WO2012035942A1 - 新規含フッ素ビニルエーテル化合物およびその製造法 - Google Patents
新規含フッ素ビニルエーテル化合物およびその製造法 Download PDFInfo
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- WO2012035942A1 WO2012035942A1 PCT/JP2011/069037 JP2011069037W WO2012035942A1 WO 2012035942 A1 WO2012035942 A1 WO 2012035942A1 JP 2011069037 W JP2011069037 W JP 2011069037W WO 2012035942 A1 WO2012035942 A1 WO 2012035942A1
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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
- C07C43/14—Unsaturated ethers
- C07C43/17—Unsaturated ethers containing halogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
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- 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
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy 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
- C07C41/14—Preparation of ethers by exchange of organic parts on the ether-oxygen for other organic parts, e.g. by trans-etherification
Definitions
- the present invention relates to a novel fluorine-containing vinyl ether compound and a method for producing the same. More specifically, the present invention relates to a novel fluorine-containing vinyl ether compound having a perfluoroalkyl group having 6 or less carbon atoms and a method for producing the same.
- PFOA perfluorooctanoic acid
- PFCA perfluoroalkyl group-containing carboxylic acid having a perfluoroalkyl group having 8 or more carbon atoms
- the vinyl ether reported in each of the above documents often uses perfluoroalkylethyl alcohol, which is a perfluorocarboxylic acid precursor, as a raw material. In such reactions, perfluorocarbons having a carbon number of 8 or more are used in the environment.
- perfluorocarboxylic acid having a fluoroalkyl group has been suggested and has been regarded as a problem, and therefore, an alternative functional group is required.
- An object of the present invention is to provide a novel fluorine-containing vinyl ether having a perfluoroalkyl group having 6 or less carbon atoms, which is said to have low bioaccumulation, and a method for producing the same.
- Such fluorine-containing vinyl ether compounds have the general formula C n F 2n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c OH [II] (Wherein n, a, b and c are as defined above) and the general formula XCH 2 CH 2 OCH ⁇ CH 2 [III] (Wherein, X is halogen atom) and a 2-halo-ethyl vinyl ether represented by the presence of a palladium catalyst and an aliphatic amine, is prepared by reacting de-XCH 2 CH 2 OH of.
- the use of an aliphatic amine as a polymerization inhibitor for a raw material vinyl ether gives an almost quantitative conversion rate, thereby improving the yield of the fluorinated vinyl ether compound.
- the use ratio relative to the raw material vinyl ether can be reduced by about one digit.
- perfluoroalkyl ethyl vinyl ethers may undergo chemical changes in perfluorocarboxylic acids when they are subjected to any decomposition or compounds containing C n F 2n + 1 groups that are included as impurities.
- the perfluoroalkyl group has 6 or less carbon atoms with low bioaccumulation, and the CH 2 CF 2 group derived from vinylidene fluoride in the molecule is easily deHFed. Since a double bond is formed and is easily decomposed by ozonolysis, it is expected that long-chain fluoroalkyl units do not remain in the environment for a long time.
- fluorine-containing vinyl ether compound represented by the general formula [I] examples include the following compounds.
- fluorine-containing vinyl ether compounds [I] comprise a fluorine-containing alcohol represented by the general formula [II] and 2-haloethyl vinyl ether represented by the general formula [III] in the presence of a palladium catalyst and an aliphatic amine. This is produced by deoxidizing XCH 2 CH 2 OH.
- Examples of the fluorine-containing alcohol [II] as one reaction raw material include the following (see Patent Document 4). CF 3 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) OH CF 3 (CH 2 CF 2 ) 2 (CF 2 CF 2 ) (CH 2 CH 2 ) OH CF 3 (CH 2 CF 2 ) 4 (CF 2 CF 2 ) (CH 2 CH 2 ) OH CF 3 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) OH CF 3 (CH 2 CF 2 ) (CF 2 CF 2 ) 3 (CH 2 CH 2 ) OH CF 3 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) 3 OH C 3 F 7 (CH 2 CF 2 ) 2 (CF 2 CF 2 ) 2 (CH 2 CH 2 ) 2 OH C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (
- 2-haloethyl vinyl ether As the other reaction raw material 2-haloethyl vinyl ether to be reacted with these fluorine-containing alcohols, 2-haloethyl vinyl ether in which X is a halogen atom, preferably a chlorine atom or a bromine atom, more preferably a chlorine atom is preferred. Used.
- 2-haloethyl vinyl ether By using 2-haloethyl vinyl ether, the reaction conversion reaches 90% or more. This is because the de-XCH 2 CH 2 OH reaction is a reversible reaction, but 2-haloethyl vinyl ether with excellent elimination ability improves the conversion rate of the reaction and suppresses the reverse reaction. A significant improvement is expected.
- 2-haloethyl vinyl ether is used in an amount of 2 times mol or more, preferably 5 times mol or more, particularly preferably about 10 times mol of the fluorine-containing alcohol.
- the de-XCH 2 CH 2 OH reaction between the fluorinated alcohol and 2-haloethyl vinyl ether is performed in the presence of a palladium-based catalyst and an aliphatic amine.
- the palladium-based catalyst As the palladium-based catalyst, (1,10-phenanthroline) palladium acetate, (2,2′-bipyridyl) palladium acetate, bis (triphenylphosphino) palladium acetate and the like are used, and (1,10-phenanthroline is particularly preferable. ) Palladium acetate is used. These catalysts are used in an amount of 0.5 mol% or more, particularly preferably 0.5 to 2.5 mol%, based on the fluorinated alcohol.
- aliphatic amines those that are soluble in the raw material vinyl ether are used as polymerization inhibitors for vinyl ether, and for example, carbon number such as triethanolamine, diethanolamine, monoethanolamine, triisopropanolamine, diisopropanolamine, monoisopropanolamine, etc.
- Trialkylamines having an alkyl group of 1 to 8 carbon atoms such as monoamine, tributylamine, trihexylamine, trioctylamine having at least one hydroxyalkyl group of 1 to 4, hexamethylenediamine, octamethylenediamine, etc. Examples thereof include alkylene diamines having an alkylene group having 1 to 8 carbon atoms, or mixtures thereof.
- Triethanolamine, trioctylamine, and hexamethylenediamine are preferably used as the raw material vinyl ether. On the other hand, it is used in the range of 5 to 1000 ppm, preferably 300 to 700 ppm.
- the present applicant has previously proposed a method for producing a fluorine-containing vinyl ether compound using an alkali metal hydroxide such as potassium hydroxide as a polymerization inhibitor (see Patent Document 5).
- an alkali metal hydroxide such as potassium hydroxide as a polymerization inhibitor
- alkali metal hydroxides are almost insoluble in organic solvents and their effects are limited, further improvement in yield has been desired.
- the present invention by using the above-mentioned amine as a polymerization inhibitor, it is possible to further improve the yield with a smaller usage rate.
- reaction is carried out without solvent, but a solvent can also be used.
- a hydrocarbon solvent such as toluene or xylene or a cyclic ether solvent such as tetrahydrofuran or 1,4-dioxane is used.
- the reaction temperature is not particularly limited, but it is generally performed between room temperature and 80 ° C, particularly preferably between 40 ° C and 70 ° C.
- Unreacted 2-haloethyl vinyl ether, by-product 2-haloethanol and the target fluorine-containing vinyl ether compound are purified by fractional distillation, and those having a large molecular weight and high boiling point are purified by molecular distillation. Subject to reaction.
- Example 1 In a nitrogen atmosphere, 688 g (6.46 mol) of 2-chloroethyl vinyl ether was added to 3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12, 12,12 nonadecamethylene fluoro dodecanol C 4 F 9 (CH 2 CF 2) (CF 2 CF 2) 2 (CH 2 CH 2) OH (LC / MS / MS C 8 or more perfluorocarboxylic acids and analysis The content of the derivative is below the detection limit of 10 ppb or less) 341 g (0.646 mol), (1,10-phenanthroline) palladium acetate 2.4 g (0.006 mol; 1.0 mol% with respect to nonadecafluorododecanol) and 0.34 g (0.002 mol; 500 ppm based on 2-chloroethyl vinyl ether) of triethanolamine was added, and the mixture was stirred at 65 ° C.
- the obtained nonadecafluorododecyl vinyl ether was distilled and purified to a purity of 91 GC% or more using a distillation apparatus equipped with a vacuum pump.
- This purified reaction product was confirmed to be a compound represented by the following formula from the results of 1 H-NMR and 19 F-NMR.
- the content of C 8 or more perfluorocarboxylic acids and their derivatives by LC / MS / MS analysis were completely undetected.
- Example 2 In Example 1, instead of 0.34 g (0.002 mol; 500 ppm relative to 2-chloroethyl vinyl ether) of triethanolamine, 0.48 g (0.001 mol; 700 ppm relative to 2-chloroethyl vinyl ether) of trioctylamine was used. 3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-nonadecafluorododecyl vinyl ether C 4 F 9 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) OCH ⁇ CH 2 378 g (89.0 GC%) was obtained. The yield was 94%.
- Example 2 In the comparative example using potassium hydroxide as the polymerization inhibitor, the yield is only 88%, whereas in Example 1 using triethanolamine as the polymerization inhibitor, the yield is 95%. In Example 2 using trioctylamine, the yield was 90%, and it was confirmed that the yield and purity were improved by using an aliphatic amine as a polymerization inhibitor.
- the fluorine-containing vinyl ether compound according to the present invention has a large fluorine-containing content, it has a low refractive index, and can be used for an antireflection film such as a display or a clad material such as an optical fiber.
- its high fluorine content makes it possible to improve and improve various physical properties such as resin hardness, strength, heat resistance, weather resistance, chemical resistance, etc. .
- it can be used as a component for forming water and oil repellents, various surface coating agents, various release coating agents and surface modifiers.
Abstract
Description
Rf(CH2)nOH + H(CH2)mOCH=CH2 → Rf(CH2)nOCH=CH2
n:2~6、m:1~6
C6F13CH2CH2OH + C2H5OCH=CH2 → C6F13CH2CH2OCH=CH2
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cOCH=CH2 〔I〕
(ここで、nは1~6の整数であり、aは1~4の整数であり、bは1~3の整数であり、cは1~3の整数である)で表わされる含フッ素ビニルエーテル化合物が提供される。
かかる含フッ素ビニルエーテル化合物は、一般式
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cOH 〔II〕
(ここで、n、a、bおよびcは上記定義と同じである)で表わされる含フッ素アルコールと一般式
XCH2CH2OCH=CH2 〔III〕
(ここで、Xはハロゲン原子である)で表わされる2-ハロエチルビニルエーテルとを、パラジウム系触媒および脂肪族アミンの存在下で、脱XCH2CH2OH化反応させることによって製造される。
CF3(CH2CF2)(CF2CF2)(CH2CH2)OCH=CH2
CF3(CH2CF2)2(CF2CF2)(CH2CH2)OCH=CH2
CF3(CH2CF2)4(CF2CF2)(CH2CH2)OCH=CH2
CF3(CH2CF2)(CF2CF2)2(CH2CH2)OCH=CH2
CF3(CH2CF2)(CF2CF2)3(CH2CH2)OCH=CH2
CF3(CH2CF2)(CF2CF2)(CH2CH2)3OCH=CH2
C3F7(CH2CF2)2(CF2CF2)2(CH2CH2)2OCH=CH2
C4F9(CH2CF2)(CF2CF2)2(CH2CH2)OCH=CH2
C6F13(CH2CF2)3(CF2CF2)(CH2CH2)OCH=CH2
C6F13(CH2CF2)4(CF2CF2)2(CH2CH2)2OCH=CH2
CF3(CH2CF2)(CF2CF2)(CH2CH2)OH
CF3(CH2CF2)2(CF2CF2)(CH2CH2)OH
CF3(CH2CF2)4(CF2CF2)(CH2CH2)OH
CF3(CH2CF2)(CF2CF2)2(CH2CH2)OH
CF3(CH2CF2)(CF2CF2)3(CH2CH2)OH
CF3(CH2CF2)(CF2CF2)(CH2CH2)3OH
C3F7(CH2CF2)2(CF2CF2)2(CH2CH2)2OH
C4F9(CH2CF2)(CF2CF2)2(CH2CH2)OH
C6F13(CH2CF2)3(CF2CF2)(CH2CH2)OH
C6F13(CH2CF2)4(CF2CF2)2(CH2CH2)2OH
窒素雰囲気下、2-クロロエチルビニルエーテル688g(6.46モル)に、3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-ノナデカフルオロドデカノール C4F9(CH2CF2)(CF2CF2)2(CH2CH2)OH(LC/MS/MS分析によるC8以上のパーフルオロカルボン酸およびその誘導体の含有量は、検出限界である10ppb以下である)341g(0.646モル)、(1,10-フェナントロリン)酢酸パラジウム 2.4g(0.006モル;ノナデカフルオロドデカノールに対して1.0モル%)およびトリエタノールアミン 0.34g(0.002モル;2-クロロエチルビニルエーテルに対して500ppm)を加え、65℃で8時間撹拌した。未反応の2-クロロエチルビニルエーテルを減圧下で留去し、3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-ノナデカフルオロドデシルビニルエーテル C4F9(CH2CF2)(CF2CF2)2(CH2CH2)OCH=CH2 377g(90.1 GC%)を得た。収率は、95%であった。
C4F9(CH2CF2)(CF2CF2)2(CH2CH2)OCH=CH2
1H-NMR(d-アセトン,TMS):ppm 6.58~6.41、4.29~4.24(CH=CH 2 )
4.08~4.04(CH=CH2、CH2CH 2 )
2.71~2.55(CH 2 CH2)
3.59~3.48(CF2CH 2 CF2)
19F-NMR(d-アセトン,C6F6):ppm -80.34~-79.94(CF 3 )
-124.9(CF3CF 2 CF2CF2)
-122.69~-122.59(CF3CF2CF 2 CF2、
CF2CF2CF2CF 2 CF2CH2)
-110.34(CF3CF2CF2CF 2 、CF 2 CF2CF2CF2CF2CH2)
-120.26(CF2CF 2 CF2CF2CF2CH2)
-121.93(CF2CF2CF 2 CF2CF2CH2)
-112.81~112.17(CF2CF2CF2CF2CF 2 CH2)
実施例1において、トリエタノールアミン 0.34g(0.002モル;2-クロロエチルビニルエーテルに対して500ppm)の代りに、トリオクチルアミン0.48g(0.001モル;2-クロロエチルビニルエーテルに対して700ppm)を用い、3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-ノナデカフルオロドデシルビニルエーテル C4F9(CH2CF2)(CF2CF2)2(CH2CH2)OCH=CH2 378g(89.0 GC%)を得た。収率は、94%であった。
窒素雰囲気下、2-クロロエチルビニルエーテル807g(7.57モル)に、3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-ノナデカフルオロドデカノール C4F9(CH2CF2)(CF2CF2)2(CH2CH2)OH 400g(0.757モル)、(1,10-フェナントロリン)酢酸パラジウム 15.4g(0.038モル;ノナデカフルオロドデカノールに対して5.0モル%)および水酸化カリウム 0.4g(0.007モル;2-クロロエチルビニルエーテルに対して500ppm)を加え、室温で72時間撹拌した。未反応の2-クロロエチルビニルエーテルを減圧下留去し、3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-ノナデカフルオロドデシルビニルエーテル C4F9(CH2CF2)(CF2CF2)2(CH2CH2)OCH=CH2 490g(75.2 GC%)を得た。収率は、88%であった。
Claims (10)
- 一般式
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cOCH=CH2 〔I〕
(ここで、nは1~6の整数であり、aは1~4の整数であり、bは1~3の整数であり、cは1~3の整数である)で表わされる新規含フッ素ビニルエーテル化合物。 - C8以上のパーフルオロアルキル基を有するカルボン酸およびその誘導体の含有量が、LC/MS/MSで非検出である請求項1記載の新規含フッ素ビニルエーテル化合物。
- 一般式
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cOH 〔II〕
(ここで、nは1~6の整数であり、aは1~4の整数であり、bは1~3の整数であり、cは1~3の整数である)で表わされる含フッ素アルコールと一般式
XCH2CH2OCH=CH2 〔III〕
(ここで、Xはハロゲン原子である)で表わされる2-ハロエチルビニルエーテルとを、パラジウム系触媒および脂肪族アミン重合禁止剤の存在下で、脱XCH2CH2OH化反応させることを特徴とする請求項1記載の新規含フッ素ビニルエーテル化合物の製造法。 - 2-ハロエチルビニルエーテルが、含フッ素アルコールに対して2倍モル量以上用いられる請求項3記載の新規含フッ素ビニルエーテル化合物の製造法。
- 2-ハロエチルビニルエーテルが、2-クロロエチルビニルエーテルまたは2-ブロモエチルビニルエーテルである請求項3記載の新規含フッ素ビニルエーテル化合物の製造法。
- 脂肪族アミンが炭素数1~4のヒドロキシアルキル基を少くとも1個有するモノアミン、炭素数1~8のアルキル基を有するトリアルキルアミンまたは炭素数1~8のアルキレン基を有するアルキレンジアミンである請求項3記載の新規含フッ素ビニルエーテル化合物の製造法。
- 脂肪族アミンが、トリエタノールアミン、トリオクチルアミンまたはヘキサメチレンジアミンである請求項6記載の新規含フッ素ビニルエーテル化合物の製造法。
- 脂肪族アミンが原料ビニルエーテルに対して5~1000ppmの割合で用いられる請求項3または6記載の新規含フッ素ビニルエーテル化合物の製造法。
- パラジウム系触媒が、(1,10-フェナントロリン)酢酸パラジウム、(2,2′-ビピリジル)酢酸パラジウムまたはビス(トリフェニルホスフィノ)酢酸パラジウムである請求項3記載の新規含フッ素ビニルエーテル化合物の製造法。
- パラジウム系触媒が含フッ素アルコールに対して0.5~2.5モル%の割合で用いられた請求項3または9記載の新規含フッ素ビニルエーテル化合物の製造法。
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KR1020137007748A KR20140001847A (ko) | 2010-09-14 | 2011-08-24 | 신규 함불소 비닐에테르 화합물 및 그 제조법 |
JP2012533929A JP5585658B2 (ja) | 2010-09-14 | 2011-08-24 | 新規含フッ素ビニルエーテル化合物およびその製造法 |
CN201180044285.3A CN103189342B (zh) | 2010-09-14 | 2011-08-24 | 含氟乙烯基醚化合物及其制备方法 |
EP11824950.7A EP2617700B1 (en) | 2010-09-14 | 2011-08-24 | Novel fluorinated vinyl ether compound and manufacturing method therefor |
US13/822,718 US9024077B2 (en) | 2010-09-14 | 2011-08-24 | Fluorine-containing vinyl ether compound and method for producing the same |
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- 2011-08-24 JP JP2012533929A patent/JP5585658B2/ja active Active
- 2011-08-24 US US13/822,718 patent/US9024077B2/en active Active
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KR20140001847A (ko) | 2014-01-07 |
EP2617700A4 (en) | 2014-02-19 |
CN103189342B (zh) | 2015-10-21 |
US9024077B2 (en) | 2015-05-05 |
US20130178659A1 (en) | 2013-07-11 |
JP5585658B2 (ja) | 2014-09-10 |
EP2617700A1 (en) | 2013-07-24 |
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