FLUOROPOLYETHER GROUP CONTAINING COMPOUND AND METHOD FOR PRODUCING THE SAME

Abstract

A fluoropolyether-containing compound of the following formula (1a): R.sup.a—R.sup.2—R.sup.1—R.sup.b (1a) wherein the symbols are as defined in the specification. Also disclosed is a fluoropolyether-containing compound of the following formula (1b): R.sup.a—R.sup.2′—R.sup.1—R.sup.b (1b), as well as a method for producing a compound of the formula (A): FOC—R.sup.2—R.sup.1—COOR.sup.12 (A) wherein the symbols are as defined in the specification.

Claims

1. A fluoropolyether-containing compound of the following formula (1a):
R.sup.a—R.sup.2—R.sup.1—R.sup.b (1a) wherein R.sup.a is COF, COOR.sup.11, CH.sub.2OH, or CHO; R.sup.b is COF, COOR.sup.11, CH.sub.2OH, or CHO; here, R.sup.a and R.sup.b are groups different from each other; R.sup.11 is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms optionally substituted with fluorine; R.sup.1 is an alkylene group having 2 to 10 carbon atoms optionally substituted with fluorine; R.sup.2 is —R.sup.6a—(OR.sup.5a).sub.n—O—; R.sup.5a is a linear alkylene group having 2 to 10 carbon atoms substituted with fluorine; R.sup.6a is a linear alkylene group having 1 to 9 carbon atoms substituted with fluorine; and n is an integer of 2 to 200.

2. The fluoropolyether-containing compound according to claim 1, wherein R.sup.5a is a linear alkylene group having 2 to 4 carbon atoms substituted with fluorine; and R.sup.6a is a linear alkylene group having 1 to 3 carbon atoms substituted with fluorine.

3. The fluoropolyether-containing compound according to claim 1, R.sup.5a is a linear alkylene group having 3 carbon atoms substituted with fluorine; and R.sup.6a is a linear alkylene group having 2 carbon atoms substituted with fluorine.

4. The fluoropolyether-containing compound according to claim 1, wherein R.sup.5a is CF.sub.2CF.sub.2CH.sub.2 or CF.sub.2CF.sub.2CF.sub.2.

5. A fluoropolyether-containing compound of the following formula (1b)::
R.sup.a—R.sup.2′—R.sup.1—R.sup.b   (1b): wherein R.sup.a is COF, COOR.sup.11, CH.sub.2OH, or CHO; R.sup.b is COF, COOR.sup.11, CH.sub.2OH, or CHO; R.sup.11 is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms optionally substituted with fluorine; R.sup.1 is an alkylene group having 2 to 10 carbon atoms optionally substituted with fluorine; R.sup.2′ is —R.sup.6a—(OR.sup.5a).sub.n—O—; R.sup.5b is CF.sub.2CF.sub.2CH.sub.2; R.sup.6b is CF.sub.2CH.sub.2; and n is an integer of 2 to 200.

6. The fluoropolyether group-containing compound according to claim 1, wherein R.sup.a is COF, R.sup.b is COOR.sup.11, and RH is an alkyl group having 1 to 6 carbon atoms.

7. The fluoropolyether group-containing compound according to claim 1, wherein R.sup.1 is a perfluoroalkylene group having 2 to 10 carbon atoms.

8. A method for producing a compound of the formula (A):
FOC—R.sup.2—R.sup.1—COOR.sup.12   (A) wherein R.sup.1 is an alkylene group having 2 to 10 carbon atoms optionally substituted with fluorine; R.sup.2 is —R.sup.6a—(OR.sup.5a).sub.n—O—; R.sup.5 is a linear alkylene group having 2 to 10 carbon atoms substituted with fluorine; R.sup.6 is a linear alkylene group having 1 to 9 carbon atoms substituted with fluorine; R.sup.12 is an alkylene group having 1 to 6 carbon atoms optionally substituted with fluorine; and n is an integer of 2 to 200, the method comprising: reacting an acid fluoride compound of the formula (a):
FOC—R.sup.13—-COOR.sup.12   (a) wherein R.sup.13 is an alkylene group having 1 to 9 carbon atoms optionally substituted with fluorine; and R.sup.12 is an alkylene group having 1 to 6 carbon atoms optionally substituted with fluorine, with a cyclic ether compound of the formula (b): ##STR00007## wherein R.sup.15 is a linear alkylene group having 2 to 10 carbon atoms substituted with fluorine.

9. The production method according to claim 8, wherein R.sup.13 is a perfluoroalkylene group having 1 to 9 carbon atoms.

10. The production method claim 8, wherein R.sup.15 is a linear alkylene group having 2 to 4 carbon atoms substituted with fluorine.

11. The production method according to claim 8, wherein R.sup.15 is CF.sub.2CF.sub.2CH.sub.2.

Description

EXAMPLES

Example 1: (Synthesis of Compound A1)

[0176] To a nitrogen-purged reaction container, 27.3 g of cesium fluoride, 662 mL of diglyme, and 198.2 g of methyl 2,2,3-trifluoro-3-oxopropanoate were added, and the mixture was stirred at 5° C. for 10 minutes under an ice bath. Subsequently, at 5° C. under the ice bath, 892.2 g of 2,2,3,3-tetrafluorooxetane was added dropwise from the dropping funnel to the reaction container over 20 minutes and stirred for 2 hours. Then, the ice bath was removed and the mixture was stirred for 48 hours. The obtained reaction solution was filtered under pressure with a 5 μm PTFE filter, and diglyme was evaporated to obtain compound Al. (Number-average molecular weight: 912 (NMR), initiation efficiency from the acid fluoride: 100%)

.SUP.19.F-NMR Assignment of Compound A1

[0177] ##STR00003##

[0178] Chemical shift is based on m-xylene hexafluoride standard (−80.0 ppm)

a: 3.5 ppm, b: −130.3 ppm, c: −106.9 to −106.2 ppm, d: −140.4 to −140.7 ppm, e: −106.0 ppm, f: −137.9 ppm

Example 2: (Synthesis of Compound A2)

[0179] To a nitrogen-purged reaction container, 15.4 g of cesium fluoride, 290 mL of diglyme, and 107.0 g of methyl 2,2,3-trifluoro-3-oxopropanoate were added, and the mixture was stirred at 5° C. for 10 minutes under an ice bath. Subsequently, at 5° C. under the ice bath, 526.0 g of 2,2,3,3-tetrafluorooxetane was added dropwise from the dropping funnel to the reaction container over 20 minutes and stirred for 2 hours. Then, the ice bath was removed and the mixture was stirred for 50 hours. To the obtained reaction solution, 60 mL of methanol was added dropwise over 20 minutes, and the mixture was stirred for 24 hours. After evaporating volatile contents from the reaction solution under reduced pressure, 80 g of m-xylene hexafloride and 40 g of water were added for separation and washing, and 5 g of magnesium sulfate was added to the extracted organic layer for drying. Volatile contents were evaporated from the resulting treated solution to obtain compound A2.

(Number-average molecular weight: 865 (NMR), initiation efficiency from the acid fluoride: 100%)

.SUP.19.F-NMR Assignment of Compound A2

[0180] ##STR00004##

[0181] Chemical shift is based on m-xylene hexafluoride standard (−80.0 ppm)

b: −131.0 ppm, c: −106.4 to −106.8 ppm, d: −140.7 ppm, e: −106.0 ppm, f: −138.0 ppm

Example 3: (Synthesis of Compound B1)

[0182] To a nitrogen-purged reaction container, 4.23 g of cesium fluoride, 101 g of tetraglyme, and 4.22 g of methyl 2,2,3-trifluoro-3-oxopropanoate were added, and the mixture was stirred at 0° C. for 2 hours. Subsequently, a total of 200 g of hexafluoropropylene oxide was added in 10 g increments over 60 minutes at 0° C., and the mixture was then stirred. The obtained reaction solution was filtered under pressure with a 5 μm PTFE filter, and tetraglyme was evaporated to obtain compound B1 (COF and methyl ester). (Number-average molecular weight: 2,000 (NMR), initiation efficiency from the acid fluoride: 40%)

.SUP.19.F-NMR Assignment of Compound B1

[0183] ##STR00005##

[0184] Chemical shift is based on m-xylene hexafluoride standard (−65.0 ppm)

a: −122.4 ppm, c: −145.9 to −146.3 ppm, d,e: −79.5 to −83.3 ppm, f: −131.0 ppm, g: −82.2 to −82.6 ppm, h: 25.0 ppm

Example 4: (Synthesis of Compound B2)

[0185] To the obtained B1 reaction solution, 10 mL of methanol was added dropwise over 5 minutes at 0° C., and the mixture was stirred for 2 hours. For separation and washing, 130 g of m-xylene hexafloride and 200 g of water were added, and 5 g of magnesium sulfate was added to the extracted organic layer for drying. Volatile contents were evaporated from the resulting treated solution to obtain compound B2 (methyl ester at both ends).

(Number-average molecular weight: 2,000 (NMR), initiation efficiency from the acid fluoride: 40%)

.SUP.19.F-NMR Assignment of Compound B2

[0186] ##STR00006##

[0187] Chemical shift is based on m-xylene hexafluoride standard (−65.0 ppm)

a: −122.5 ppm, c: −145.4 to −146.2 ppm, d,e: −79.6 to −82.5 ppm, f: −132.5 ppm, g: −83.7 to −84.1 ppm

Example 5: (Synthesis of Compound B3)

[0188] To a nitrogen-purged reaction container, 3.85 g of cesium fluoride, 100 g of tetraglyme, and 3.98 g of methyl 2,2,3-trifluoro-3-oxopropanoate were added, and the mixture was stirred at 0° C. for 2 hours. Subsequently, a total of 200 g of hexafluoropropylene oxide was added in 5 g increments over 60 minutes at −30° C., and the mixture was then stirred. To the obtained reaction solution, 10 mL of methanol was added dropwise over 5 minutes at 0° C., and the mixture was stirred for 2 hours. For separation and washing, 130 g of m-xylene hexafloride and 200 g of water were added, and 5 g of magnesium sulfate was added to the extracted organic layer for drying. Volatile contents were evaporated from the resulting treated solution to obtain compound B3 (methyl ester at both ends). (Number-average molecular weight: 3,000 (NMR), initiation efficiency from the acid fluoride: 70%)

Example 6: (Synthesis of Compound B4)

[0189] To a nitrogen-purged reaction container, 1.94 g of potassium fluoride, 13 g of tetraglyme, 130 g of m-xylene hexafloride, and 5.20 g of methyl 2,2,3-trifluoro-3-oxopropanoate were added, and the mixture was stirred at 0° C. for 2 hours. Subsequently, a total of 140 g of hexafluoropropylene oxide was added in 10 g increments over 60 minutes at 0° C., and the mixture was then stirred. The obtained reaction solution was filtered under pressure with a 5 μm PTFE filter, and tetraglyme was evaporated to obtain compound B4 (COF and methyl ester).

(Number-average molecular weight: 2,900 (NMR), initiation efficiency from the acid fluoride: 60%, Mw/Mn=1.07 (GPC))

Example 7: (Synthesis of Compound B5)

[0190] To the obtained B4 reaction solution, 10 mL of methanol was added dropwise over 5 minutes at 0° C., and the mixture was stirred for 2 hours. For separation and washing, 200 g of water was added, and 5 g of magnesium sulfate was added to the extracted organic layer for drying. Volatile contents were evaporated from the resulting treated solution to obtain compound B5 (methyl ester at both ends). (Number-average molecular weight: 2,900 (NMR), initiation efficiency from the acid fluoride: 60%)

Example 8: (Synthesis of Compound B6)

[0191] To a nitrogen-purged reaction container, 1.87 g of potassium fluoride, 13 g of tetraglyme, 130 g of m-xylene hexafloride, and 5.15 g of methyl 2,2,3-trifluoro-3-oxopropanoate were added, and the mixture was stirred at 0° C. for 2 hours. Subsequently, a total of 140 g of hexafluoropropylene oxide was added in 5 g increments over 60 minutes at −30° C., and the mixture was then stirred. To the obtained reaction solution, 10 mL of methanol was added dropwise over 5 minutes at 0° C., and the mixture was stirred for 2 hours. To the reaction solution, 200 g of water was added for separation and washing, and 5 g of magnesium sulfate was added to the extracted organic layer for drying. Volatile contents were evaporated from the resulting treated solution to obtain compound B6 (methyl ester at both ends). (Number-average molecular weight: 4,000 (NMR), initiation efficiency from the acid fluoride: 86%)

Example 9: (Synthesis of Compound B7)

[0192] To a nitrogen-purged reaction container, 4.23 g of cesium fluoride, 11 g of tetraglyme, 120 g of m-xylene hexafloride, and 4.22 g of methyl 2,2,3-trifluoro-3-oxopropanoate were added, and the mixture was stirred at 0° C. for 2 hours. Subsequently, a total of 200 g of hexafluoropropylene oxide was added in 10 g increments over 60 minutes at 0° C., and the mixture was then stirred. To the obtained reaction solution, 10 mL of methanol was added dropwise over 5 minutes at 0° C., and the mixture was stirred for 2 hours. To the reaction solution, 200 g of water was added for separation and washing, and 5 g of magnesium sulfate was added to the extracted organic layer for drying. Volatile contents were evaporated from the resulting treated solution to obtain compound B7 (methyl ester at both ends). (Number-average molecular weight: 3,500 (NMR), initiation efficiency from the acid fluoride: 43%)

Example 10: (Synthesis of Compound B8)

[0193] To a nitrogen-purged reaction container, 4.23 g of cesium fluoride, 11 g of tetraglyme, 120 g of Novec 7200 (manufactured by 3M), and 4.22 g of methyl 2,2,3-trifluoro-3-oxopropanoate were added, and the mixture was stirred at 0° C. for 2 hours. Subsequently, a total of 200 g of hexafluoropropylene oxide was added in 10 g increments over 60 minutes at 0° C., and the mixture was then stirred. To the obtained reaction solution, 10 mL of methanol was added dropwise over 5 minutes at 0° C., and the mixture was stirred for 2 hours. To the reaction solution, 200 g of water was added for separation and washing, and 5 g of magnesium sulfate was added to the extracted organic layer for drying.

[0194] Volatile contents were evaporated from the resulting treated solution to obtain compound B8 (methyl ester at both ends). (Number-average molecular weight: 3,400 (NMR), initiation efficiency from the acid fluoride: 45%)

Example 11: (Synthesis of Compound B9)

[0195] To a nitrogen-purged reaction container, 4.23 g of cesium fluoride, 11 g of tetraglyme, 135 g of Novec 7100 (manufactured by 3M), and 4.22 g of methyl 2,2,3-trifluoro-3-oxopropanoate were added, and the mixture was stirred at 0° C. for 2 hours. Subsequently, a total of 200 g of hexafluoropropylene oxide was added in 10 g increments over 60 minutes at 0° C., and the mixture was then stirred. To the obtained reaction solution, 10 mL of methanol was added dropwise over 5 minutes at 0° C., and the mixture was stirred for 2 hours. To the reaction solution, 200 g of water was added for separation and washing, and 5 g of magnesium sulfate was added to the extracted organic layer for drying. Volatile contents were evaporated from the resulting treated solution to obtain compound B9 (methyl ester at both ends).

[0196] (Number-average molecular weight: 3,500 (NMR), initiation efficiency from the acid fluoride: 45%)

Example 12: (Synthesis of Compound B10)

[0197] To a nitrogen-purged reaction container, 4.23 g of cesium fluoride, 11 g of tetraglyme, 115 g of 1,1,1,3,3-pentafluorobutane, and 4.22 g of methyl 2,2,3-trifluoro-3-oxopropanoate were added, and the mixture was stirred at 0° C. for 2 hours. Subsequently, a total of 200 g of hexafluoropropylene oxide was added in 10 g increments over 60 minutes at 0° C., and the mixture was then stirred. To the obtained reaction solution, 10 mL of methanol was added dropwise over 5 minutes at 0° C., and the mixture was stirred for 2 hours. To the reaction solution, 200 g of water was added for separation and washing, and 5 g of magnesium sulfate was added to the extracted organic layer for drying. Volatile contents were evaporated from the resulting treated solution to obtain compound B10 (methyl ester at both ends). (Number-average molecular weight: 2,500 (NMR), initiation efficiency from the acid fluoride: 40%)

Example 13: (Synthesis of Compound B11)

[0198] To a nitrogen-purged reaction container, 2.9 g of potassium fluoride, 101 g of tetraglyme, and 9 g of methyl 2,2,3-trifluoro-3-oxopropanoate were added, and the mixture was stirred at 0° C. for 2 hours. Subsequently, a total of 200 g of hexafluoropropylene oxide was added in 10 g increments over 60 minutes at 0° C., and the mixture was then stirred. To the obtained reaction solution, 10 mL of methanol was added dropwise over 5 minutes at 0° C., and the mixture was stirred for 2 hours. To the reaction solution, 200 g of water was added for separation and washing, and 5 g of magnesium sulfate was added to the extracted organic layer for drying. Volatile contents were evaporated from the resulting treated solution to obtain compound B11 (methyl ester at both ends).

(Number-average molecular weight: 900 (NMR), initiation efficiency from the acid fluoride: 74%)

Example 14: (Synthesis of Compound B12)

[0199] To a nitrogen-purged reaction container, 2.9 g of potassium fluoride, 20 g of tetraglyme, 120 g of m-xylene hexafloride, and 9 g of methyl 2,2,3-trifluoro-3-oxopropanoate were added, and the mixture was stirred at 0° C. for 2 hours. Subsequently, a total of 200 g of hexafluoropropylene oxide was added in 10 g increments over 60 minutes at 0° C., and the mixture was then stirred. To the obtained reaction solution, 10 mL of methanol was added dropwise over 5 minutes at 0° C., and the mixture was stirred for 2 hours. To the reaction solution, 200 g of water was added for separation and washing, and 5 g of magnesium sulfate was added to the extracted organic layer for drying. Volatile contents were evaporated from the resulting treated solution to obtain compound B12 (methyl ester at both ends). (Number-average molecular weight: 2,100 (NMR), initiation efficiency from the acid fluoride: 76%)

Example 15: (Synthesis of Compound B13)

[0200] To a nitrogen-purged reaction container, 2.9 g of potassium fluoride, 20 g of tetraglyme, 120 g of Novec 7200 (manufactured by 3M), and 9 g of methyl 2,2,3-trifluoro-3-oxopropanoate were added, and the mixture was stirred at 0° C. for 2 hours. Subsequently, a total of 200 g of hexafluoropropylene oxide was added in 10 g increments over 60 minutes at 0° C., and the mixture was then stirred. To the obtained reaction solution, 10 mL of methanol was added dropwise over 5 minutes at 0° C., and the mixture was stirred for 2 hours. To the reaction solution, 200 g of water was added for separation and washing, and 5 g of magnesium sulfate was added to the extracted organic layer for drying.

[0201] Volatile contents were evaporated from the resulting treated solution to obtain compound B13 (methyl ester at both ends). (Number-average molecular weight: 1,900 (NMR), initiation efficiency from the acid fluoride: 75%)

INDUSTRIAL APPLICABILITY

[0202] According to the production method of the present disclosure, a fluoropolyether group-containing compound having functional groups at both ends can be easily produced.