Claims
- 1. A mono-substituted fluorinated oxetane monomer, said mono-substituted fluorinated oxetane monomer having the structure: ##STR14## wherein: a) n is 1 to 3;
- b) R is selected from the group consisting of methyl and ethyl; and
- c) R.sub.f is selected from the group consisting of linear perfluorinated alkyl, linear perfluorinated isoalkyl, branched chain perfluorinated alkyl, branched chain perfluorinated isoalkyl, and oxaperfluorinated polyether having from 4 to about 60 carbons, said linear and branched alkyls and isoalkyls having from 1 to 20 carbons.
- 2. A monosubstituted fluorinated oxetane monomer as in claim 1, wherein said mono-substituted fluorinated oxetane monomer is a member selected from the group consisting of 3-(2,2,2-trifluoroethoxymethyl)-3-methyloxetane; 3-(2,2,3,3,4,4,4-heptafluorobutoxymethyl)-3-methyloxetane; 3-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyloxymethyl)-3-methyloxetane; 3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyloxymethyl)-3-methyloxetane; 3-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyloxymethyl)-3-methyloxetane; and 3-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluorododecyloxymethyl)-3-methyloxetane.
- 3. A mono-substituted fluorinated oxetane (FOX) monomer, said mono-substituted fluorinated oxetane monomer produced by the process comprising the steps of:
- a) providing a mono-substituted oxetane premonomer having the structure: ##STR15## where R is selected from the group consisting of methyl and ethyl and X is a leaving group selected from the group consisting of bromo, chloro, iodo and aryl sulfonate, said mono-substituted oxetane premonomer being diluted in a solvent to provide a mono-substituted oxetane premonomer solution;
- b) suspending a dispersion of a strong base in an aprotic solvent to provide a strong base suspension;
- c) adding a fluorinated alcohol to said strong base suspension to produce a fluorinated alkoxide solution, said fluorinated alcohol having the structure:
- R.sub.f (CH.sub.2).sub.n OH
- where n is 1-3 and R.sub.f is a linear or branched chain fluorinated alkyl or isoalkyl having from 1 to 20 carbons, or an oxaperfluorinated polyether having from 4 to about 60 carbon atoms; and
- d) adding said mono-substituted oxetane premonomer solution to said fluorinated alkoxide solution while heating the reaction mixture to a temperature of from about 50.degree. C. to about 125.degree. C. to permit a displacement reaction, whereby the fluorinated alkoxide displaces said leaving group to produce said mono-substituted fluorinated oxetane monomer.
- 4. A mono-substituted FOX monomer produced by the process as in claim 3 which includes the steps of:
- a) quenching the displacement reaction upon consumption of the starting materials; and
- b) separating said mono-substituted fluorinated oxetane monomer product from the reaction mixture.
- 5. A mono-substituted FOX monomer produced by the process as in claim 3, wherein:
- said fluorinated alcohol is selected from the group consisting of trifluoroethanol, heptafluorobutanol, pentadecafluorooctanol, tridecafluorooctanol and other fluorinated alcohols having the following formulas:
- HO(CH.sub.2).sub.n (CF.sub.2).sub.x --F a);
- HOCH.sub.2 CF.sub.2 (OCF.sub.2 CF.sub.2).sub.x --F b); ##STR16## wherein n is 1 to 3 and x is 1 to 20 and mixtures thereof.
- 6. A mono-substituted FOX monomer produced by the process as in claim 5, wherein:
- said strong base is selected from the group consisting of sodium hydride, potassium hydride, potassium t-butoxide, calcium hydride, sodium hydroxide, potassium hydroxide, NaNH.sub.2, n-butyl lithium and lithium diisopropylamide.
- 7. A mono-substituted FOX monomer produced by the process as in claim 6, wherein:
- said solvent is selected from the group consisting of dimethylformamide (DMF), dimethylacetamide, DMSO, hexamethylene phosphoramide (HMPA) and mixtures thereof.
- 8. A mono-substituted FOX monomer produced by the process as in claim 7, wherein:
- said temperature is from about 75.degree. to about 85.degree. C.
- 9. A mono-substituted FOX monomer produced by the process as in claim 4, wherein said FOX monomer is a member selected from the group consisting of 3-(2,2,2-trifluoroethoxymethyl)-3-methyloxetane; 3-(2,2,3,3,4,4,4-heptafluorobutoxymethyl)-3-methyloxetane; 3-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyloxymethyl)-3- methyloxetane; 3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyloxymethyl)-3-methyloxetane; 3-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyloxymethyl)-3-methylxetane; 3-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluorododecyloxymethyl)-3-methyloxetane; and mixtures thereof.
- 10. A mono-substituted fluorinated monomer produced by the process comprising the steps of:
- a) providing a mono-substituted oxetane premonomer having the structure: ##STR17## where R is selected from the group consisting of methyl and ethyl, and X is a leaving group selected from the group consisting of bromo, chloro and iodo, said mono-substituted oxetane premonomer being dissolved in water to provide an aqueous mixture of said mono-substituted oxetane premonomer;
- b) charging a reaction vessel with said aqueous mixture of said mono-substituted oxetane premonomer, a fluoroalcohol, a phase transfer catalyst and a strong base to form a reaction mixture, said fluoroalcohol having the structure:
- R.sub.f (CH.sub.2).sub.n OH
- where n is 1-3 and R.sub.f is a linear or branched chain fluorinated alkyl or isoalkyl having from 1 to 20 carbons, or an oxaperfluorinated polyether having from 4 to about 60 carbon atoms;
- c) heating said reaction mixture to a temperature of 80.degree.-85.degree. C. until the reaction is complete and forms said FOX monomer as an organic layer;
- d) cooling said reaction mixture; and
- e) separating said mono-substituted fluorinated oxetane monomer as an organic layer from the aqueous reaction mixture.
- 11. A mono-substituted fluorinated monomer produced by the process of claim 10 wherein:
- said phase transfer catalyst is selected from the group consisting of tetrabutylammonium bromide, tetraethylammonium bromide, trimethylbutylammonium bromide, tetramethylammonium iodide, cetyltributylammonium bromide, crown ethers, glycols and mixtures thereof.
- 12. A mono-substituted fluorinated monomer produced by the process of claim 11, wherein:
- said fluorinated alcohol is selected from the group consisting of trifluoroethanol, heptafluorobutanol, pentadecafluorooctanol, tridecafluorooctanol and other fluorinated alcohols having the following formulas:
- HO(CH.sub.2).sub.n (CF.sub.2).sub.x --F a);
- HOCH.sub.2 CF.sub.2 (OCF.sub.2 CF.sub.2).sub.x --F b); ##STR18## wherein n is 1 to about 3 and x is 1 to about 20 and mixtures thereof.
- 13. A mono-substituted fluorinated monomer produced by the process of claim 12, wherein:
- said strong base is selected from the group consisting of sodium hydroxide and potassium hydroxide, calcium hydroxide, magnesium hydroxide, tetrabutylammonium hydroxide and mixtures thereof.
- 14. A mono-substituted fluorinated monomer produced by the process of claim 13, wherein:
- said strong base is potassium hydroxide and said phase transfer catalyst is tetrabutylammonium bromide.
- 15. A mixture of mono-substituted fluorinated oxetane monomers, said mono-substituted fluorinated oxetane monomers being selected from the group consisting of 3-(2,2,2-trifluoroethoxymethyl)-3-methyloxetane; 3-(2,2,3,3,4,4,4-heptafluoro-butoxymethyl)-3-methyloxetane; 3-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-octyloxymethyl)-3-methyloxetane; 3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-octyloxymethyl)-3-methyloxetane; 3-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyloxymethyl)-3-methyloxetane; and 3-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluorododecyloxymethyl)-3-methyloxetane.
CROSS REFERENCE TO RELATED APPLICATIONS
This Application is a Divisional Application of our parent application Ser. No. 08/371,914, filed Jan. 12, 1995, abandoned which in turn is a Continuation-In-Part application of application entitled "Preparation and Polymerization of Perfluoroalkoxy Alkylene Oxides to Prepare Hydrophobic Ethers", Ser. No. 08/206,618, filed March 7, 1994, now abandoned, which in turn is a Continuation application of application of that same title, Ser. No. 08/080,614, filed Jun. 21, 1993, now abandoned, which in turn is a Continuation application of Ser. No. 07/911,461, filed Jul. 10, 1992, now abandoned.
US Referenced Citations (25)
Foreign Referenced Citations (1)
Number |
Date |
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348350A1 |
Dec 1989 |
EPX |
Divisions (1)
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371914 |
Jan 1995 |
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Continuations (2)
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80614 |
Jun 1993 |
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Parent |
911461 |
Jul 1992 |
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Continuation in Parts (1)
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206618 |
Mar 1994 |
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