본 발명에 있어서, 화합물 5 가 생성하는 기구는 아래와 같이 추정된다.In the present invention, the mechanism generated by compound 5 is estimated as follows.

즉, 디올 (화합물 4) 이 알칼리 금속 화합물에 의해 알콕시드 화합물이 되고, 그 알콕시드 화합물이 화합물 3 에 부가되고 다시 금속 부분이 수소원자로 치환되어 화합물 5 이 생성된다. 디올을 사용함으로써, 한쪽 수산기가 반응하더라도 다른쪽 수산기가 남기 때문에 불소함유 알코올을 제조할 수 있다.In other words, the diol (compound 4) becomes an alkoxide compound by the alkali metal compound, the alkoxide compound is added to compound 3, and the metal part is further substituted with a hydrogen atom to produce compound 5. By using a diol, even if one hydroxyl group reacts, since the other hydroxyl group remains, a fluorine-containing alcohol can be manufactured.

본 발명에 의하면, 신규인 불소함유 알코올을 합성할 수 있다. 그 불소함유 알코올은 세정제, 각종 화합물의 중간체로서 유용하다. 예를 들어, 화합물 1 을 아크릴산과 반응시켜 얻을 수 있는 불소함유 아크릴레이트는 UV 경화 수지의 원료, 발수발유제로서 유용하다. 또, 화합물 2 를 우레탄 등의 축합계 수지의 공중합 성분으로서 사용하면, 그 수지의 표면을 개질할 수 있다.According to the present invention, a novel fluorine-containing alcohol can be synthesized. The fluorine-containing alcohol is useful as an detergent and an intermediate of various compounds. For example, the fluorine-containing acrylate obtained by reacting Compound 1 with acrylic acid is useful as a raw material for a UV curable resin and a water / oil repellent agent. Moreover, when compound 2 is used as a copolymerization component of condensed-system resin, such as urethane, the surface of this resin can be modified.

또한 본 발명의 불소함유 알코올의 원료인 화합물 3 은, Adv. Synth. Catal. 2001, 343, No.2 에 기재된 직접 불소화를 사용하여 합성할 수 있고, 직접 불소화로는 원료의 구조를 선택할 수 있기 때문에, 얻어진 불소함유 알코올도 여러 가지 구조인 것을 얻을 수 있다.Moreover, the compound 3 which is a raw material of the fluorine-containing alcohol of this invention is Adv. Synth. Catal. Since it can synthesize | combine using the direct fluorination as described in 2001, 343, No. 2, and since the structure of a raw material can be selected as a direct fluorination, the obtained fluorine-containing alcohol can also be obtained by various structures.

실시예Example

이하에 본 발명의 실시예를 들어 구체적으로 설명하는데, 본 발명은 이들에 한정되지 않는다.Although the Example of this invention is given to the following and it demonstrates concretely, this invention is not limited to these.

[예 1][Example 1]

내용적 50㎖ 인 스테인리스제 반응 용기에 1,4-디옥산 30g, C3F7OCF = CF2 10g, HO(CH2)2OH 4.67g 및 KOH 0.55g 을 넣은 후 밀폐하여 교반하면서 70℃ 에서 8시간 반응시켰다. 물을 50㎖ 넣어 2층 분리한 후 유기층을 증류하여, 생성물인 CF3CF2CF2OCFHCF2OCH2CH2OH 와 C3 F7OCFHCF2OCH2CH2OCF2CFHOC3F 7 10.9g 을 얻었다. 그 생성물 중 전자 : 후자의 비율은 75 : 25 (몰비) 이었다.30 g of 1,4-dioxane, C 3 F 7 OCF = CF 2 10 g, HO (CH 2 ) 2 OH 4.67 g and KOH 0.55 g were added to a 50 mL stainless steel reaction vessel, and then sealed and stirred at 70 ° C. The reaction was carried out for 8 hours. 50 ml of water was added to separate the two layers, and the organic layer was distilled to obtain 10.9 g of CF 3 CF 2 CF 2 OCFHCF 2 OCH 2 CH 2 OH and C 3 F 7 OCFHCF 2 OCH 2 CH 2 OCF 2 CFHOC 3 F 7 . Got it. The former: latter ratio in the product was 75:25 (molar ratio).

CF3CF2CF2OCFHCF2OCH2CH2OH 에 대한 측정결과를 이하에 나타낸다.The measurement results for CF 3 CF 2 CF 2 OCFHCF 2 OCH 2 CH 2 OH are shown below.

[예 2][Example 2]

내용적 50㎖ 인 스테인리스제 반응 용기에 1,4-디옥산 30g, C3F7OCF = CF2 10g, HO(CH2)4OH 13.55g 및 KOH 0.55g 을 넣고 밀폐하여 교반하면서 70℃ 에서 8시간 반응시켰다. 물을 50㎖ 넣어 2층 분리한 후 유기층을 증류하여, 생성물인 CF3CF2CF2OCFHCF2O(CH2)4OH 와 C3 F7OCFHCF2O(CH2)4OCF2CFHOC3F 7 12.8g 을 얻었다. 그 생성물 중 전자 : 후자의 비율은 94 : 6 (몰비) 이었다.30 g of 1,4-dioxane, C 3 F 7 OCF = CF 2 10 g, 13.55 g of HO (CH 2 ) 4 OH and 0.55 g of KOH were added to a 50 ml stainless steel reaction vessel at a temperature of 70 ° C. with stirring. The reaction was carried out for 8 hours. 50 ml of water was added to separate the two layers, and the organic layer was distilled. The product was CF 3 CF 2 CF 2 OCFHCF 2 O (CH 2 ) 4 OH and C 3 F 7 OCFHCF 2 O (CH 2 ) 4 OCF 2 CFHOC 3 F 7 12.8 g was obtained. The former: latter ratio in the product was 94: 6 (molar ratio).

CF3CF2CF2OCFHCF2O(CH2)4OH 에 대한 측정결과를 이하에 나타낸다.The measurement results for CF 3 CF 2 CF 2 OCFHCF 2 O (CH 2 ) 4 OH are shown below.

[예 3]Example 3

내용적 50㎖ 인 스테인리스제 반응 용기에 1,4-디옥산 30g, C3F7OCF = CF2 10g, HOCH2CH2CH2OH 5.72g 및 KOH 0.55g 을 넣고 밀폐하여 교반하면서 70℃ 에서 8시간 반응시켰다. 물을 50㎖ 넣어 2층 분리한 후 유기층을 증류하여, 생성물인 CF3CF2CF2OCFHCF2OCH2CH2CH2OH 와 C3F7OCFHCF2OCH2CH2CH2OCF2 CFHOC3F7 11.6g 을 얻었다. 생성물 중 전자 : 후자의 비율은 89 : 11 (몰비) 이었다.30 g of 1,4-dioxane, C 3 F 7 OCF = CF 2 10 g, 5.72 g of HOCH 2 CH 2 CH 2 OH, and 0.55 g of KOH were added to a 50 ml stainless steel reaction vessel at a temperature of 70 ° C. with stirring. The reaction was carried out for 8 hours. 50 ml of water was added to separate the two layers, and the organic layer was distilled. The product was CF 3 CF 2 CF 2 OCFHCF 2 OCH 2 CH 2 CH 2 OH and C 3 F 7 OCFHCF 2 OCH 2 CH 2 CH 2 OCF 2 CFHOC 3 F 7 11.6g was obtained. The former: latter ratio in the product was 89:11 (molar ratio).

CF3CF2CF2OCFHCF2OCH2CH2CH2OH 에 대한 측정결과를 이하에 나타낸다.The measurement results for CF 3 CF 2 CF 2 OCFHCF 2 OCH 2 CH 2 CH 2 OH are shown below.

[예 4]Example 4

내용적 50㎖ 인 스테인리스제 반응 용기에 1,4-디옥산 30g, C3F7OCF = CF2 10g, HO(CH2)6OH 8.88g 및 KOH 0.55g 을 넣고 밀폐하여 교반하면서 70℃ 에서 8시간 반응시켰다. 물을 50㎖ 넣어 2층 분리한 후 유기층을 증류하여, 생성물인 CF3CF2CF2OCFHCF2O(CH2)6OH 와 C3 F7OCFHCF2O(CH2)6OCF2CFHOC3F 7 의 13.0g 을 얻었다. 생성물 중 전자 : 후자의 비율은 87 : 13 (몰비) 이었다.30 g of 1,4-dioxane, C 3 F 7 OCF = CF 2 10 g, 8.88 g of HO (CH 2 ) 6 OH, and 0.55 g of KOH were added to a 50 mL stainless steel reaction vessel at a temperature of 70 ° C. with stirring. The reaction was carried out for 8 hours. 50 ml of water was added to separate the two layers, and the organic layer was distilled. The product was CF 3 CF 2 CF 2 OCFHCF 2 O (CH 2 ) 6 OH and C 3 F 7 OCFHCF 2 O (CH 2 ) 6 OCF 2 CFHOC 3 F 13.0 g of 7 was obtained. The former: latter ratio in the product was 87:13 (molar ratio).

CF3CF2CF2OCFHCF2O(CH2)6OH 에 대한 측정결과를 이하에 나타낸다.The measurement results for CF 3 CF 2 CF 2 OCFHCF 2 O (CH 2 ) 6 OH are shown below.

[예 5]Example 5

내용적 50㎖ 인 스테인리스제 반응 용기에 1,4-디옥산 30g, CF2 = CFO(CF2)2OCF = CF2 10g, HO(CH2)4OH 12.26g 및 KOH 0.55g 을 넣고 밀폐하여 교반하면서 70℃ 에서 8시간 반응시켰다. 물을 50㎖ 넣어 2층 분리한 후 유기층을 증류하여, 생성물인 HO(CH2)4OCF2HCFO(CF2)2OCFHCF 2O(CH2)4OH 13.2g 을 얻었다.30 g of 1,4-dioxane, CF 2 = CFO (CF 2 ) 2 OCF = CF 2 10 g, HO (CH 2 ) 4 OH 12.26 g and KOH 0.55 g were sealed in a 50 ml stainless steel reaction vessel. It was made to react at 70 degreeC for 8 hours, stirring. 50 mL of water was added to separate the two layers, and the organic layer was distilled off to obtain 13.2 g of HO (CH 2 ) 4 OCF 2 HCFO (CF 2 ) 2 OCFHCF 2 O (CH 2 ) 4 OH.

HO(CH2)4OCF2HCFO(CF2)2OCFHCF2O(CH 2)4OH 에 대한 측정결과를 이하에 나타낸다.The measurement results for HO (CH 2 ) 4 OCF 2 HCFO (CF 2 ) 2 OCFHCF 2 O (CH 2 ) 4 OH are shown below.

Claims (5)

아래 식 1 또는 아래 식 2 로 나타내는 불소함유 알코올.Fluorine-containing alcohol represented by the following formula 1 or the following formula 2. R1CY1HCY2Y3OQ1OH ···식 1R 1 CY 1 HCY 2 Y 3 OQ 1 OH HOQ2OCZ1Z2CZ3HR2CZ4HCZ5Z 6OQ3OH ···식 2HOQ 2 OCZ 1 Z 2 CZ 3 HR 2 CZ 4 HCZ 5 Z 6 OQ 3 OH 단, 식 1, 식 2 에서의 기호는 이하의 의미를 나타낸다.However, the symbol in Formula 1 and Formula 2 represents the following meaning. R1 : 1가 유기기, 할로겐원자 또는 수소원자.R 1 : monovalent organic group, halogen atom or hydrogen atom. R2 : 2가 유기기.R 2 : divalent organic group. Y1, Y2, Y3 : 각각 독립하여 수소원자 또는 불소원자이고, R1 이 불소원자가 아닌 경우는 Y1, Y2, Y3 중 하나 이상은 불소원자이다.Y 1 , Y 2 and Y 3 are each independently a hydrogen atom or a fluorine atom, and when R 1 is not a fluorine atom, at least one of Y 1 , Y 2 and Y 3 is a fluorine atom. Z1, Z2, Z3, Z4, Z5, Z6 : 각각 독립하여 수소원자 또는 불소원자이고, Z1, Z2, Z3 중 하나 이상은 불소원자이며, 또한 Z4, Z5, Z6 중 하나 이상은 불소원자이다.Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 : are each independently a hydrogen atom or a fluorine atom, at least one of Z 1 , Z 2 , Z 3 is a fluorine atom, and Z 4 , Z 5 , At least one of Z 6 is a fluorine atom. Q1, Q2, Q3 : 각각 독립하여 2가 유기기.Q 1 , Q 2 , Q 3 : each independently a divalent organic group. 아래 식 3 으로 나타내는 기를 갖는 화합물과 아래 식 4 로 나타내는 디올을, 알칼리 금속 화합물의 존재 하에 반응시키는 것을 특징으로 하는, 아래 식 5 로 나타내는 기를 갖는 불소함유 알코올의 제조방법.A method for producing a fluorine-containing alcohol having a group represented by the following formula (5), wherein the compound having a group represented by the following formula (3) and the diol represented by the following formula (4) are reacted in the presence of an alkali metal compound. -CX1 = CX2X3 ···식 3CX 1 = CX 2 X 3 Equation 3 HOQOH ···식 4HOQOH ... -CX1HCX2X3OQOH ···식 5-CX 1 HCX 2 X 3 OQOH ... 단, 식 3, 식 4, 식 5 에서의 기호는 이하의 의미를 나타낸다.However, the symbol in Formula 3, Formula 4, and Formula 5 shows the following meaning. X1, X2, X3 : 각각 독립하여 수소원자 또는 불소원자이고, X1, X2, X3 중 하나이상은 불소원자이다.X 1 , X 2 and X 3 are each independently a hydrogen atom or a fluorine atom, and at least one of X 1 , X 2 and X 3 is a fluorine atom. Q : 2가 유기기.Q: A divalent organic group. 제 1 항에 있어서, 상기 식 1 에서의 R1 이 에테르성 산소원자를 함유하는 1가 퍼플루오로 탄화수소기, 상기 식 2 에서의 R2 가 에테르성 산소원자를 함유하는 2가 퍼플루오로 탄화수소기인, 불소함유 알코올.The method of claim 1, wherein the formula R 1 is a hydrocarbon with a first containing ethereal oxygen atom perfluoroalkyl groups of from 1, the formula 2, R 2 is an ether hydrocarbon as sex divalent perfluoroalkyl group containing an oxygen atom in Fluorine-containing alcohols. 제 1 항 또는 제 2 항에 있어서, 상기 식 1 에서의 Q1, 상기 식 2 에서의 Q2, Q3 이 -(CH2)t- (t 는 1 이상의 정수) 인, 불소함유 알코올.According to claim 1 or 2, wherein the formula Q 2, Q 3 Q 1 in the formula 2 is from 1 - (CH 2) t - it is a fluorine-containing alcohol (t is an integer of 1 or greater). 제 2 항에 있어서, 상기 식 5 에서의 Q 가 -(CH2)t- (t 는 1 이상의 정수) 인, 불소함유 알코올의 제조방법.The method for producing a fluorine-containing alcohol according to claim 2, wherein Q in the formula (5) is- (CH 2 ) t- (t is an integer of 1 or more).
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101511399B1 (en) * 2007-08-06 2015-04-10 이 아이 듀폰 디 네모아 앤드 캄파니 Mixed fluoroalkyl-alkyl surfactants
KR20150120527A (en) * 2013-03-06 2015-10-27 유니마테크 가부시키가이샤 Fluorine-containing calcium composite particles, preparation method therefor, and surface treatment agent using same as active component
KR20210022061A (en) * 2018-06-20 2021-03-02 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. (Fur) fluoropolyether polymer

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101511399B1 (en) * 2007-08-06 2015-04-10 이 아이 듀폰 디 네모아 앤드 캄파니 Mixed fluoroalkyl-alkyl surfactants
KR20150120527A (en) * 2013-03-06 2015-10-27 유니마테크 가부시키가이샤 Fluorine-containing calcium composite particles, preparation method therefor, and surface treatment agent using same as active component
KR20210022061A (en) * 2018-06-20 2021-03-02 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. (Fur) fluoropolyether polymer

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