JP2007238583A - Fluorine-containing polyether compound and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new fluorine-containing polyether compound which contains no chlorine and containing fluorine and hydrogen and is useful as a lubricant, detergent, solvent, heat transfer medium, fire-extinguishing agent, power-circulating working fluid, reaction medium, desiccant (water-separating agent) or the like, and to provide its production method. <P>SOLUTION: The new fluorine-containing polyether compound is represented by formula (1) (wherein Rf is a perfluoroalkyl group; and n is 0 or 1), and is produced by reacting a fluorovinylether compound with a polyalcohol compound in the presence of a transition metal catalyst. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is useful as a lubricating oil, cleaning agent, solvent, heat transfer medium, fire extinguishing agent, power circulation working fluid, reaction medium, desiccant (draining agent), etc. The present invention relates to a fluorine polyether compound.

  Fluorine-containing compounds are widely used industrially for polymer materials, refrigerants, cleaning agents, solvents, foaming agents, pharmaceuticals, agricultural chemicals, and the like. In particular, the fluorine-containing polyether compound is expected to be used as a lubricating oil, a cleaning agent, a solvent, a heat transfer medium, a fire extinguisher, a power circulation working fluid, a reaction solvent, a desiccant (water draining agent) and the like.

  As such a fluorinated polyether compound, a perfluoropolyether having a linear perfluorocarbon skeleton bonded by oxygen or a branched structure of a trifluoromethyl group in part is known. Lexis Galden (registered trademark), Fomblin (registered trademark), DuPont Krytox (registered trademark), Daikin Industries, Ltd. Demnam (registered trademark), etc. are marketed as known compounds.

  However, perfluoropolyethers have low solubility in common hydrocarbon-based organic solvents. For example, operations such as coating, dipping, and spraying require the use of fluorine-based organic solvents. May be incurred. There are also many problems such as the need for recovery due to the expensive solvent (Patent Document 1).

In recent years, hydrofluoroether (HFE) has attracted attention as a new refrigerant, cleaning agent, and foaming agent that replaces chlorofluorocarbon (CFC) and hydrochlorofluorocarbon (HCFC). In particular, in the cleaning field, HFE having a structure of R _F —CHFCF ₂ —O—R (where R _F is a fluorine atom or a perfluoroalkyl group) does not destroy the ozone layer and has a warming effect. It is expected as a low cleaning agent (Non-patent Document 1).

Among the above-mentioned HFEs having the structure of —CHFCF ₂ —O—, as polyethers having two ether oxygens, diethers synthesized from trifluoromethyl trifluorovinyl ether and alcohol are known (Patent Literature). 2).
However, since these polyethers have low boiling points and high volatility, they are not suitable for uses such as lubricating oils.

  Polyethers synthesized from 1,1,2-trifluoro- (2′-heptafluoropropoxy) -2-hexafluoropropoxyethylene and polyols containing a branched ether skeleton are also known (non-patent) In literature 2), many of these compounds lack stability and their physical properties have not been clarified.

Thus, the compound having a -O-CHFCF ₂ -O- structures known hitherto, the boiling point is low and is intended to lack of stability, extremely be used for example in applications such as the lubricating oil It was difficult.

J. Fluorine Chem., 101, 215 (2000) J. Fluorine Chem., 117, 149 (2002) JP-A-8-259482 Japanese Patent Laid-Open No. 11-147847

  It is an object of the present invention to provide a novel fluorine-containing polyether that has no influence on the global environment without destroying the ozone layer, has low volatility, and can be suitably used as a lubricating oil or the like. .

（式中、Rfは、ペルフルオロアルキル基を示し、nは0または1を示す。）
（２）下記一般式（２）で表されるフルオロビニルエーテル化合物と、

（式中、Rfはペルフルオロアルキル基を示す。）
と、下記一般式（３）で表されるポリアルコール化合物

（式中、nは0または1を示す。）
とを遷移金属触媒の存在下で反応させることを特徴とする上記（１）に記載の含フッ素ポリエーテル化合物の製造方法。
（３）遷移金属がパラジウムであることを特徴とする上記（２）に記載の含フッ素ポリエーテル化合物の製造方法。 As a result of intensive studies to solve the above problems, the present inventor has completed the present invention.
That is, according to this application, the following invention is provided.
(1) A fluorine-containing polyether compound represented by the following general formula (1).

(In the formula, Rf represents a perfluoroalkyl group, and n represents 0 or 1.)
(2) a fluorovinyl ether compound represented by the following general formula (2);

(In the formula, Rf represents a perfluoroalkyl group.)
And a polyalcohol compound represented by the following general formula (3)

(In the formula, n represents 0 or 1.)
In the presence of a transition metal catalyst. The method for producing a fluorinated polyether compound according to (1) above.
(3) The method for producing a fluorinated polyether compound as described in (2) above, wherein the transition metal is palladium.

（式中、Rfは、ペルフルオロアルキル基を示し、nは0または1を示す。）
一般式（１）において、Rfは分岐していてもよいペルフルオロアルキル基であり、好ましくは炭素数１から１２までのペルフルオロアルキル基、さらに好ましくは炭素数１〜３のCF₃, CF₂CF₃, CF₂CF₂CF₃である。
本発明の新規な含フッ素ポリエーテル化合物の代表例としては、以下のようなものが例示される。

The novel fluorine-containing polyether compound of the present invention is represented by a fluorine-containing polyether compound represented by the following general formula (1).

(In the formula, Rf represents a perfluoroalkyl group, and n represents 0 or 1.)
In the general formula (1), Rf is an optionally branched perfluoroalkyl group, preferably a perfluoroalkyl group having 1 to 12 carbon atoms, and more preferably CF ₃ or CF ₂ CF ₃ having 1 to ₃ carbon atoms. , CF ₂ CF ₂ CF ₃ .
The following are illustrated as typical examples of the novel fluorine-containing polyether compound of the present invention.

These compounds can be produced by reacting the fluorovinyl ether compound represented by the general formula (2) with the polyalcohol compound represented by the general formula (3).
Rf of the fluorovinyl ether compound represented by the general formula (2) represents a perfluoroalkyl group similar to that of the general formula (1).
The polyalcohol compound represented by the general formula (3) is not particularly limited, and examples thereof include HOCH ₂ CH ₂ OH and HOCH ₂ CH (OH) CH ₂ OH.
The reaction between the fluorovinyl ether and the polyalcohol can be suitably performed in the presence of a transition metal catalyst or an alkaline catalyst. Preferably, it is carried out in the presence of a transition metal catalyst.

The transition metal catalyst is preferably a catalyst containing a Group 10 transition metal, and examples of the transition metal include nickel, palladium, and platinum, with palladium being preferred.
These Group 10 transition metal catalysts may be simple metals, or metal complexes in which the metal is a central metal and a ligand containing a Group 15 element is coordinated thereto. Nitrogen, phosphorus, arsenic and the like are exemplified as the group 15 element, but phosphorus is preferable. The phosphorus ligand is not particularly limited as long as it can be applied as the metal ligand, and examples thereof include trivalent or pentavalent phosphorus compounds. Preferably, triphenylphosphine, tris (2-methylphenyl) phosphine, tris Examples include (4-methoxyphenyl) phosphine, diphenylphosphinomethane, diphenylphosphinoethane, diphenylphosphinopropane, diphenylphosphinobutane, diphenylphosphinoferrocene and the like. In using the catalyst, a single metal or a metal complex may be used alone, or a ligand as described above may coexist therewith.

  The amount of the fluorovinyl ether represented by the general formula (2) relative to the polyalcohol represented by the general formula (3) is not particularly limited as long as this reaction can be applied, but is usually 0.1 to 10 equivalents, preferably 0.5. ~ 3 equivalents. Moreover, you may react in a solvent. The solvent is not particularly limited as long as this reaction can be applied, and examples thereof include acetonitrile, tetrahydrofuran, dioxane, dimethyl sulfoxide, dichloromethane and the like.

  The reaction temperature is usually 0 ° C to 150 ° C, preferably 10 ° C to 100 ° C, more preferably 20 ° C to 60 ° C.

  The reaction time varies depending on the reaction temperature, the type of substrate, etc., but is usually in the range of 0.5 to 500 hours, preferably 1 to 200 hours.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited by the following examples.

Example 1
Tetrakistriphenylphosphine palladium (Pd (PPh ₃ ) ₄ : 116 mg; 0.10 mmol) and 1,4-bis (diphenylphosphino) butane (dppb: 85 mg; 0.20 mmol) A glass reactor with a vacuum valve made of Teflon (registered trademark) was vacuum-dried, and then ethylene glycol (62 mg; 1.0 mmol) and acetonitrile (3.0 mL) were added, followed by vacuum degassing. Next, trifluoromethyl trifluorovinyl ether (3.0 mmol) was charged using a vacuum line while cooling with liquid nitrogen. The reactor was kept at room temperature and stirred for 48 hours. The crude product obtained by the reaction was analyzed by ¹ H-NMR and ¹⁹ F-NMR. As a result, the desired 1,2-di [1 ′, 1 ′, 2′-trifluoro-2 ′-(trifluoro It was confirmed that (methoxy) ethoxy] ethane (CF ₃ OCHFCF ₂ OCH ₂ CH ₂ OCF ₂ CHFOCF ₃ ) was obtained (yield 98%). ¹ H-NMR (CD ₃ CN, TMS)
δ 4.23 (s, -OC H ₂ C H ₂ O-, 4H)
δ 6.06 ~ 6.29 (dm, -CF ₂ C H FO-, 2H, J _HF = 53Hz)
¹⁹ F-NMR (CD ₃ CN, CFCl ₃ )
δ -58.9 to -59.2 (m, -OCF ₃ , 6F)
δ -88.2 to -89.8 (m, -OC F ₂ CHF-, 4F)
δ -145.3 to -145.7 (m, -OCF ₂ CH F- , 2F, J _HF = 51Hz)

Example 2
Tetrakistriphenylphosphine palladium (Pd (PPh ₃ ) ₄ : 116 mg; 0.10 mmol) and 1,4-bis (diphenylphosphino) butane (dppb: 85 mg; 0.20 mmol) A glass reactor with a vacuum valve made of Teflon (registered trademark) was vacuum-dried, and then ethylene glycol (62 mg; 1.0 mmol) and acetonitrile (3.0 mL) were added, followed by vacuum degassing. Next, pentafluoroethyl trifluorovinyl ether (3.0 mmol) was charged using a vacuum line while cooling with liquid nitrogen. The reactor was kept at room temperature and stirred for 144 hours. The crude product obtained by the reaction was purified by distillation and analyzed by ¹ H-NMR and ¹⁹ F-NMR. As a result, the desired 1,2-di [1 ′, 1 ′, 2′-trifluoro-2 ′ was obtained. It was confirmed that-(pentafluoroethoxy) ethoxy] ethane (CF ₃ CF ₂ OCHFCF ₂ OCH ₂ CH ₂ OCF ₂ CHFOCF ₂ CF ₃ ) was obtained (yield 77%). Bp 80 ℃ / 15 mmHg;
¹ H-NMR (CD ₃ CN, TMS)
δ 4.20 (s, -OC H ₂ C H ₂ O-, 4H)
δ 5.75 to 5.95 (dt, -CF ₂ C H FO-, 2H, J ₂ = 53Hz, J ₃ = 3Hz)
¹⁹ F-NMR (CD ₃ CN, CFCl ₃ )
δ -86.8 (s, -CF ₂ C F ₃ , 6F)
δ -89.4 to -92.0 (m, -C F ₂ CF ₃ , 4F)
δ -89.7 to -91.4 (m, -OC F ₂ CHF-, 4F)
δ -144.9 to -145.2 (m, -OCF ₂ CH F- , 2F, J _HF = 53Hz)

Example 3
Tetrakistriphenylphosphine palladium (Pd (PPh ₃ ) ₄ : 116 mg; 0.10 mmol) and 1,4-bis (diphenylphosphino) butane (dppb: 85 mg; 0.20 mmol) A glass reactor with a vacuum valve made of Teflon (registered trademark) was vacuum-dried, and then ethylene glycol (62 mg; 1.0 mmol) and acetonitrile (3.0 mL) were added, followed by vacuum degassing. Next, heptafluoropropyl trifluorovinyl ether (3.0 mmol) was charged using a vacuum line while cooling with liquid nitrogen. The reactor was kept at room temperature and stirred for 144 hours. The crude product obtained by the reaction was purified by distillation and analyzed by ¹ H-NMR and ¹⁹ F-NMR. As a result, the desired 1,2-di [1 ′, 1 ′, 2′-trifluoro-2 ′ was obtained. It was confirmed that-(heptafluoropropoxy) ethoxy] ethane (CF ₃ CF ₂ CF ₂ OCHFCF ₂ OCH ₂ CH ₂ OCF ₂ CHFO CF ₂ CF ₂ CF ₃ ) was obtained (yield 75%). Bp 94 ℃ / 15 mmHg;
¹ H-NMR (CD ₃ CN, TMS)
δ 4.19 (s, -OC H ₂ C H ₂ O-, 4H)
δ 5.77 to 5.98 (dt, -CF ₂ C H FO-, 2H, J ₂ = 53Hz, J ₃ = 3Hz)
¹⁹ F-NMR (CD ₃ CN, CFCl ₃ )
δ -82.0 (t, -CF ₂ CF ₂ C F ₃ , 6F, J = 7Hz)
δ -85.1 to -88.0 (m, -C F ₂ CF ₂ CF ₃ , 4F)
δ -89.8 to -91.4 (m, -OC F ₂ CHF-, 4F)
δ -130.4 (s, -CF ₂ C F ₂ CF ₃ , 4F)
δ -144.8 to -145.4 (m, -OCF ₂ CH F- , 2F, J _HF = 53Hz)

Example 4
Teflon with an internal volume of 5-8 mL charged with tetrakistriphenylphosphine palladium (Pd (PPh ₃ ) ₄ : 218 mg; 0.19 mmol) and 1,4-bis (diphenylphosphino) butane (dppb: 161 mg; 0.38 mmol) A glass reactor equipped with a vacuum valve (registered trademark) was vacuum-dried, and glycerol (116 mg; 1.3 mmol) and acetonitrile (3.0 mL) were added thereto, followed by vacuum deaeration. Next, trifluoromethyl trifluorovinyl ether (5.0 mmol) was charged using a vacuum line while cooling with liquid nitrogen. The reactor was kept at room temperature and stirred for 72 hours. The crude product obtained by the reaction was purified by distillation and analyzed by ¹ H-NMR and ¹⁹ F-NMR. As a result, the desired 1,2,3-tri [1 ′, 1 ′, 2′-trifluoro- It was confirmed that 2 ′-(trifluoromethoxy) ethoxy] propane (CF ₃ OCHFCF ₂ OCH ₂ CH (OCF ₂ CHFOCF ₃ ) CH ₂ OCF ₂ CHFOCF ₃ ) was obtained (yield 71%). Bp 160 ° C / 20 mmHg;
¹ H-NMR (CD ₃ CN, TMS)
δ 4.15 to 4.30 (m, -C H ₂ O-, 4H)
δ 4.83 to 4.90 (m, -C H (OCF ₂ -)-, 1H)
δ 6.06 ~ 6.29 (dm, -CF ₂ C H FO-, 3H, J _HF = 54Hz)
¹⁹ F-NMR (CD ₃ CN, CFCl ₃ )
δ -59.0 to -59.2 (m, -OCF ₃ , 9F)
δ -85.7 to -90.5 (m, -OC F ₂ CHF-, 6F)
δ -145.4 to -145.9 (m, -OCF ₂ CH F- , 3F, J _HF = 53Hz)

Example 5
Tetrakistriphenylphosphine palladium (Pd (PPh ₃ ) ₄ : 173 mg; 0.15 mmol) and 1,4-bis (diphenylphosphino) butane (dppb: 128 mg; 0.30 mmol) charged with an internal volume of 5-8 mL A glass reactor equipped with a vacuum valve made of Teflon (registered trademark) was vacuum-dried, and glycerol (117 mg; 1.3 mmol) and acetonitrile (3.0 mL) were added, followed by vacuum degassing. Next, pentafluoroethyl trifluorovinyl ether (4.0 mmol) was charged using a vacuum line while cooling with liquid nitrogen. The reactor was kept at room temperature and stirred for 144 hours. The crude product obtained by the reaction was purified by distillation and analyzed by ¹ H-NMR and ¹⁹ F-NMR. As a result, the desired 1,2,3-tri [1 ′, 1 ′, 2′-trifluoro- 2 ′-(pentafluoroethoxy) ethoxy] propane (CF ₃ CF ₂ OCHFCF ₂ OCH ₂ CH (OCF ₂ CHFOCF ₂ CF ₃ ) CH ₂ OCF ₂ CHFOCF ₂ CF ₃ ) was confirmed to be obtained (yield 61 %). Bp 127 ° C / 15 mmHg;
¹ H-NMR (CD ₃ CN, TMS)
δ 4.11 to 4.26 (m, -C H ₂ O-, 4H)
δ 4.70 to 4.78 (m, -C H (OCF ₂ -)-, 1H)
δ 5.77 to 6.00 (dm, -CF ₂ C H FO-, 3H, J _HF = 53Hz)
¹⁹ F-NMR (CD ₃ CN, CFCl ₃ )
δ -86.6 to -86.9 (s, -CF ₂ C F ₃ , 9F)
δ -89.4 to -90.4 (m, -C F ₂ CF ₃ , 6F)
δ -89.7 to -92.0 (m, -OC F ₂ CHF-, 6F)
δ -145.0 to -145.3 (m, -OCF ₂ CH F- , 3F, J _HF = 54Hz)

Example 6
Tetrakistriphenylphosphinepalladium (Pd (PPh ₃ ) ₄ : 173 mg; 0.15 mmol) and 1,4-bis (diphenylphosphino) butane (dppb: 129 mg; 0.30 mmol) charged with an internal volume of 5-8 mL A glass reactor equipped with a vacuum valve made of Teflon (registered trademark) was vacuum-dried, and glycerol (111 mg; 1.2 mmol) and acetonitrile (3.0 mL) were added thereto, followed by vacuum degassing. Next, heptafluoropropyl trifluorovinyl ether (4.0 mmol) was charged using a vacuum line while cooling with liquid nitrogen. The reactor was kept at room temperature and stirred for 144 hours. The crude product obtained by the reaction was purified by distillation and analyzed by ¹ H-NMR and ¹⁹ F-NMR. As a result, the desired 1,2,3-tri [1 ′, 1 ′, 2′-trifluoro- 2 '-(heptafluoropropoxy) ethoxy] propane (CF ₃ CF ₂ CF ₂ OCHFCF ₂ OCH ₂ CH (OCF ₂ CHFOCF ₂ CF ₂ CF ₃ ) CH ₂ OCF ₂ CHFOCF ₂ CF ₂ CF ₃ ) Confirmed (yield 59%). Bp 136 ° C / 15 mmHg;
¹ H-NMR (CD ₃ CN, TMS)
δ 4.12 to 4.20 (m, -C H ₂ O-, 4H)
δ 4.68 to 4.76 (m, -C H (OCF ₂ -)-, 1H)
δ 5.78 to 6.02 (dm, -CF ₂ C H FO-, 3H, J _HF = 53Hz)
¹⁹ F-NMR (CD ₃ CN, CFCl ₃ )
δ -81.7 ~ -82.1 (t, -CF 2 CF 2 C F 3, 9F, J = 7Hz)
δ -85.0 to -88.0 (m, -C F ₂ CF ₂ CF ₃ , 6F)
δ -87.0 to -92.0 (m, -OC F ₂ CHF-, 6F)
δ -130.1 to -120.5 (s, -CF ₂ C F ₂ CF ₃ , 6F)
δ -144.6 to -145.3 (m, -OCF ₂ CH F- , 3F)

Claims (3)

A fluorine-containing polyether compound represented by the following general formula (1).

(In the formula, Rf represents a perfluoroalkyl group, and n represents 0 or 1.)
A fluorovinyl ether compound represented by the following general formula (2);

(In the formula, Rf represents a perfluoroalkyl group.)
And a polyalcohol compound represented by the following general formula (3)

(In the formula, n represents 0 or 1.)
The method for producing a fluorinated polyether compound according to claim 1, wherein the compound is reacted in the presence of a transition metal catalyst. The method for producing a fluorinated polyether compound according to claim 2, wherein the transition metal is palladium.