JPS6330441A - Polyhexafluoropropylene oxide derivative and its preparation - Google Patents
Polyhexafluoropropylene oxide derivative and its preparationInfo
- Publication number
- JPS6330441A JPS6330441A JP17364886A JP17364886A JPS6330441A JP S6330441 A JPS6330441 A JP S6330441A JP 17364886 A JP17364886 A JP 17364886A JP 17364886 A JP17364886 A JP 17364886A JP S6330441 A JPS6330441 A JP S6330441A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- oxide
- formula
- polyhexafluoropropylene
- polyhexafluoropropylene oxide
- 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
Links
- -1 Polyhexafluoropropylene Polymers 0.000 title claims description 16
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 8
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 8
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 5
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 7
- 239000011630 iodine Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical class FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 27
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 5
- 239000003381 stabilizer Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 abstract description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010702 perfluoropolyether Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 125000002346 iodo group Chemical group I* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、新規ポリへキサフルオロプロピレンオキシド
誘導体及びその製造法に関する０本発明による化合物は
例えば１合成中間体、ポリマ等の固体表面安定化剤とし
て利用できる。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel polyhexafluoropropylene oxide derivative and a method for producing the same. It can be used as a drug.
本発明による化合物は、ペルフルオロポリエーテルの一
種であり、次の刊行物は、ペルフルオロポリエーテル類
の従来技術の代表的なものである。The compounds according to the invention are a type of perfluoropolyether, and the following publications are representative of the prior art of perfluoropolyethers.
特開昭５６−７２２０２号公報は、
式−〇 （ＣＦ ＣＦ２０） ｐ ＣＦ ｓ Ｃ０２
Ｈ（７）ぺＣＦ３
ンダント基を含むフルオロ化ポリマーを過酸化物の存在
下に、ヨウ素またはヨウ素含有化合物と反応させること
により、
式−〇 （ＣＦ ＣＦ２０）ｐ （ＣＦｚ）ｑＩ （
式中Ｉ
ＣＦ ３ 。JP-A-56-72202 has the following formula: (CF CF20) p CF s C02
By reacting a fluorinated polymer containing a H(7)peCF3 dandant group with iodine or an iodine-containing compound in the presence of a peroxide, the formula -〇 (CF CF20)p (CFz)qI (
In the formula I CF 3 .
Ｐ：０〜５．ｑ：１〜ｌＯである）のペンダント基を含
む、フッ素化ポリマーの製造法を開示している。P: 0-5. q: 1 to 1O) is disclosed.
特開昭６０−３４９２４は、二官能性末端ポリペルフル
オロアルキレンオキシドの末端官能基としてヨウ素基を
有する化合物を開示している。しかし、ペルフルオロポ
リエーテル鋼が、ＣＦ ｇｏ （ＣＦ ＣＦ ２０）ｍ
（ＣＦｚｏ）ｎＣＦ、（ただし、ｍｌ ｎは不規！Ｉ
＋ ！：分布されたペルフルオロエチレンオキシ、およ
びペルフルオロメチレンオキシ骨格反復車位数を示し、
ｍ／ｎは０．２／１〜５／１である。）である化合物に
限定されている。JP-A-60-34924 discloses a compound having an iodine group as the terminal functional group of a difunctional terminal polyperfluoroalkylene oxide. However, perfluoropolyether steel is CF go (CF CF 20)m
(CFzo)nCF, (However, ml n is irregular!I
＋! : Indicates the number of distributed perfluoroethyleneoxy and perfluoromethyleneoxy skeleton repeat positions,
m/n is 0.2/1 to 5/1. ) is limited to compounds that are
特開昭５８−９０５２４は。Japanese Patent Application Laid-Open No. 58-90524.
Ｆ （ＣＦ ＣＦ ２０）ｎ −Ｉ ＣＦ ＣＨ２０Ｈ
（式％式％
中、ｎは２〜７の整数）で示されるフッ素含有アルコー
ルおよびその誘導体である化合物を開示している。F (CF CF 20)n -I CF CH20H
Discloses compounds that are fluorine-containing alcohols and derivatives thereof represented by the formula % (where n is an integer from 2 to 7).
米国特許３２５０８０８は、ポリへキサフルオロプロピ
レンオキシド酸誘導体について開示しであるが、ヨウ化
物あるいは臭化物ついては開示されていない。US Pat. No. 3,250,808 discloses polyhexafluoropropylene oxide acid derivatives, but not iodides or bromides.
従来より、ハロゲン化物（特に臭化物、ヨウ化物）は１
分子へ官能基を導入したり、ある官能基を他の官能基に
変えたりする際の重要な合成中間体であることが知られ
ている。Traditionally, halides (especially bromides and iodides)
It is known to be an important synthetic intermediate when introducing functional groups into molecules or changing one functional group to another.
一方、ペルフルオロアルキルポリエーテルの一種である
ポリヘキサプロピレンオキシドは、化学的安定性、安定
な粘度特性、潤滑性能、撲水撲油性等の優れた物性を有
する有用な工業資材である。On the other hand, polyhexapropylene oxide, which is a type of perfluoroalkyl polyether, is a useful industrial material that has excellent physical properties such as chemical stability, stable viscosity characteristics, lubrication performance, and anti-hydrolytic properties.
しかし、ポリへキサフルオロプロピレンオキシドは、カ
ルボン酸誘導体のみしか知られておらず、化学修飾によ
り、新規な機能性材料を得るための原料は、限定されて
いた。However, only carboxylic acid derivatives of polyhexafluoropropylene oxide are known, and raw materials for obtaining novel functional materials through chemical modification are limited.
本発明の目的は、新規なポリへキサフルオロプロピレン
オキシド誘導体を提供することにある。An object of the present invention is to provide novel polyhexafluoropropylene oxide derivatives.
本発明による化合物は１例えば合成中間体、固体表面安
定化剤等の用途を有し、工業的にも有用である。The compounds according to the present invention have uses such as synthetic intermediates and solid surface stabilizers, and are also industrially useful.
ｃ問題点を解決するための手段〕
上記目的は、弐Ｆ （ＣＦ ＣＦ ｓ Ｏ）ｎ ＣＦ
ＸＣＦ ３ＣＦ ｓ
（式中、ｎは１〜１０’ Ｏあ整数、Ｘは−Ｂｒ。c Means for solving the problem] The above purpose is 2F (CF CF s O)n CF
XCF 3CF s (wherein, n is an integer from 1 to 10', and X is -Br.
−Ｉ）で示されるように、ポリへキサフルオロプロピレ
ンオキシド鎖の片端にブロモ基、あるいはヨード基を有
することを特徴とする化合物によって達成される。As shown in -I), this is achieved by a compound characterized by having a bromo group or an iodo group at one end of a polyhexafluoropropylene oxide chain.
本発明による含フツ素オリゴマー誘導体（１）のＦ （
ＣＦ ＣＦ ｘ Ｏ） ｎ ＣＦ Ｘ＋
１ （１）ＣＦ ３ＣＦ ３
（ｎは、前記と同じ、ＸはＢｒｔ Ｉ）合成法は、例え
ば式（２）で表わされる化合物Ｆ （ＣＦ ＣＦ、
０）ｎＣＦ Ｃ０２Ｍ＋ １
（２）ＣＦ ｓ
ＣＦ ｓ
（ｎは、前記と同じ、ＭはＡｇ、等）で表わされる化合
物を合成し、臭素あるいはヨウ素の有性下で加熱し、脱
炭素を行う方法がある。F (
CF CF x O) n CF X+
1 (1) CF 3 CF 3 (n is the same as above, X is Brt I) The synthesis method is, for example, a compound F (CF CF,
0)nCF C02M+ 1
(2) CFs
There is a method in which a compound represented by CF s (n is the same as above, M is Ag, etc.) is synthesized and heated in the presence of bromine or iodine to decarbonize the compound.
上記反応における反応溶媒は、使用しなくてもかまわな
いが、ハロゲン化炭化水素等を使用しても良い。また脱
炭酸を行うためには、高温に加熱する必要があるが、加
熱に伴い生成物の分解を利発するので、２００℃以下、
好ましくは、７０″〜１７０℃の温度において行なうこ
とができる。Although the reaction solvent in the above reaction does not have to be used, a halogenated hydrocarbon or the like may be used. In addition, in order to perform decarboxylation, it is necessary to heat to a high temperature, but since heating promotes decomposition of the product, it is necessary to heat the product to a temperature below 200°C.
Preferably, it can be carried out at a temperature of 70'' to 170°C.
また化合物（２）に対してハロゲン（Ｂｒ、Ｉ）の量は
、当モル以上である必要があり、臭素、ヨウ素は、加熱
により気化し、反応系外に放出されやすいので過剰量使
用することが望ましく、反応容器の状態によっても異な
るが１．２〜３倍モルの範囲で使用するのが好ましい。In addition, the amount of halogen (Br, I) relative to compound (2) must be at least the equivalent molar amount, and bromine and iodine should not be used in excessive amounts as they tend to vaporize and be released outside the reaction system when heated. is desirable, and it is preferably used in a range of 1.2 to 3 times the mole, although it varies depending on the condition of the reaction vessel.
なお、反応を密ぺいした容器内で行うことにより、使用
するハロゲンの量を低減させることが可能である。Note that by conducting the reaction in a tightly sealed container, it is possible to reduce the amount of halogen used.
また、上記反応においては、水分により収率が著しく低
下するので、化合物（２）、および反応容器等は、充分
乾燥することが望ましく、乾燥剤としては、無水硫酸マ
グネシウム、モレキュラーシーブ（３Ａ）等を使用する
ことができる。In addition, in the above reaction, the yield is significantly reduced by moisture, so it is desirable to thoroughly dry the compound (2) and the reaction container, etc. As a drying agent, anhydrous magnesium sulfate, molecular sieve (3A), etc. can be used.
化合物（２）の合成法は、ｍ々考えられるが、例えば１
次のような方法がある。式（３）で表わされる含フツ素
オリゴマー
Ｆ （ＣＦ ＣＦ ２０）ｎＣＦ Ｃ０２Ｈ＋
１ （３）ＣＦ ３Ｃ
Ｆ ３
（ｎは前記と同じ）を直接あるいは、溶液とし、酸化銀
を作用させる。上記反応における溶媒は、フッ素系の溶
媒が好ましく、例えば、１．１．２−トリクロロトリフ
ルオロエタン等を使用することができる６反応温度は、
常温でもかまわないが加熱しても良い。There are many ways to synthesize compound (2), but for example, 1
There are following methods. Fluorine-containing oligomer F (CF CF 20)nCF C02H+ represented by formula (3)
1 (3) CF 3C
Silver oxide is allowed to act on F 3 (n is the same as above) directly or in the form of a solution. The solvent in the above reaction is preferably a fluorine-based solvent, for example, 1.1.2-trichlorotrifluoroethane or the like can be used.6 The reaction temperature is as follows:
It can be served at room temperature, but it can also be heated.
化合物（３）に対し、使用する酸化銀の量は当モル以上
である必要があり、大過剰量加えても差しつかえないが
、未反応物の除去が困難になるので、１〜１．５倍モル
の範囲で使用するのが好ましい。The amount of silver oxide used must be at least the equivalent molar amount of compound (3), and it is okay to add a large excess amount, but since it becomes difficult to remove unreacted materials, the amount of silver oxide used is 1 to 1.5 molar. It is preferable to use it in twice the molar range.
次に実施例および応用例を示し、本発明を具体的に説明
する。Next, the present invention will be specifically explained by showing examples and application examples.
実施例１ （１）〜１（３）（ポリへキサフルオロプロ
ピレンオキシド酸銀の合成）
ビーカーに、ポリへキサフルオロプロピレンオキシドＩ
Ｍ！５０ｍ ｍｏｎ （平均分子：ｔ２５００の時１２
５ ｒ： ＊平均分子量４５００の時２２５ ｇ＋平均
分子量７０００の時３５０ ｇ）を含む、１，１゜２−
トリフルオロトリクロロエタン溶液を仕込み、攪拌しな
がら酸化銀５４ ｍ ｍｏｎ （１２，５ｇ）を加え
、約２時間加熱で攪拌した０次いで未反応の酸化銀を３
則し、３液を無水硫酸マグネシウムで乾燥後、溶媒を減
圧下で留去（２７ｍ ｍ Ｈｚ３０℃）し、かっ色油状
物質である
Ｆ （ＣＦ ｃＦ、○）ｎ ＣＦ ＣＯ５Ａｇ
ＣＦ ３ ＣＦ ３を得た。Example 1 (1) to 1(3) (Synthesis of silver polyhexafluoropropylene oxide acid) In a beaker, add polyhexafluoropropylene oxide I.
M! 50m mon (average molecule: 12 at t2500
5 r: *1,1゜2-, including 225 g when the average molecular weight is 4500 + 350 g when the average molecular weight is 7000)
A trifluorotrichloroethane solution was charged, 54 m mon (12.5 g) of silver oxide was added with stirring, and the mixture was heated and stirred for about 2 hours.
After drying the three liquids over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure (27 mm Hz, 30°C) to obtain a brown oily substance, F (CF cF, ○) n CF CO5Ag.
CF3CF3 was obtained.
得られた化合物の収率および赤外吸収スペクトルによる
カルボニル基の吸収波数を表１に示した。Table 1 shows the yield of the obtained compound and the absorption wave number of the carbonyl group according to the infrared absorption spectrum.
表 １
また、実施例１ （１）〜ｌ （３）の化合物は、元素
分析の結果、生成物１ｇあたり約１当量の銀が含まれて
いた。これらのことより、はぼ定量的にカルボン酸から
銀塩に反応していることがわかった・
実施例２（１）〜２（３）
（ポリへキサフルオロプロピレンオキシド臭化物の合成
）
乾燥窒素ガス導入口、滴下ロート、および塩化カルシウ
ム管をとりつけたフラスコに実施例１で合成した銀塩２
０ｍｍｏｕ （Ｎ材料のポリへキサフルオロプロピレン
オキシド酸の平均分子量２５００の時５２ｇ、平均分子
量４５００の時９２ｇ、平均分子量７０００の時１４２
ｇ）を入れ、窒素ガスを吹きこみながら７０℃にて約２
時間加熱し充分に乾燥させた１次いで冷却管をとりつけ
、滴下ロートより臭素２４ｍｍｏ１２ （３，８ｇ）
を徐々に滴下しながら窒素雰囲気中、７０〜１２０℃で
約６時間還流した。Table 1 Furthermore, as a result of elemental analysis, the compounds of Example 1 (1) to l (3) contained about 1 equivalent of silver per 1 g of the product. From these results, it was found that carboxylic acid reacted to silver salt in a quantitative manner. Examples 2(1) to 2(3) (Synthesis of polyhexafluoropropylene oxide bromide) Dry nitrogen gas Silver salt 2 synthesized in Example 1 was placed in a flask equipped with an inlet, a dropping funnel, and a calcium chloride tube.
0 mmou (52 g when the average molecular weight of N material polyhexafluoropropylene oxide acid is 2500, 92 g when the average molecular weight is 4500, 142 when the average molecular weight is 7000)
g) and heated at 70℃ while blowing nitrogen gas for about 2 hours.
After heating for a long time and thoroughly drying, attach a cooling tube and add 24 mmol of bromine (3.8 g) through the dropping funnel.
The mixture was refluxed at 70 to 120° C. for about 6 hours in a nitrogen atmosphere while gradually dropping the mixture.
常温まで冷却後、１，１．２−トリフルオロトリクロロ
エタン５００ ｍ Ｑを加え真化銀を３別し、３液より
溶媒を減圧下で留去して下記のＦ （ＣＦ ＣＦ ２０
）ｎ ＣＦ Ｂ ｒＣＦ３ ＣＦ３
を得た。After cooling to room temperature, 500 mQ of 1,1,2-trifluorotrichloroethane was added, the silver oxide was separated into three parts, and the solvent was distilled off from the three liquids under reduced pressure to obtain the following F (CF CF 20
) n CF B rCF3 CF3 was obtained.
得られた化合物の収率および分析結果を表２゜表３に示
した。The yield and analysis results of the obtained compound are shown in Tables 2 and 3.
表 ２
ｅ） ｃ） ｆ）
ＣＦ ｓ ＣＦ ２ ＣＦ ２０ （ＣＦ ＣＦ ＊
Ｏ） ｎ ＣＦ ＢＲａ） ｂ） ｃ）
ｌ ｌＣＦ３ ＣＦ。Table 2 e) c) f) CF s CF 2 CF 20 (CF CF *
O) n CF BRa) b) c)
l lCF3 CF.
ｄ） ｄ） のどとくフッ素原子を表示し表３に示した。d) d) The fluorine atoms that are present in the throat are shown in Table 3.
表 ３
以上の結果は、上記の構造を支持しているものと考えら
れる。Table 3 The above results are considered to support the above structure.
実施例３（１）〜３（３）
（ポリへキサフルオロプロピレンオキシドヨウ化物の合
成）
実施例１で合成した銀塩２０ｍｍｏｊｌ（原材料のポリ
へキサフルオロプロピレンオキシド酸の平均分子量２５
００の時、５２ｇ、平均分子量４５００の時９２ｇ、平
均分子量７０００の時１４２ ｇ）およびヨウ＄２４ｍ
ｍｏｎを１．１゜２−トリクロロトリフルオロエタンに
溶解し、モレキュラーシーブ３Ａで乾燥した０次いで、
溶媒を減圧下で留去後、乾燥窒素ガス導入口、塩化カル
シウム管、冷却管を取りつけたフラスコに入れ、１４０
〜１５０℃で還流を行ない、ヨウ素を追加しながら、フ
ラスコ内の生成物を赤外吸収スペクトルで分析し、カル
ボキシレートによる吸収νｃ＝ｏ＝１６９０ｃｓ＋−’
のピークが消失したところを反応終点とした６反応終了
まで約７時間要し、使用したヨウ素の総量は、２６ｍｍ
ｏｎ （平均分子量２５００の時）から５８ｍｍｏΩ（
平均分子！７０００の時）であった。Examples 3 (1) to 3 (3) (Synthesis of polyhexafluoropropylene oxide iodide) 20 mmojl of the silver salt synthesized in Example 1 (average molecular weight of raw material polyhexafluoropropylene oxide acid: 25
00, 52g, average molecular weight 4500, 92g, average molecular weight 7000, 142g) and iodine $24m
mon was dissolved in 1.1°2-trichlorotrifluoroethane and dried with molecular sieve 3A.
After distilling off the solvent under reduced pressure, it was placed in a flask equipped with a dry nitrogen gas inlet, a calcium chloride tube, and a cooling tube, and heated to 140 ml.
While refluxing at ~150°C and adding iodine, the product in the flask was analyzed by infrared absorption spectroscopy, and the absorption due to carboxylate νc=o=1690cs+-'
It took about 7 hours to complete the 6 reactions, with the end point of the reaction being when the peak of
on (when the average molecular weight is 2500) to 58 mmoΩ (
Average molecule! 7000).
次いで、上記生成物を常温まで冷却後、ｌ、１゜２−ト
リクロロトリフルオロエタン溶液とし、ヨウ化銀を３別
し、３液より溶媒を減圧下で留去し、下記の構造を有す
るヨウ化物を得た。Next, after cooling the above product to room temperature, it was made into a 1,1°2-trichlorotrifluoroethane solution, the silver iodide was separated into three parts, and the solvent was distilled off from the three liquids under reduced pressure to obtain an iodide having the following structure. I got a monster.
Ｆ （ＣＦ ＣＦ ｓ Ｏ） ｎ ＣＦ １ＣＦ ３
ＣＦ ａ
得られた化合物の収率および分析結果を表４゜表５に示
した。F (CF CF s O) n CF 1CF 3
CF a The yield and analysis results of the obtained compound are shown in Tables 4 and 5.
表 ４
ｅ） ｃ） ｆ）
ＣＦｓ ＣＦ ２ＣＦ２０ （ＣＦ ＣＦ ２ｏ）ＣＦ
１ａ） ｂ） ｃ） ｌ
ｌＣＦ 、 ＣＦ ３
ｄ） ｄ）
のどとくフッＩＲ原子を表示し１表５に示した。Table 4 e) c) f) CFs CF 2CF20 (CF CF 2o) CF
1a) b) c) l
lCF, CF 3 d) d) Throat Fluorine IR atoms are shown in Table 5.
表 ５
これらの結果は、上記構造を支持しているものと考える
ことができる。Table 5 These results can be considered to support the above structure.
本発明による化合物の代表的な応用例を示す。Representative examples of applications of compounds according to the invention are shown.
応用例
前述の実施例で合成したブロモ基あるいはヨード基を有
する重合体の１．１．２−トリクロロトリフルオロエタ
ン溶液を調製し、磁気ディスク表面に塗布した０次いで
、窒素雰囲気中６００ＷＨＫ −Ｘ ｅランプで約３０
分間露光したものを試料とした。Application Example A 1.1.2-trichlorotrifluoroethane solution of the polymer having a bromo group or iodo group synthesized in the above example was prepared and applied to the surface of a magnetic disk. Approximately 30 with a lamp
The sample was exposed for one minute.
次いでフレオン洗浄前後の接触角測定により、表面エネ
ルギー、付着性を評価した。結果を表６に示す。Next, surface energy and adhesion were evaluated by measuring contact angles before and after Freon cleaning. The results are shown in Table 6.
表 ６ ｅＯ３θｓａｔ ｃｏｓθＯ ただし、θはフレオン洗浄後の接触角。Table 6 eO3θsat cosθO However, θ is the contact angle after Freon cleaning.
θ０は、未塗布試料の接触角 ｅＦｌａｔは、接触角の飽和値 接触角の測定には、ｎ−ヘキサデカンを使用した。θ0 is the contact angle of the uncoated sample eFlat is the saturation value of the contact angle n-hexadecane was used to measure the contact angle.
化合物■
Ｆ （ＣＦ ＣＦ ｇｏ）ｎ ＣＦ ＊ ＣＦ ｓＣ
Ｆ。Compound ■ F (CF CF go) n CF * CF sC
F.
（平均分子量２５００）
化合物■
Ｆ （ＣＦ ＣＦ ５ｏ）ｎ ＣＦ Ｂ ｒＣＦ３
ＣＦ３
（平均分子量２５００）
化合物■
Ｆ （ＣＦ ＣＦ ｘ Ｏ） ｎ ＣＦ ＩＩ
ＣＦ ３ ＣＦ ３
（平均分子量２５００）
この例から、わかるように本発明による化合物は、付着
性の良好な表面安定化剤として、有用である。(Average molecular weight 2500) Compound ■ F (CF CF 5o)n CF B rCF3
CF3 (average molecular weight 2500) Compound ■ F (CF CF x O) n CF II CF 3 CF 3 (average molecular weight 2500) As can be seen from this example, the compound according to the present invention is effective as a surface stabilizer with good adhesion. , useful.
なお、応用例では示さなかったが、本発明による化合物
を固体表面に塗布した場合、撲水接油性。Although not shown in the application example, when the compound according to the present invention is applied to a solid surface, it has anti-water and oil-wetting properties.
潤滑性の向上あるいは、光の屈折率の低下による反射防
止効果も我々は確認している。We have also confirmed an anti-reflection effect due to improved lubricity or a decrease in the refractive index of light.
以上の例に示したように、本発明の化合物は。 As shown in the above examples, the compounds of the present invention.
合成中間体、固体表面安定化剤等の多くの用途を有し、
工業上の利用価値は極めて大きい。It has many uses such as synthetic intermediates and solid surface stabilizers.
The industrial value is extremely large.
、）,)
Claims (1)
ヘキサフルオロプロピレンオキシド誘導体。 ２、 式：▲数式、化学式、表等があります▼ （ｎは１〜１００までの整数）で表わされるポリヘキサ
フルオロプロピレンオキシド酸と酸化銀を反応せしめ、
次いで生成する銀塩に、臭素あるいはヨウ素を反応させ
ることを特徴とするポリヘキサフルオロプロピレンオキ
シド誘導体の製造法。[Claims] 1. Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (where n is an integer from 1 to 100, and X is -Br or -I). Hexafluoropropylene oxide derivative. 2. Formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (n is an integer from 1 to 100) by reacting polyhexafluoropropylene oxide acid with silver oxide,
A method for producing a polyhexafluoropropylene oxide derivative, which comprises then reacting the produced silver salt with bromine or iodine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17364886A JPS6330441A (en) | 1986-07-25 | 1986-07-25 | Polyhexafluoropropylene oxide derivative and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17364886A JPS6330441A (en) | 1986-07-25 | 1986-07-25 | Polyhexafluoropropylene oxide derivative and its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6330441A true JPS6330441A (en) | 1988-02-09 |
Family
ID=15964510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17364886A Pending JPS6330441A (en) | 1986-07-25 | 1986-07-25 | Polyhexafluoropropylene oxide derivative and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6330441A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0472423A2 (en) * | 1990-08-23 | 1992-02-26 | Shin-Etsu Chemical Co., Ltd. | Preparation of perfluorooligoether iodides |
| JPH04103559A (en) * | 1990-08-23 | 1992-04-06 | Shin Etsu Chem Co Ltd | Oligohexafluoropropylene oxide derivative and its production |
| JP2006512449A (en) * | 2002-12-30 | 2006-04-13 | スリーエム イノベイティブ プロパティズ カンパニー | Fluorinated polyether composition |
| JP2008255179A (en) * | 2007-04-03 | 2008-10-23 | Yunimatekku Kk | Fluorine-containing polyether compound, its manufacturing method, and curable composition containing the same |
-
1986
- 1986-07-25 JP JP17364886A patent/JPS6330441A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0472423A2 (en) * | 1990-08-23 | 1992-02-26 | Shin-Etsu Chemical Co., Ltd. | Preparation of perfluorooligoether iodides |
| JPH04103559A (en) * | 1990-08-23 | 1992-04-06 | Shin Etsu Chem Co Ltd | Oligohexafluoropropylene oxide derivative and its production |
| JP2006512449A (en) * | 2002-12-30 | 2006-04-13 | スリーエム イノベイティブ プロパティズ カンパニー | Fluorinated polyether composition |
| JP2008255179A (en) * | 2007-04-03 | 2008-10-23 | Yunimatekku Kk | Fluorine-containing polyether compound, its manufacturing method, and curable composition containing the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hasek et al. | The Chemistry of Sulfur Tetrafluoride. II. The Fluorination of Organic Carbonyl Compounds1 | |
| US6156937A (en) | Functionalized fluoropolyethers | |
| US4987254A (en) | Fluorinated carboxylic acid fluorides | |
| IE68409B1 (en) | Process for preparing peroxidic perflouropolyethers | |
| EP0428709A1 (en) | Reactive compounds containing perfluorovinyl groups. | |
| EP0340740A2 (en) | Perfluoropolyethers containing a halogen different from fluorine and having an acid end group | |
| JPH0222326A (en) | Production of perfluoropolyether controlled in its molecular weight having perfluoroalkyl or perfluoroalkyl terminal group | |
| DE69231235T2 (en) | Process for the preparation of perfluoropolyoxyalkylenes with high viscosity and low peroxide oxygen content | |
| Gambaretto et al. | Synthesis and characterization of a new class of polyfluorinated alkanes: tetrakis (perfluoroalkyl) alkane | |
| JPS6330441A (en) | Polyhexafluoropropylene oxide derivative and its preparation | |
| US5506309A (en) | Perfluorinates polyethers | |
| JP2532885B2 (en) | Hypofluorite and bis-hypofluorite, and method for producing the same | |
| KR101125168B1 (en) | Process for preparing fluorohalogenethers | |
| US6191314B1 (en) | Process for obtaining (per)fluoropolyethers substituted at one or at both end groups with a halogen atom | |
| KR101125167B1 (en) | Process for preparing fluorohalogenethers | |
| JPS6340773B2 (en) | ||
| CN111116900A (en) | Method for synthesizing surface treating agent by one-pot boiling | |
| JPS63255288A (en) | Fluorine-containing organosilicon compound | |
| JPH0819229B2 (en) | Method for producing substituted polyether compound | |
| Conte et al. | Synthesis and characterization of tri-block fluorinated-n-alkanes | |
| JP2004043402A (en) | Unsaturated fluorocompound and method for producing the same | |
| JPH0469358A (en) | Asymmetric diacetylene compound | |
| JP2528861B2 (en) | Fluorine-containing azide compounds | |
| JPS63265920A (en) | Polyfluoropolyether | |
| JPS61122234A (en) | Perchlorofluorinated hydrocarbon and manufacture |