Polyfluorinated epoxides and associated polymers and processes

Details Polyfluorinated epoxides and associated polymers and processes Polyfluorinated epoxides and associated polymers and processes

2001-10-03

2003-11-25

Dawson, Robert (Department: 1712)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S242000, C526S243000, C528S408000, C528S417000, C528S421000, C549S519000, C549S523000, C549S524000, C549S539000, C549S563000

Reexamination Certificate

active

06653419

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention is in the field of polyfluorinated epoxides and includes methods for producing these epoxides, certain chemical reactions these epoxides undergo, and monomers and polymers derived from these epoxides and/or their derivatives.
2. Description of Related Art
Various polyfluorinated epoxides are known. As an illustrative example, 1,1-bis(trifluoromethyl)ethylene oxide is known and can be produced by reaction of diazomethane and hexafluoroacetone: see Chang, I. S., Willis, C. J., Can. J. Chem. 1997, 55, 2465. While this production method can be done on a lab scale, it does involve use of hazardous diazomethane and is not capable of being scaled up for producing larger quantities. As a second illustrative example, the compound illustrated below is also known.
The production of this compound, again involving a hazardous reagent, has been reported via oxidation of the corresponding olefin with ozone. See JP Patent Publication 08333302 A2. Neither of the aforementioned production processes is attractive for commercial production for the reasons presented above.
The preparation of perfluorinated or perhalogenated epoxides using sodium hypochlorite or sodium hypobromide is known. See: Kolenko, I. P., Filaykova, T. I., Zapevalov, A. Yu., Lur'e, E. P. Izv. AN USSR. Ser. Khim. 1979, p. 2509; and Coe, P. L., Mott, A. W., Tatlow, J. C., J. Fluorine Chemistry, 1985, V30, p. 297.
There is a need for a safe and efficient production method for producing polyfluorinated epoxide compounds as well as safe efficient processes for converting them into useful polymeric products.
SUMMARY OF THE INVENTION
In one embodiment, the invention is a method for producing a fluorinated epoxide in high yield, said method comprising the step of reacting a fluorinated ethylenically unsaturated compound having the structure:
 (R
1
)(R
2
)C═C(R
3
)(R
4
)
with a metal hypohalite oxidizing agent in the presence of a phase transfer catalyst to produce the fluorinated epoxide having the structure:
wherein R
1
is selected from the group consisting of H and OR, where R is C
1
-C
10
alkyl; R
2
is selected from the group consisting of H and F; and R
3
and R
4
are selected from the group consisting of C
1
-C
10
perfluoroalkyl and C
1
-C
10
perfluroalkoxy.
In another embodiment, the invention is a method for producing a fluorinated epoxide in high yield, said method comprising the step of reacting a fluorinated ethylenically unsaturated compound having the structure:
(R
1
)(R
2
)C═C(R
3
)(R
4
)
with a metal hypohalite oxidizing agent in the presence of a phase transfer catalyst to produce the fluorinated epoxide having the structure:
wherein R
1
is selected from the group consisting of H and OR, where R is C
1
-C
10
alkyl; R
2
is selected from the group consisting of H, F, C
1
-C
10
perfluoroalkyl, and X-substituted C
1
-C
10
alkyl, wherein X is F, Cl, Br, I, OH, or OR; R
3
and R
4
are each independently selected from the group consisting of C
1
-C
10
perfluoroalkyl.
In another embodiment, the invention is a method for producing a fluorinated epoxide in high yield, said method comprising the step of reacting a fluorinated ethylenically unsaturated compound having the structure:
(R
1
)(R
2
)C═C(R
3
)(R
4
)
with a metal hypohalite oxidizing agent in the presence of a phase transfer catalyst to produce the fluorinated epoxide having the structure:
wherein R
1
is selected from the group consisting of H and OR, where R is C
1
-C
10
alkyl; R
2
is selected from the group consisting of H, F, C
1
-C
10
perfluoroalkyl, and X-substituted C
1
-C
10
alkyl, wherein X is F, Cl, Br, I, OH, or OR; R
3
and R
4
are each independently selected from the group consisting of C
1
-C
10
perfluoroalkyl, C(R
f
)(R
f
′)OH where R
f
and R
f
′ are C
1
-C
10
perfluoroalkyl groups, C
1
-C
10
perfluoroalkoxy, C
1
-C
10
carboalkoxy, and hydroxy-substituted C
3
-C
10
carboalkoxymethyl-substituted C
1
-C
4
perfluoroalkyl.
In another embodiment, the invention is a fluorine-containing polymer comprising a repeat unit derived from at least one ethylenically unsaturated compound containing a fluoroalcohol functional group having the structure:
—XCH
2
C(R
f
)(R
f
′)OH
wherein R
f
and R
f
′ are the same or different fluoroalkyl groups of from 1 to about 10 carbon atoms or taken together are (CF
2
)
n
wherein n is 2 to 10; and X is selected from the group consisting of sulfur, oxygen, nitrogen, phosphorous and any other element selected from Group Va and Group VIa.
In yet another embodiment, the invention is a perfluorinated epoxide having the structure:
where R
f
and R
f
′ are are the same or different perfluoroalkyl groups of from 1 to about 10 carbon atoms or taken together are (CF
2
)
n
wherein n is 2 to 10; and Y is selected from the group consisting of sulfur and oxygen.
In still another embodiment, the invention is a method for incorporating a fluoroalcohol functional group having the structure:
—XCH
2
C(R
f
)(R
f
′)OH
into a polymer as a pendant group, wherein R
f
and R
f
′ are the same or different fluoroalkyl groups of from 1 to about 10 carbon atoms or taken together are (CF
2
)
n
wherein n is 2 to 10; and X is selected from the group consisting of sulfur, oxygen, nitrogen, phosphorous and any other element selected from Group Va and Group VIa;
said method comprising the steps of:
a. reacting an epoxide having the structure:
with an ethylenically unsaturated compound containing substituent X to produce an ethylenically unsaturated comonomer comprised of the structure:
—XCH
2
C(R
f
)(R
f
′)OH;
and
b. polymerizing a reaction mixture comprised of the ethylenically unsaturated comonomer to produce the polymer.
In still another embodiment, the invention is a compound of structure
R
a
XCH
2
C(R
f
)(R
f
′)OH
where R
a
is an ethylenically unsaturated alkyl group of from 2 to 20 carbon atoms, optionally substituted by one or more ether oxygens and R
f
and R
f
′ are the same or different perfluoroalkyl groups of from 1 to about 10 carbon atoms or taken together are (CF
2
)
n
wherein n is 2 to 10, and X is selected from the group consisting of sulfur, oxygen, nitrogen, phosphorous and any other element selected from Group Va and Group VIa.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)
In one embodiment, the invention is a method for producing a fluorinated epoxide comprising the step of reacting a fluorinated ethylenically unsaturated compound (structure given supra) with a metal hypohalite oxidizing agent in the presence of a phase transfer catalyst to produce the fluorinated epoxide (structure also given supra).
A suitable oxidizing agent is a metal hypohalite. Exemplary metal hypohalites include, but are not limited to, various metal hypochlorites or metal hypobromites, including lithium, sodium, potassium, and calcium hypochlorites or hypobromites. Preferred oxidizing agents are sodium, calcium, or potassium hypochlorite and sodium or potassium hypobromite.
Examples of suitable phase-transfer catalysts include, but are not limited to, tetraethylammonium chloride, tetraethylammonium bromide, tetramethylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydroxide, trimethylbenzylammonium chloride, trimethylbenzylammonium bromide, methyltricaprylyl halide, methyltricaprylyl hydroxide, and trimethylbenzylammonium hydroxide. Preferred are methyltricaprylyl halide or hydroxide.
In another embodiment, the invention is a method for producing a polyfluorinated polyether comprising the step of reacting a fluorinated epoxide having the structure given supra with a basic compound in solvent or neat to produce the polyfluorinated polyether as given supra. Suitable bases for use in this reaction include, but are not limited to, trialkylamines of formula R
1
R
2
R
3
N, where R
1
-R
3
are independently C
1
-C
6
alkyl; pyridine, sodium or potassium alkoxides (e.g., methoxide, ethoxide, t-butoxide), and sodium or potassium hydroxide.
Th

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