Perfluoropolyether primary bromides and iodides

Details Perfluoropolyether primary bromides and iodides Perfluoropolyether primary bromides and iodides

2002-09-09

2003-11-25

Richter, Johann (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

C568S591000, C568S614000, C568S604000, C568S685000, C424S078370, C424S078080

Reexamination Certificate

active

06653511

ABSTRACT:

FIELD OF THE INVENTION
The invention replaces to a perfluoropolyether primary bromide or iodide and to a process therefor.
BACKGROUND OF THE INVENTION
The trademarks and trade names used herein are shown in upper cases.
Perfluoropolyether primary bromides and iodides are a family of highly useful and reactive chemicals that can be used, for example, as lubricants, surfactants, and additives for lubricants and surfactants. See, e.g.,
Journal of Fluorine Chemistry
1999, 93, 1 and 2001, 108, 147 (hereinafter “Brace”). Brace discloses addition of iodides to alkenes, alkynes, allyls, etc to produce secondary iodides that have limited uses. Brace does not disclose the synthesis of valuable primary perfluoropolyether iodides.
The Hundsdiecker reaction (
Journal of Organic Chemistry
1967, 32, 833) deals with reacting silver salts of the perfluoroalkyl carboxylic acid with free iodine. Such a reaction involves expensive reagents and is of limited commercial utility.
Journal of Fluorine Chemistry
1993, 65, 59 (hereinafter “Eapen”) discloses converting a hexafluoropropylene oxide (HFPO) tetramer acid fluoride to a secondary iodide. See also, U.S. Pat. Nos. 5,278,340 and 5,288,376 (halogen exchange of the fluorine in the acid fluoride with iodine using metal iodides and aprotic/polar solvent and exposing the acid iodide to ultraviolet irradiation, forming only the secondary iodide).
Journal of Fluorine Chemistry
1997, 83, 117 discloses exposing a molar excess of lithium iodide to low molecular weight perfluoroether acid fluorides at 180° C. for at least 6.5 hours to produce two low molecular weight perfluoropolyether iodides, one primary and one secondary.
U.S. Pat. No. 5,453,549 discloses a low molecular weight ethylene derivative of a primary iodide. It does not disclose the value of higher molecular weight products. Nor does it disclose the method of synthesis of the starting materials.
Journal of Fluorine Chemistry,
1990, 47, 163 discloses the feasibility of the formation of a primary iodide, in the gas phase, from dimer and trimer of hexafluoropropylene oxide.
While a polyfluorocarbon acid halide can likewise be converted to an iodide in a perhalogened solvent using iodine and a metal carbonate, U.S. Pat. No. 4,973,762, subsequent removal of the solvent can be expensive and undesired traces can be left behind.
Mono-functional ((&PHgr;-CF(CF
3
)CF
2
OCF(CF
3
)C(O)—F; Formula I) and di-functional (FC(O)CF(CF
3
)OCF
2
CF(CF
3
)-&PHgr;′-CF(CF
3
)CF
2
OCF(CF
3
)C(O)F; Formula II) acid fluorides, which can be used in the present invention can be prepared according to Moore, U.S. Pat. No. 3,332,826 and Koike et al., U.S. Pat. No. 5,278,340 where &PHgr; and &PHgr;′ are respectively monovalent and divalent perfluoropolyether moieties. Additionally, other acid fluorides of Formulae I and II are the reaction products formed from the polymerization of hexafluoropropylene oxide alone or with suitable starting materials, 2,2,3,3-tetrafluorooxetane, or the photooxidation of hexafluoropropylene or tetrafluoroethylene.
Secondary iodides from said acid fluorides can be prepared, for example at 0-60° C. using radiation from a photochemical lamp (for instance a lamp with an ultra-violet light output in the wavelength range of 220-280 nm (U.S. Pat. No. 5,288,376)).
The usefulness of this invention is demonstrated, for example, by the reactions of primary perfluoropolyether iodides with bromobenzene which could lead directly to perfluoropolyether substituted bromobenzene without the use of toxic or pyrophoric chemicals such as sulfur tetrafluoride or butyl lithium. These functionalized perfluoropolyether (PFPE) intermediates are used to form readily soluble, high temperature additives for fluorinated oils in boundary lubrication, as disclosed in, Eapen and U.S. Pat. No. 5,550,277. These primary bromides or iodides described herein can also be used as intermediates in the production of fluorous phase media for applications such as catalysis (Horváth, I., Acc. Chem. Res. 1998, 31, 641) or separations (Curran, D. P. Angew. Chem., Int. Ed. Engl. 1998, 37, 1174), fluorosurfactants, and mold release agents.
Because there are few useful perfluoropolyether primary bromides or iodides and processes for producing them are not readily available to one skilled in the art, there is an ever increasing need to develop such products and processes.
SUMMARY OF THE INVENTION
A perfluoropolyether and a composition comprising the perfluoropolyether are provided in which the perfluoropolyether comprises at least one halogen atom at the primary position of one or more end groups of the perfluoropolyether and the halogen atom is bromine or iodine.
Also provided is a process for producing the composition in which the process comprises contacting either (1) a perfluoropolyether acid fluoride with a metal bromide or metal iodide or (2) heating a perfluoropolyether secondary halide under a condition sufficient to effect the production of a perfluoropolyether comprising at least one bromine or iodine at the primary position of one or more end groups of the perfluoropolyether.
DETAILED DESCRIPTION OF THE INVENTION
A common characteristic of perfluoropolyethers is the presence of perfluoroalkyl ether moieties. Perfluoropolyether is synonymous to perfluoropolyalkylether. Other synonymous terms frequently used include “PFPE”, “PFPE oil”, “PFPE fluid”, and “PFPAE”.
Examples of the inventive perfluoropolyether primary bromide or iodide include, but are not limited to, those having the formulae of F(C
3
F
6
O)
z
CF(CF
3
)CF
2
X, X(CF
2
)
a
(CF
2
O)
m
(CF
2
CF
2
O)
n
(CF
2
)
a
X, F(C
3
F
6
O)
x
(CF
2
O)
m
CF
2
X, F(C
3
F
6
O)
x
(C
2
F
4
O)
n
(CF
2
O)
m
CF
2
X, XCF
2
CF(CF
3
)O(C
3
F
6
O)
p
R
f
2
O(C
3
F
6
O)
n
CF(CF
3
)CF
2
X, XCF
2
CF
2
O(C
3
F
6
O)
x
CF(CF
3
)CF
2
X, (R
f
1
)(R
f
1
)CFO(C
3
F
6
O)
x
CF(CF
3
)CF
2
X, and combinations of two or more thereof where X is I or Br; x is a number from 2 to about 100; z is a number of about 5 to about 100, preferably 5 to about 100, more preferably at least about 6, and even more preferably 6 to 90, or 8 to 90 such as, for example, about 6, about 7, about 8, or about 52; p is a number from 2 to about 50, n is a number from 2 to about 50, m is a number from 2 to about 50, a is 1 or 2, each R
f
1
can be the same or different and is independently a monovalent C
1
to C
20
branched or linear fluoroalkanes, R
f
2
is a divalent C
1
to C
20
branched or linear fluoroalkanes, and C
3
F
6
O is linear or branched.
The composition of the invention can be produced by any means known to one skilled in the art. It is preferred that it be produced by the process disclosed herein.
According to the invention, a process for producing the composition disclosed above can comprise, consist essentially of, or consist of contacting either (1) a perfluoropolyether acid fluoride or diacid fluoride containing a COF moiety with a metal bromide or metal iodide or (2) heating a perfluoropolyether secondary halide under a condition sufficient to effect the production of a perfluoropolyether comprising at least one bromine or iodine at the primary position of one or more end groups of the perfluoropolyether. The process generally involves a &bgr;-scission reaction. The process is preferably carried out under a condition or in a medium that is substantially free of a solvent or iodine or both. The process can also be carried out substantially free of a metal salt that is not a metal halide.
The acid fluoride including monoacid fluoride and diacid fluoride of Formula I and II, respectively, can be contacted with a metal iodide such as lithium iodide, calcium iodide, or barium iodide to make either a secondary or primary perfluoropolyalkylether iodide with the evolution of carbon monoxide and formation of the metal fluoride according to Reaction 1 for the monofunctional acid fluoride and Reaction 2 for the difunctional acid fluoride. These reactions can be carried out at or above about 180° C., preferably at or above about 220° C.
&PHgr;-CF(CF
3
)CF
2
OCF(CF
3
)C(O)—F+M
(1/v)
I→&PHgr;-CF(CF
3
)CF
2

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