Claims
- 1. A process for preparing a di(fluoroalkyl containing group-substituted alkyl) phosphate salt of the formula:
- [R.sub.f --A.sup.1.sub.k --(CH.sub.2).sub.m --O].sub.2 PO--OA.sup.2(I)
- which comprises hydrolyzing a mon-sec. or tert.-alkyl or alkenyl di(fluoroalkyl containing group-substituted alkyl) phosphate of the formula:
- [R.sub.f --A.sup.1.sub.k --(CH.sub.2).sub.m --O].sub.2 PO--OR(II)
- with a base selected from the group consisting of an alkali hydroxide, an ammonium hydroxide and an amine, at a temperature of 80.degree. to 100.degree. C., the base being used in an amount of 1 to 10 equivalents per mole of the alkyl or alkenyl di(fluoroalkyl containing group-substituted alkyl) phosphate (II), wherein
- each R.sub.f is independently a perfluoroalkyl group or .omega.-hydroperfluoroalkyl group having 3 to 21 carbon atoms and may be linear, branched, cyclic or a combination thereof,
- each A.sup.1 is independently a divalent group which is selected from the group consisting of --COO--, SO.sub.2 --, --O--, --(CH.sub.2).sub.3 --O--, --S--, --(CH.sub.2).sub.p --NR'--, --CH.sub.2 CH(OR')--, --CO--NR'-- or --SO.sub.2 --NR'--in which R' is a hydrogen or an alkyl group having 1 to 5 carbon atoms, and p is a integer of 1 to 6,
- A.sup.2 is an alkaline metal or an ammonium group which may be substituted with an alkyl and/or hydroxyalkyl group,
- R is a secondary or tertiary alkyl or alkenyl group having 3 to 9 carbon atoms,
- k is 0 to 1, and
- m is an integer of 1 to 4.
- 2. The process of claim 1, wherein the di(fluoroalkyl containing group-substituted alkyl) phosphate salt of formula (I) is selected from the group consisting of:
- (C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 O).sub.2 POONH.sub.2 (C.sub.2 H.sub.4 OH).sub.2
- [(CF.sub.3).sub.2 CF(CF.sub.2).sub.6 CH.sub.2 CH.sub.2 O].sub.2 POONH.sub.2 (C.sub.2 H.sub.4 OH).sub.2
- (C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 O).sub.2 POONH.sub.2 (C.sub.2 H.sub.4 OH).sub.2
- (C.sub.6 F.sub.13 CH.sub.2 CH.sub.2 O).sub.2 POONH.sub.2 (C.sub.2 H.sub.4 OH).sub.2
- (C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 O).sub.2 POONH.sub.2 (C.sub.2 H.sub.4 OH).sub.2
- (C.sub.12 F.sub.25 CH.sub.2 CH.sub.2 O).sub.2 POONH.sub.2 (C.sub.2 H.sub.4 OH).sub.2
- (C.sub.14 F.sub.29 CH.sub.2 CH.sub.2 O).sub.2 POONH.sub.2 (C.sub.2 H.sub.4 OH).sub.2
- (C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 O).sub.2 POONH.sub.4
- (C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 O).sub.2 POONH(C.sub.2 H.sub.4 OH).sub.3
- [C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 O].sub.2 POONH.sub.4
- [C.sub.6 F.sub.13 SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 O].sub.2 POONH.sub.4
- [C.sub.10 F.sub.21 SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 O].sub.2 POONH.sub.4
- [C.sub.12 F.sub.25 SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 O].sub.2 POONH.sub.4
- [C.sub.14 F.sub.29 SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 O].sub.2 POONH.sub.4
- [C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 O].sub.2 POONH.sub.2 (CH.sub.2 CH.sub.2 OH).sub.2
- [C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 O].sub.2 POONH(CH.sub.2 CH.sub.2 OH).sub.3
- [C.sub.8 F.sub.17 SO.sub.2 N(C.sub.3 H.sub.7)CH.sub.2 CH.sub.2 O].sub.2 POONH(CH.sub.2 CH.sub.2 OH).sub.2
- [C.sub.8 F.sub.17 CON(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 O].sub.2 POONH(CH.sub.2 CH.sub.2 OH).sub.3
- (C.sub.8 F.sub.17 COOCH.sub.2 CH.sub.2 O).sub.2 POONH.sub.4
- (C.sub.8 F.sub.17 SO.sub.2 CH.sub.2 CH.sub.2 O).sub.2 POONH.sub.4
- [C.sub.8 F.sub.17 (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 O].sub.2 POONH.sub.4, and
- [C.sub.8 F.sub.17 CH.sub.2 CH(OH)CH.sub.2 O].sub.2 POONH.sub.4.
- 3. The process of claim 1, wherein the alkyl ester of the di(fluoro-alkyl containing group substituted alkyl) phosphate of formula (II) is selected from the group consisting of:
- (C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 O).sub.2 POOCH(CH.sub.3).sub.2
- [(CF.sub.3).sub.2 CF(CF.sub.2).sub.6 CH.sub.2 CH.sub.2 O].sub.2 POOCH(CH.sub.3).sub.2
- (C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 O).sub.2 POOCH(CH.sub.3).sub.2
- (C.sub.6 F.sub.13 CH.sub.2 CH.sub.2 O).sub.2 POOCH(CH.sub.3).sub.2
- (C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 O).sub.2 POOCH(CH.sub.3).sub.2
- (C.sub.12 F.sub.25 CH.sub.2 CH.sub.2 O).sub.2 POOCH(CH.sub.3).sub.2
- (C.sub.14 F.sub.29 CH.sub.2 CH.sub.2 O).sub.2 POOCH(CH.sub.3).sub.2
- (C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 O).sub.2 POOC(CH.sub.3).sub.3
- (C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 O).sub.2 POOCH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2
- [C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 O].sub.2 POOCH(CH.sub.3).sub.2
- [C.sub.6 F.sub.13 SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 O].sub.2 POOCH(CH.sub.3).sub.2
- [C.sub.10 F.sub.21 SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 O].sub.2 POOCH(CH.sub.3).sub.2
- [C.sub.12 F.sub.25 SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 O].sub.2 POOCH(CH.sub.3).sub.2
- [C.sub.14 F.sub.29 SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 O].sub.2 POOCH(CH.sub.3).sub.2
- [C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 O].sub.2 POOCH(CH.sub.3).sub.3
- [C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 O].sub.2 POOCH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2
- [C.sub.8 F.sub.17 SO.sub.2 N(C.sub.3 H.sub.7)CH.sub.2 CH.sub.2 O].sub.2 POOCH(CH.sub.3).sub.2
- [C.sub.8 F.sub.17 CON(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 O].sub.2 POOCH(CH.sub.3).sub.2
- [C.sub.8 F.sub.17 COOCH.sub.2 CH.sub.2 ].sub.2 POOCH(CH.sub.3).sub.2
- [C.sub.8 F.sub.17 SO.sub.2 CH.sub.2 CH.sub.2 O].sub.2 POOCH(CH.sub.3).sub.2
- [C.sub.8 F.sub.17 (CH.sub.2)OCH.sub.2 CH.sub.2 O].sub.2 POOCH.sub.2 CH(CH.sub.3).sub.2, and
- [C.sub.8 F.sub.17 CH.sub.2 CH(OH)CH.sub.2 O].sub.2 POOCH(CH.sub.3).sub.2.
- 4. The process of claim 1, wherein the alkali hydroxide is selected from the group consisting of potassium hydroxide and sodium hydroxide.
- 5. The process of claim 1, wherein the amine is selected from the group consisting of trimethylamine, triethylamine, tripropylamine, tributylamine, triethanolamine, diethylamine, dipropylamine, diethanolamine, ethylamine, propylamine and ethanolamine.
- 6. The process of claim 4, wherein the alcohol of formula (III) is selected from the group consisting of:
- C.sub.4 F.sub.9 CH.sub.2 CH.sub.2 OH
- (CF.sub.3).sub.2 CF(CF.sub.2).sub.6 CH.sub.2 CH.sub.2 OH
- C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 OH
- C.sub.10 F.sub.21 CH.sub.2 CH.sub.2 OH
- C.sub.8 F.sub.17 SO.sub.2 N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 OH
- C.sub.8 F.sub.17 SO.sub.2 N(C.sub.3 H.sub.7)CH.sub.2 CH.sub.2 OH, and
- C.sub.8 F.sub.17 SO.sub.2 N(CH.sub.3)CH.sub.2 CH.sub.2 OH.
- 7. The process according to claim 4, wherein the molar ratio of the alcohol of formula (III) to the phosphoryl monoalkoxide dihalide of formula (IV) is 2:1 to 2:1.2.
- 8. The process of claim 1, wherein the base is selected from the group consisting of diethanolamine, sodium hydroxide and diethylamine.
- 9. A process for preparing a di(fluoroalkyl containing group-substituted alkyl) phosphate salt of formula (I)
- [R.sub.f --A.sup.1.sub.k --(CH.sub.2).sub.m --O].sub.2 PO--OA.sup.2(I)
- which comprises:
- reacting a secondary or tertiary alcohol with phosphoryl trihalide in a molar ratio of the secondary or tertiary alcohol to the phosphoryl trihalide of 0.9:1 to 1:1 at a temperature of room temperature to 70.degree. C. to produce a phosphoryl monoalkoxide dihalide,
- reacting the phosphoryl monoalkoxide dihalide with a fluoroalkyl containing group-substituted alcohol in a molar ratio of said dihalide to the fluoroalkyl containing group-substituted alcohol of 1:2 to 1.2:2 at a temperature of 80.degree. to 100.degree. C. to produce a mono sec.- or tert.-alkyl di(fluoroalkyl containing group-substituted alkyl) phosphate of formula (II)
- [R.sub.f --A.sup.1.sub.k --(CH.sub.2).sub.m --O].sub.2 PO--OR(II)
- and
- hydrolyzing the mono-sec.- or tert.-alkyl di(fluoroalkyl containing group-substituted alkyl) phosphate of formula (II) with a base at a temperature of 80.degree. to 100.degree. C., the base being used in an amount of 1 to 10 equivalent per mole of the alkyl or alkenyl di(fluoroalkyl containing group-substituted alkyl) phosphate of formula (II),
- wherein each R.sub.f is independently a perfluoroalkyl group or .omega.-hydroperfluoroalkyl group having 3 to 21 carbon atoms and may be linear, branched, cyclic or a combination thereof,
- each A.sup.1 is independently a divalent group which is selected from the group consisting of --COO--, SO.sub.2 --, --O--, --(CH.sub.2).sub.3 --O--, --S--, --(CH.sub.2).sub.p --NR'--, --CH.sub.2 CH(OR')--, --CO--NR'-- or --SO.sub.2 --NR'-- in which R' is a hydrogen or an alkyl group having 1 to 5 carbon atoms, and p is a integer of 1 to 6,
- A.sup.2 is an alkaline metal or an ammonium group which may be substituted with an alkyl and/or hydroxyalkyl group,
- R is a secondary or tertiary alkyl or alkenyl group having 3 to 9 carbon atoms,
- k is 0 to 1, and
- m is an integer of 1 to 4.
- 10. A process for preparing a di(fluoroalkyl containing group-substituted alkyl) phosphate salt of the formula:
- [R.sub.f --A.sup.1.sub.k --(CH.sub.2).sub.m --O].sub.2 PO--OA.sup.2(I)
- which comprises reacting a secondary or tertiary alcohol of the formula:
- ROH (V)
- with a phosphoryl trihalide of the formula:
- POX.sub.3 (VI)
- in a molar ratio of the secondary or tertiary alcohol to the phosphoryl trihalide of 0.9:1 to 1:1 at a temperature of room temperature to 70.degree. C. to produce a phosphoryl monoalkoxide dihalide of the formula:
- RO--POX.sub.2 (IV)
- and reacting the phosphoryl monoalkoxide dihalide of the formula (IV) with a fluoroalkyl containing group-substituted alcohol of the formula:
- R.sub.f --A.sup.1.sub.k --(CH.sub.2).sub.m --OH (III)
- in a molar ratio of said dihalide to the fluoroalkyl containing group-substituted alcohol of 1:2 to 1.2:2 at a temperature of 80.degree. to 100.degree. C. to produce an alkyl ester of di(fluoroalkyl containing group-substituted alkyl) phosphate of the formula:
- [R.sub.f --A.sup.1.sub.k --(CH.sub.2).sub.m --O].sub.2 PO--OR(II)
- and then hydrolyzing the alkyl ester of di(fluoroalkyl containing group-substituted alkyl) phosphate of the formula (II) with a base selected from the group consisting of an alkali hydroxide, an ammonium hydroxide and an amine, at a temperature of 80.degree. to 100.degree. C., the base being used in an amount of 1 to 10 equivalent per mole of the alkyl or alkenyl di(fluoroalkyl containing group-substituted alkyl) phosphate of formula (II), wherein each R.sub.f is independently a perfluoroalkyl group or .omega.-hydroperfluoroalkyl group having 3 to 21 carbon atoms,
- each A.sup.1 is independently a divalent group which is selected from the group consisting of --COO--, SO.sub.2 --, --O--, --(CH.sub.2).sub.3 --O--, --S--, --(CH.sub.2).sub.p --NR'--, --CH.sub.2 CH(OR')--, --CO--NR'-- or --SO.sub.2 --NR'-- in which R' is a hydrogen or an alkyl group having 1 to 5 carbon atoms, and p is a integer of 1 to 6,
- A.sup.2 is an alkaline metal or an ammonium group which optionally have an alkyl and/or hydroxyalkyl substituent,
- R is a secondary or tertiary alkyl or alkenyl group having 3 to 9 carbons,
- each X is independently halogen,
- k is 0 to 1, and
- m is an integer of 1 to 4.
Priority Claims (1)
Number |
Date |
Country |
Kind |
62-100868 |
Apr 1987 |
JPX |
|
Parent Case Info
This is a continuation-in-part application of Ser. No. 07/184,673 filed on Apr. 22, 1988, now abandoned.
US Referenced Citations (3)
Foreign Referenced Citations (2)
Number |
Date |
Country |
2755530 |
Jun 1978 |
DEX |
54-7776 |
Oct 1979 |
JPX |
Non-Patent Literature Citations (4)
Entry |
Hayashi et al., Chem. Abst. 89-108132W (1978). |
English Abstract of Japanese 60-64990, 8/85. |
English Abstract of Japanese 56-25190, 5/81. |
English Abstract of Japanese 52-65222, 9/77. |
Continuation in Parts (1)
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Number |
Date |
Country |
Parent |
184673 |
Apr 1988 |
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