JP5407980B2 - Fluorine-containing polyether compound and method for producing the same - Google Patents

Description

  The present invention relates to a fluorine-containing polyether compound and a method for producing the same. More specifically, the present invention relates to a fluorine-containing polyether compound having a reactive site at both ends of a polymer main chain and a method for producing the same.

で表わされる化合物が知られている(特許文献１参照)。 As the fluorine-containing polyether compound having a functional group at the molecular end, for example, a general formula

Is known (see Patent Document 1).

で表わされる化合物が知られている(特許文献２参照)。 Further, as a more general compound obtained by oligomerizing the main chain structure of the above compound, a general formula

Is known (see Patent Document 2).

  The compounds represented by these general formulas are cured by a fluorine-containing organohydrogensiloxane compound having a plurality of Si-H groups in the molecule and a platinum compound catalyst, and have excellent properties (chemical resistance, heat resistance, low temperature It is said that an elastomeric molded product having characteristics) can be provided, and in particular, it can be used without loss of flexibility even under a low temperature condition of about -50 ° C. Moreover, the curable composition which has these as a main component has outstanding moldability, and also enables RIM molding. However, since this cured product has a siloxane bond in its intramolecular cross-linked structure, its mechanical strength decreases due to chemical degradation when used under conditions where acidic substances such as hydrogen fluoride are present. May give undesirable results.

Japanese Patent Laid-Open No. 11-343336 Japanese Patent No. 2990646 WO 2008/126436 A1 WO 90/15042 A2

Polymer 41 6213 (2000) Tetrahedron Letters 36 6375 (1995) Tetrahedron Letters 38 (5831) (1997)

(ここで、R¹は水素原子、炭素数1〜3のアルキル基またはフェニル基であり、Xはヨウ素原子または臭素原子であり、Xのフェニル基上の置換位置はNR¹結合置換基に対してm-またはp-位であり、lおよびmはそれぞれ独立に10以上の整数であり、l+mは30〜130である)で表わされる含フッ素ポリエーテル化合物を提案している(特許文献３参照)。 The present inventor previously can cure without the need for a fluorine-containing organohydrogensiloxane compound having a Si—H bond, and is excellent in heat resistance, low temperature characteristics and moldability, and used under acidic conditions. As a fluorine-containing polyether compound that gives a cured product that can withstand

(Wherein R ¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, X is an iodine atom or a bromine atom, and the substitution position on the phenyl group of X is relative to the NR ¹ bond substituent. M- or p-position, l and m are each independently an integer of 10 or more, and l + m is 30 to 130) (Patent Document) 3).

  This fluorine-containing polyether compound can be cured with a boronic acid ester compound to give an elastomeric molded product, but is not suitable for peroxide crosslinking, which is a more general crosslinking method.

  An object of the present invention is to provide a fluorine-containing polyether compound having a halogenoalkoxy group having excellent reactivity at both ends of a polymer main chain and capable of peroxide crosslinking, and a method for producing the same.

(ここで、R¹は水素原子、炭素数1〜3のアルキル基またはフェニル基であり、Xは臭素原子またはヨウ素原子であり、lおよびmはそれぞれ独立に10以上の整数であり、l+mは30〜200である)で表わされる含フッ素ポリエーテル化合物が提供される。 According to the present invention, the general formula [I]

(Wherein R ¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, X is a bromine atom or an iodine atom, l and m are each independently an integer of 10 or more, and l + m is 30 to 200).

(ここで、lおよびmはそれぞれ独立に10以上の整数であり、l+mは30〜200である)で表わされる含フッ素ジカルボン酸フルオリド化合物を、一般式〔III〕

(ここで、R¹は水素原子、炭素数1〜3のアルキル基またはフェニル基であり、R²は水素原子またはトリメチルシリル基であり、Xは臭素原子またはヨウ素原子である)で表わされるアニリン化合物と、好ましくはピリジンまたはトリエチルアミン等の3級アミン化合物の存在下で、反応させることにより製造される。 Such a fluorine-containing polyether compound has the general formula [II]

(Wherein l and m are each independently an integer of 10 or more, and l + m is 30 to 200), a fluorine-containing dicarboxylic acid fluoride compound represented by the general formula [III]

Where R ¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, R ² is a hydrogen atom or a trimethylsilyl group, and X is a bromine atom or an iodine atom. And preferably in the presence of a tertiary amine compound such as pyridine or triethylamine.

  The fluorine-containing polyether compound according to the present invention has a 2-bromotetrafluoroethoxy group or a 2-iodotetrafluoroethoxy group as a reactive site at both ends of the polymer main chain. The product can be crosslinked, and an elastomeric molded product can be obtained by peroxide crosslinking. Molded products obtained by curing such compositions are excellent in low-temperature characteristics, chemical resistance, etc., so that they are excellent in automobile fuel supply system seal materials, oil seal materials, aircraft fuel systems and hydraulic system seal materials, and semiconductor manufacturing equipment seals. It is suitably used for various applications such as materials.

において、lおよびmはそれぞれ独立に10以上の整数であり、l+mは30〜200の整数である。特に、エラストマー性高分子材料の主原料として用いる場合には、硬化後十分な機械的強度を有する成形物を得るために、l+mは50〜150であることが好ましい。R¹は水素原子、炭素数1〜3のアルキル基またはフェニル基である。なお、R¹がアルキル基またはフェニル基の場合、分子間水素結合の形成が妨げられることにより、含フッ素ポリエーテル化合物の粘度を低下させることができる。 Fluorinated polyether compound of the present invention

In the formula, l and m are each independently an integer of 10 or more, and l + m is an integer of 30 to 200. In particular, when used as a main raw material for an elastomeric polymer material, l + m is preferably 50 to 150 in order to obtain a molded product having sufficient mechanical strength after curing. R ¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group. In the case where R ¹ is an alkyl group or a phenyl group, the viscosity of the fluorinated polyether compound can be lowered by preventing the formation of intermolecular hydrogen bonds.

注) HFPO：ヘキサフルオロプロペンオキシド
HFP：ヘキサフルオロプロペン The fluorine-containing polyether compound (X = Br) of the present invention can be produced, for example, through the following series of steps.

Note) HFPO: Hexafluoropropene oxide
HFP: Hexafluoropropene

In the aniline compound [III] used in the second step, R ¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ² is a hydrogen atom or a trimethylsilyl group. The substitution position on the benzene ring of the ₂ -bromotetrafluoroethoxy group (BrCF ₂ CF ₂ O—) is the o-, m-, or p-position with respect to the amino group (—NR ¹ − ). Specific examples of the aniline compound [III] include 2- (2-bromotetrafluoroethoxy) aniline, 3- (2-bromotetrafluoroethoxy) aniline, 4- (2-bromotetrafluoroethoxy) aniline, 2- ( 2-bromotetrafluoroethoxy) -N-methylaniline, 3- (2-bromotetrafluoroethoxy) -N-methylaniline, 4- (2-bromotetrafluoroethoxy) -N-methylaniline or their N-trimethylsilyl Derivatives and the like. The terminal bromine atom of the 2-bromotetrafluoroethoxy group may be an iodine atom.

  In the aniline compound [III], the primary aniline compound is prepared by reacting 1,2-dibromotetrafluoroethane with acetamidophenol or methyl hydroxybenzoate as described in Patent Document 4 and Non-Patent Document 1. After that, it can be manufactured through several steps. The secondary aniline compound can be produced by N-alkylating the primary aniline compound with an alkylating agent such as dialkyl sulfuric acid or alkyl iodide. In this case, an N, N-dialkylated product is produced as a by-product in addition to the N-alkylated product, and thus separation and purification are necessary.

  A more preferable method of N-monoalkylation is the selective N-monoalkylation described in Non-Patent Documents 2 and 3. Specifically, a primary aniline compound is reacted with 2-nitrobenzenesulfonyl chloride or 2,4-dinitrobenzenesulfonyl chloride, sulfonamidated, then N-alkylated with alkyl iodide or the like, and then thiophenol or mercapto. By reacting with acetic acid, the desired secondary aniline compound can be selectively obtained.

  The reaction between the fluorine-containing dicarboxylic acid fluoride [II] and the aniline compound [III] is carried out in the presence of a basic nitrogen-containing heterocyclic compound having no active hydrogen such as pyridine or a tertiary amine compound such as triethylamine. In a fluorine-containing solvent such as fluorocarbon, hydrofluorocarbon, hydrofluoroether, or a mixed solvent of these fluorine-containing solvent and aprotic non-fluorine solvent, a reaction temperature of -50 to 150 ° C, preferably 0 to 100 ° C Done in Specific examples of the fluorine-containing solvent include HCFC-225, HFE-449 (Sumitomo 3M product HFE7100), HFE-569 (Sumitomo 3M product HFE-7200), 1,3-bis (trifluoromethyl) benzene, and the like. . Examples of the aprotic non-fluorinated solvent include diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane and the like. Considering the solubility of the aniline compound [III], it is more preferable to use a mixed solvent of a fluorinated solvent and an aprotic non-fluorinated solvent.

またはこれらに対応するヨウ素化物等が例示される。 As a specific example of the fluorine-containing polyether compound of the present invention,

Or the iodinated thing etc. corresponding to these are illustrated.

  The fluorine-containing polyether compound according to the present invention can be peroxide-crosslinked with an organic peroxide. In peroxide crosslinking, it is preferable to use a polyfunctional unsaturated compound in combination.

  Examples of the organic peroxide include 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, benzoyl peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, tert-butyl peroxybenzene, 1,1-bis (3 butyl peroxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxy peroxide, dicumyl peroxide, etc. is about 0.1 to 5 per 100 parts by weight of the fluorinated polyether compound. Part by weight, preferably about 0.1 to 2 parts by weight is used.

  In addition, as the polyfunctional unsaturated compound, for example, triallyl isocyanurate, triallyl cyanurate, triacryl formal, triallyl trimellitate and the like are about 0.1 to 10 parts by weight with respect to 100 parts by weight of the fluorine-containing polyether compound. , Preferably about 0.5 to 5 parts by weight.

  To cure the fluorine-containing polyether compound, an organic peroxide, preferably both an organic peroxide and a polyfunctional unsaturated compound, is added, and a reinforcing agent such as carbon black or silica is added as necessary. It is performed by compression molding at about 100 to 180 ° C. for about 5 to 30 minutes and, if necessary, oven vulcanization at about 150 to 250 ° C. for about 5 to 24 hours. The molding can also be performed by RIM molding.

  Next, the present invention will be described with reference to examples.

Reference example 1
Synthesis of 4- (2-bromotetrafluoroethoxy) -N-methylaniline
(1) To a solution consisting of 100 g (0.657 mol) of methyl 4-hydroxybenzoate and 300 ml of methanol, 43.4 g (0.657 mol) of potassium hydroxide (purity 85%) was added little by little while cooling the reaction vessel with ice water. The reaction was continued for another 3 hours. After removing methanol under reduced pressure, it was dried under reduced pressure at 140 ° C. and 27 Pa for 8 hours. 119 g (95% yield) of potassium salt of methyl 4-hydroxybenzoate was obtained as a colorless solid.
(2) In a solution of 50 g (0.26 mol) of potassium 4-hydroxybenzoate in 150 ml of dimethyl sulfoxide, 89 g (0.34 mol) of 1,2-dibromotetrafluoroethane was added at 60 ° C. in a nitrogen atmosphere. It was added dropwise over 1 hour. After completion of dropping, the reaction was further carried out at 70 ° C. for 2 hours and 90 ° C. for 30 minutes. The reaction mixture was cooled to room temperature, 150 ml of water was added, and the product was extracted with dichloromethane. Thereafter, usual post-treatment was performed to obtain 84 g of a crude product. This was distilled under reduced pressure to obtain 81 g (yield: 93%) of methyl 4- (2-bromotetrafluoroethoxy) benzoate (boiling point: 75-77 ° C., 13 Pa) as a colorless liquid.
(3) Alkaline solution consisting of 70 g (0.211 mol) of methyl 4- (2-bromotetrafluoroethoxy) benzoate and 100 ml of methanol and 18.1 g (0.274 mol) of potassium hydroxide (purity 85%) and 100 ml of methanol Was added at room temperature and the reaction was continued for another 4 hours. To the obtained solution, 110 ml of water and 43 g of concentrated hydrochloric acid were added, and the contents were mixed well. The liberated product was extracted with diethyl ether, and then subjected to usual work-up to obtain 65.8 g (yield 98%) of 4- (2-bromotetrafluoroethoxy) benzoic acid as a colorless solid.
(4) A mixture of 65.6 g (0.207 mol) 4- (2-bromotetrafluoroethoxy) benzoic acid, 32.1 g (0.270 mol) thionyl chloride, 2.0 g (0.027 mol) dimethylformamide and 160 ml chloroform was prepared at 50 ° C. The reaction was performed for 2 hours. After distilling off chloroform and unreacted thionyl chloride under reduced pressure, the residue was further distilled under reduced pressure. 67.3 g (yield 97%) of 4- (2-bromotetrafluoroethoxy) benzoyl chloride (boiling point 68-72 ° C., 9 Pa) was obtained as a colorless liquid.
(5) To a solution consisting of 67.3 g (0.201 mol) 4- (2-bromotetrafluoroethoxy) benzoyl chloride and 200 ml tetrahydrofuran, an aqueous solution consisting of 43.1 g (0.663 mol) sodium azide and 140 ml water was added. It was added while cooling. After continuing the reaction for 1.5 hours, 200 ml of water was added, and the product was extracted with dichloromethane. Thereafter, usual post-treatment was performed to obtain 67.8 g (yield 99%) of [4- (2-bromotetrafluoroethoxy) phenyl] azidomethanone as a colorless liquid.
(6) A solution comprising 67.7 g (0.198 mol) of [4- (2-bromotetrafluoroethoxy) phenyl] azidomethanone and 650 ml of toluene solvent was reacted at 100 ° C. for 1.5 hours. Conversion from azidomethanone to an isocyanato group by pyrolysis proceeds as a Curtius reaction. Toluene was distilled off under reduced pressure, and then the residue was distilled under reduced pressure. 53.8 g (yield 87%) of 4-isocyanato- (2-bromotetrafluoroethoxy) benzene (boiling point 54-56 ° C., 33 Pa) was obtained as a colorless liquid.
(7) A mixture consisting of 41.3 g (0.132 mol) of 4-isocyanato- (2-bromotetrafluoroethoxy) benzene, 74 ml of concentrated hydrochloric acid and 150 ml of 1,2-dimethoxyethane was reacted at 80 ° C. for 2 hours. To the obtained reaction mixture, an alkaline aqueous solution consisting of 56 g of potassium hydroxide (purity 85%) and 500 ml of water was added. The product was extracted with diethyl ether and then subjected to normal workup. Further, distillation under reduced pressure was carried out to obtain 33.6 g (yield 88%) of 4- (2-bromotetrafluoroethoxy) aniline (boiling point 65 to 68 ° C., 53 Pa) as a colorless liquid.
(8) To a solution consisting of 41.6 g (144 mmol) of 4- (2-bromotetrafluoroethoxy) aniline, 16.3 g (207 mmol) of pyridine and 250 ml of chloroform, 38.1 g (172 mmol) of 2-nitrobenzenesulfonyl chloride was added, The reaction was performed at room temperature for 1 hour. The usual post-reaction treatment gave 66.9 g (98% yield) of N- [4- (2-bromotetrafluoroethoxy) phenyl] -2-nitrobenzenesulfonamide as an orange solid.
(9) N- [4- (2-bromotetrafluoroethoxy) phenyl] -2-nitrobenzenesulfonamide 66.9 g (141 mmol), potassium carbonate 97 g (705 mmol) and dimethylformamide 400 ml (183 mmol) was added and the reaction was allowed to proceed for 2 hours at room temperature. After usual reaction post-treatment, 68.4 g (99% yield) of N-methyl-N- [4- (2-bromotetrafluoroethoxy) phenyl] -2-nitrobenzenesulfonamide was obtained as a yellow solid.
(10) N-methyl-N- [4- (2-bromotetrafluoroethoxy) phenyl] -2-nitrobenzenesulfonamide 55.5 g (114 mmol), lithium hydroxide monohydrate 19.1 g (456 mmol) and To a solution consisting of 400 ml of dimethylformamide was added 21.0 g (228 mmol) of mercaptoacetic acid and reacted at 60 ° C. for 2 hours. After carrying out the usual post-reaction treatment, the reaction product was distilled to give 4- (2-bromotetrafluoroethoxy) -N-methylaniline (boiling point 60-67 ° C., 13 Pa) as a pale yellow liquid, 28.5 g (Yield 83%).

攪拌装置、温度センサ、ガス導入口およびドライアイス／エタノール冷却凝縮器を備えた内容量1Lのガラス製反応容器を低温恒温槽に設置し、ジアルコキシド化合物 CsOCF₂CF(CF₃)OCF₂CF₂OCF(CF₃)CF₂OCs を23ミリモルを含むテトラグライム溶液60gを仕込んだ。内温を-33〜-30℃に調整した後、ガス導入口よりヘキサフルオロプロペンを40g仕込んだ。次に、ヘキサフルオロプロペンオキシドを10g/hr、ヘキサフルオロプロペンを4g/hrの供給速度で反応容器内に仕込んだ。42時間経過後、ガスの供給を停止し(ヘキサフルオロプロペンオキシド総仕込量428g)、さらに1時間-33〜-30℃に内温を保った。減圧下でヘキサフルオロプロペンを反応系内より除去した後、室温までゆっくり昇温した。さらに100℃まで昇温し、減圧下でヘキサフルオロプロペンオリゴマーを反応混合物より除去した。このようにして、フッ化セシウム、テトラグライムおよび含フッ素ジカルボン酸フルオリドからなる混合物を淡黄色粘稠な懸濁液として478g得た。これを精製せずに、次の工程に用いた。 Reference example 2
Preparation of fluorinated dicarboxylic acid fluoride compounds

A 1-liter glass reaction vessel equipped with a stirrer, temperature sensor, gas inlet, and dry ice / ethanol cooled condenser is placed in a low-temperature thermostatic chamber, and the dialkoxide compound CsOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ 60 g of a tetraglyme solution containing 23 mmol of OCF (CF ₃ ) CF ₂ OCs was charged. After adjusting the internal temperature to -33 to -30 ° C, 40 g of hexafluoropropene was charged from the gas inlet. Next, hexafluoropropene oxide was charged into the reaction vessel at a feed rate of 10 g / hr and hexafluoropropene at 4 g / hr. After 42 hours, the gas supply was stopped (total amount of hexafluoropropene oxide charged: 428 g), and the internal temperature was kept at -33 to -30 ° C for 1 hour. After removing hexafluoropropene from the reaction system under reduced pressure, the temperature was slowly raised to room temperature. The temperature was further raised to 100 ° C., and the hexafluoropropene oligomer was removed from the reaction mixture under reduced pressure. Thus, 478 g of a mixture composed of cesium fluoride, tetraglyme and fluorine-containing dicarboxylic acid fluoride was obtained as a pale yellow viscous suspension. This was used in the next step without purification.

s＝F^a(-131ppm)ピーク積分値
t＝F^b(-133ppm)ピーク積分値
u＝F^c(-146ppm)ピーク積分値
注) ケミカルシフトはCFCl₃基準
二官能性比＝(t／s-0.5)／(t／s+0.5)＝0.89
ヘキサフルオロプロペンオキシド数平均重合度＝4u／(2t+s)＝102 Further, after a part of the above mixture was converted to a diester form [A] with methanol, the number average polymerization degree of hexafluoropropene oxide and the bifunctional ratio (mole fraction with hexafluoropropene oxide oligomer [B] were determined by ¹⁹ F-NMR. Rate).

s = F ^a (-131ppm) Peak integrated value
t = F ^b (-133ppm) Peak integral value
u = F ^c (-146ppm) peak integral value
Note) Chemical shift is based on CFCl ₃ Bifunctional ratio = (t / s-0.5) / (t / s + 0.5) = 0.89
Hexafluoropropene oxide number average degree of polymerization = 4u / (2t + s) = 102

を、僅かに黄色味を帯びた透明な液体として65g得た。E型粘度計(東機産業製TEV-22)により粘度を測定したところ、14Pa・s(25℃)であった。
¹⁹F-NMR(ケミカルシフトはCFCl₃基準)： -125ppm(F^b)
-147ppm(F^c)
-72ppm(F^d)
-90ppm(F^e)
¹H-NMR(ケミカルシフトはTMS基準)： 7.0ppm(H^a,H^b)
3.1ppm(H^c)
IR(neat)： 1704cm^-1(C=O)
1508cm^-1(Ar) Example 78 g (about 4.5 mmol) of a mixture comprising fluorine-containing dicarboxylic acid fluoride, cesium fluoride and tetraglyme obtained in Reference Example 2 was dissolved in 90 ml of a fluorine-containing solvent (Sumitomo 3M product HFE-7100). To this was added 1.9 g (19 mmol) of triethylamine and 36 ml of diethyl ether. 4- (2-Bromotetrafluoroethoxy) -N-methylaniline (4.0 g, 13 mmol) was added thereto, and the reaction was performed at 30 ° C. for 3 hours. The obtained reaction mixture was added to saturated brine, and the separated organic layer was washed with 1.5 wt% aqueous potassium hydroxide solution, dried over anhydrous magnesium sulfate and filtered. After distilling off the fluorine-containing solvent and diethyl ether from the filtrate under reduced pressure, the resulting viscous liquid was washed several times with diethyl ether, and then diethyl ether was completely distilled off under reduced pressure. Thus, a fluorine-containing polyether compound

65 g were obtained as a slightly yellowish transparent liquid. When the viscosity was measured with an E-type viscometer (TEV-22 manufactured by Toki Sangyo), it was 14 Pa · s (25 ° C.).
¹⁹ F-NMR (chemical shift based on CFCl ₃ ): -125 ppm (F ^b )
-147ppm (F ^c )
-72ppm (F ^d )
-90ppm (F ^e )
¹ H-NMR (chemical shift is based on TMS): 7.0 ppm (H ^a , H ^b )
3.1ppm (H ^c)
IR (neat): 1704cm ^-1 (C = O)
1508cm ^-1 (Ar)

Reference example 3
100 parts by weight of the fluorinated polyether compound obtained in the examples
2,5-dimethyl-2,5-di (tert-butylperoxy) hexane 1〃
Triallyl isocyanurate 3 〃
Acetylene carbon black 13 〃
The above components were mixed using a planetary mixer to prepare a curable composition.

This curable composition was measured for curing behavior at 150 ° C. for 30 minutes using a Monsanto disc rheometer, and the following results were obtained.
ML 0.6 dN ・ m
MH 6.0 dN ・ m
t ₁₀ 1.4 minutes
t ₅₀ 6.6 min
t ₉₀ 20.4 min

  Further, a P24 O-ring was formed by compression molding at 150 ° C. for 30 minutes, and then oven vulcanization (secondary vulcanization) at 80 ° C. for 5 hours and 230 ° C. for 15 hours was performed in a nitrogen atmosphere. The compression set (according to ASTM D395 Method B; 200 ° C., 70 hours) was measured and a value of 50% was obtained.

  Further, when the glass transition temperature Tg of the P24 O-ring was measured using a differential scanning calorimeter (DSC6220 manufactured by SII Nanotechnology), a value of −55 ° C. was obtained.

Claims (5)

General formula [I]

(Wherein R ¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, X is a bromine atom or an iodine atom, l and m are each independently an integer of 10 or more, and l + m is 30 to 200). The fluorine-containing polyether compound according to claim ¹ , wherein R ¹ in the general formula [I] is a methyl group.   The fluorine-containing polyether compound according to claim 1, wherein l + m is 50 to 150 in the general formula [I]. General formula [II]

(Wherein l and m are each independently an integer of 10 or more, and l + m is 30 to 200), a fluorine-containing dicarboxylic acid fluoride compound represented by the general formula [III]

Where R ¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group, R ² is a hydrogen atom or a trimethylsilyl group, and X is a bromine atom or an iodine atom. The method for producing a fluorine-containing polyether compound according to claim 1, wherein   The method for producing a fluorinated polyether compound according to claim 4, wherein the reaction is carried out in the presence of pyridine or a tertiary amine compound.