JPH0776220B2 - Novel fluorinated polyether ester - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel fluorine-containing polyether ester.

[0002]

The present invention has the general formula:

[Chemical 3] Or

[Chemical 4] [In the formula, R is a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms. ] The fluorine-containing polyether ester shown by these is provided.

Since the fluorine-containing polyether ester of the present invention can increase the solubility in CsF and other ethers like crown ether, it can be used for fluorination reaction of organic substances. The following compounds may be mentioned as specific examples of the fluorinated polyether ester of the present invention.

[0004]

[Chemical 5]

[Chemical 6]

[0005]

[Chemical 7]

[Chemical 8]

The compound of the present invention can be produced, for example, as follows. Formula: HO-R'-OH [In formula, R'is a C2-C6 bivalent aliphatic hydrocarbon group. ] In a mixture of diol, NaH and aprotic solvent (preferably ether)
3-Tetrafluorooxetane is added as it is or after diluted with a solvent and added dropwise, and reacted at room temperature to 50 ° C. for several hours. The formed precipitate (NaF) is filtered off, and the solvent is distilled off from the filtrate to obtain a crude product. In some cases, a cyclic product and a linear product can be separated by adding a protic solvent such as methanol to this crude product, cooling and precipitating the cyclic product.

[0007]

EXAMPLES Examples will be shown below. Example 1 300 with calcium chloride drying tube and ice water condenser
ml 3.9 g (0.16 g) sodium hydride in a 3-necked flask
Mol) and 200 ml of monoglyme. 5 g (0.08 mol) of ethylene glycol was added dropwise at room temperature with stirring. Further, 2,2,3,3-tetrafluorooxetane (10.5 g, 0.08 mol) was diluted with monoglyme (50 ml) and added dropwise over 1 hour.
Reacted for hours. The deposited precipitate was filtered off, and monoglyme was distilled off from the filtrate to obtain an oily product. Further, 10 ml of methanol was added to the oily product and cooled to precipitate a precipitate, and this precipitate was collected by filtration to obtain 3.7 g of a cyclic product.

This ring is

[Chemical 9] and

[Chemical 10] 1: 1 (gas chromatography) mixture.
Further, methanol was distilled off from the filtrate to obtain 4.3 g of a linear oligomer.

The analysis results of the two kinds of cyclic substances were as follows. IR (KBr): 2900, 1780, 1460, 125
0, 1140 cm ^-1 . Gas chromatograph-mass spectrometry: (Gas chromatograph conditions: column SE-30, 3φ
× 2m, 50 ℃ to 100 ℃ (heating rate 10 ℃ / min, carrier gas helium 30 ml / min))

(I)

[Chemical 11] Gas chromatograph retention time: 15.9 minutes. Mass spectrometry: 305 (M + H), 284 (M-HF), 244 (C
H ₂ CF ₂ C (= O) OCH ₂ CH ₂ OC (= O) CF ₂ CH ₂ ), 64 (CH ₂ C
_{F 2), 60 (OCH 2} CH 2 O).

(Ii)

[Chemical 12] Gas chromatograph retention time: 16.3 minutes. Mass spectrometry: 305 (M + H), 284 (M-HF), 152
(CH ₂ CF ₂ C (= O) OCH ₂ CH ₂ O), 64 (CH ₂ CF
₂ ). The average molecular weight of the linear oligomer was about 960 (average degree of polymerization: 6.3) according to the equilibrium vapor pressure method.

Example 2 300 with calcium chloride drying tube and ice water condenser
2.7 ml of sodium hydride (0.1 g
1 mol) and 250 ml of monoglyme were charged. 5.0 g (0.05 g) of 1,4-butanediol at room temperature with stirring.
6 mol) was added dropwise. Furthermore, 7.3 g (0.056 mol) of 2,2,3,3-tetrafluorooxetane was diluted with 50 ml of monoglyme and added dropwise over about 1 hour. After the addition was completed, the reaction was continued at room temperature for about 10 hours. It was The deposited precipitate was filtered off and the filtrate was concentrated to about 5 ml by distillation and then added to 500 ml of pure water with stirring. The deposited precipitate is collected by filtration,
About 8 g of white solid was obtained.

The white solid material is a ring-shaped material.

[Chemical 13] and

[Chemical 14] It was a mixture of 1: 1 (gas chromatograph). or,
Water was distilled off from the filtrate to obtain 2.4 g of a linear oligomer.

The analysis results of the two types of cyclic substances were as follows. IR (KBr) (same for both): 2950, 177
0, 1480, 1250, 1150 cm ^-1 . Gas chromatograph-mass spectrometry: (Gas chromatograph conditions: column SE-30, 3φ ×
2m, 50 ° C to 200 ° C (heating rate 10 ° C / min, carrier gas helium 30 ml / min)

(I)

[Chemical 15] Gas chromatograph retention time: 23.6 minutes. Mass spectrometry: 361 (M + H), 341 (M-HF), 272 (C
H ₂ CF ₂ C (= O) OCH ₂ CH ₂ CH ₂ CH ₂ OC (= O) CF ₂ CH ₂ ), 88 (OCF ₂ CH ₂
CH ₂ CH ₂ O), 64 (CH ₂ CF ₂ ).

(Ii)

[Chemical 16] Gas chromatograph retention time: 24.1 minutes. Mass spectrometry: 361 (M + H), 341 (M-HF), 180 (C
_{H 2 OC (= O) CF} 2 CH 2 OCH 2 CH 2 CH 2), 64 (CH 2 CF 2). ¹ H-NMR (acetone d ⁶ ) (same for both) δ (ppm) =
7.3 (8H, m), 3.50 (4H, t), 3.83 (4H, t),
4.25 (4H, t). ¹⁹ F-NMR (acetone d ⁶ ) (same for both types): δ (ppm) =
35.2 (t). The average molecular weight of the linear oligomer was 1200 according to the equilibrium vapor pressure method.

Claims (1)

[Claims] 1. A general formula: Or [Chemical 2] [In the formula, R is a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms. ] Fluorine-containing polyether ester shown by these.