Organic compounds -- part of the class 532-570 series – Organic compounds – Halogen containing
Reexamination Certificate
2002-11-12
2004-03-23
Nazario-Gonzalez, Porfirio (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Halogen containing
C570S124000, C570S134000, C570S135000
Reexamination Certificate
active
06710214
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a highly branched perfluoroolefin, a production method of the highly branched perfluoroolefin comprising reacting a hexafluoropropene trimer with a trialkylperfluoroalkylsilane, a super-stable perfluoroalkyl radical and a method for producing a super-stable perfluoroalkyl radical by fluorinating the highly branched perfluoroolefin.
PRIOR ART
As a super-stable perfluoroalkyl radical which is highly stable, Japanese Kokoku Publication Hei-1-29175, for example, discloses perfluoro(2,4-dimethyl-3-isopropyll-3-pentyl) and the like.
In this gazette, it is described that perfluoro(2,4-dimethyl-3-isopropyl-3-pentyl) generates a free trifluoromethyl radical by, for example, heating, and this free trifluoromethyl radical can be employed, for example, as a polymerization catalyst.
A super-stable perfluoroalkyl radical is known to be obtained, for example, by fluorinating a corresponding perfluoroolefin. In this case, the perfluoroolefin acts as a precursor for the super-stable perfluoroalkyl radical.
As a method for synthesizing a perfluoroolefin, a method for oligomerizing a hexafluoropropene using an amine-based catalyst is known.
As this oligomerization method, for example, the method for producing a mixture of three kinds of hexafluoropropene trimers in the presence of tris[2(2H-hexafluoropropoxy)ethyl]amine and 1,4-diazabicyclo[2.2.2]octane using dimethyl sulfoxide as a solvent is reported (T. Martini and S. P. v. Halasz, Tetrahedron Lett., 2129-2132 (1974)).
As three kinds of hexafluoropropene trimers, there may be mentioned perfluoro(3-ethyl-2,4-dimethyl-2-pentene), perfluoro(4-methyl-3-isopropyl-2-pentene) and perfluoro(2,4-dimethyl-3-heptene).
Among those listed above, perfluoro(4-methyl-3-isopropyl-2-pentene) was reported, when being fluorinated directly, to give perfluoro(2,4-dimethyl-3-ethyl-3-pentyl) (hereinafter referred to as “super-stable perfluoroalkyl radical (dR)”) which is a super-stable perfluoroalkyl radical at a yield of about 90% by weight (K. V. Scherer, T. Ono, K. Yamanouchi, R. Fernandez, P. Henderson, J. Am. Chem. Soc., 107, 718-719 (1985), U.S. Pat. No. 4,626,608).
Perfluoro(2,4-dimethyl-3-ethyl-3-pentyl) is known to be obtained also by fluorinating perfluoro(3-ethyl-2,4-dimethyl-2-pentene) directly.
It is known that perfluoro(2,4-dimethyl-3-ethyl-3-pentyl) and perfluoro(4-methyl-3-isopropyl-2-pentene) are heated and reacted together to give perfluoro(2,4-dimethyl-3-isopropyl-3-pentyl). In this reaction, perfluoro(2,4-dimethyl-3-ethyl-3-pentyl) is considered to act as a trifluoromethylating reagent.
However, perfluoro(2,4-dimethyl-3-isopropyl-3-pentyl) is obtained only in a trace amount by the synthesis method employing perfluoro(2,4-dimethyl-3-ethyl-3-pentyl), therefore this synthesis method is not practical. No other methods for synthesizing perfluoro(2,4-dimethyl-3-isopropyl-3-pentyl) has hitherto been known.
For synthesizing perfluoro(2,4-dimethyl-3-isopropyl-3-pentyl) at a high yield, it is considered to be desirable to use a precursor perfluoro(2,4-dimethyl-3-isopropyl-2-pentene).
Nevertheless, such a highly branched and sterically complicated perfluoroolefin is regarded to be very difficult to be synthesized, and no methods for synthesizing the same has hitherto been known. The synthesis should be conducted conveniently in a high yield for an industrial application.
Highly branched perfluoroolefins having many branched chains are considered to generate radicals as a result of fluorination, and the resultant radicals are very stable due to the steric hindrance, and thus are expected to be utilized as polymerization catalysts similar to perfluoro(2,4-dimethyl-3-isopropyl-3-pentyl).
SUMMARY OF THE INVENTION
In view of the above-mentioned state of the art, it is an objective of the present invention to provide a method for producing a highly branched perfluoroolefin conveniently in a high yield, a novel highly branched perfluoroolefin, a method for producing a super-stable perfluoroalkyl radical and a novel super-stable perfluoroalkyl radical.
The present invention is a highly branched perfluoroolefin represented by the following general formula (1):
[(CF
3
)
2
CF][(CF
3
)
2
CY]C═C(CF
3
)Z (1)
in the formula, Y and Z are the same or different and each represents F or Rf, Rf represents a straight or branched perfluoroalkyl group having 1 to 16 carbon atoms, provided that Y and Z are not simultaneously F.
The present invention is a production method of a perfluoroolefin for producing the above highly branched perfluoroolefin which comprises reacting a hexafluoropropene trimer with a trialkylperfluoroalkylsilane represented by the following general formula (2):
in the formula, Rf represents a straight or branched perfluoroalkyl group having 1 to 16 carbon atoms, R
1
, R
2
and R
3
are the same or different and each represents an alkyl group having 1 to 3 carbon atoms, in an aprotic polar solvent using a fluoride ion as a catalyst.
The present invention is a production method of a super-stable perfluoroalkyl radical which comprises producing a super-stable perfluoroalkyl radical represented by the following general formula (1R):
[(CF
3
)
2
CF][(CF
3
)
2
CY]Ra—CF(CF
3
)Z (1R)
in the formula, Ra represents a carbon atom having one unpaired electron, Y and Z are the same or different and each represents F or Rf, and Rf represents a straight or branched perfluoroalkyl group having 1 to 16 carbon atoms, provided that Y and Z are not simultaneously F,
by fluorinating the above highly branched perfluoroolefin.
The present invention is a production method of a reduced-carbon super-stable perfluoroalkyl radical which comprises producing a super-stable perfluoroalkyl radical (AR) represented by the following general formula (3R):
[(CF
3
)
2
CF]
2
Ra—CF(CF
3
)Rf (3R)
in the formula, Ra represents a carbon atom having one unpaired electron and Rf represents a straight or branched perfluoroalkyl group having 1 to 16 carbon atoms, by fluorinating a highly branched perfluoroolefin (B) represented by the following general formula (4):
[(CF
3
)
2
CF][(CF
3
)
2
CRf]C═C(CF
3
)Rf (4)
in the formula, each Rf is the same or different from each other and is defined as described above.
The present invention is a super-stable perfluoroalkyl radical (BR) represented by the following general formula (4R):
[(CF
3
)
2
CF][(CF
3
)
2
CRf]Ra—CF(CF
3
)Rf (4R)
in the formula, Ra represents a carbon atom having one unpaired electron and each Rf is the same or different from each other and represents a straight or branched perfluoroalkyl group having 1 to 16 carbon atoms.
The present invention is a super-stable perfluoroalkyl radical (CR) represented by the following general formula (5R):
[(CF
3
)
2
CF][(CF3)
2
CRf]Ra—CF
2
(CF
3
) (5R)
in the formula, Ra represents a carbon atom having one unpaired electron and Rf represents a straight or branched perfluoroalkyl group having 1 to 16 carbon atoms.
DETAILED DISCLOSURE OF THE INVENTION
In the following, the present invention is described in detail.
The highly branched perfluoroolefin of the invention is represented by the above general formula (1).
Accordingly, the highly branched perfluoroolefin of the invention is a highly branched perfluoroolefin (A) represented by the following general formula (3):
[(CF
3
)
2
CF]
2
C═C(CF
3
)Rf (3)
in the formula, Rf represents a straight or branched perfluoroalkyl group having 1 to 16 carbon atoms, a highly branched perfluoroolefin (B) represented by the following general formula (4):
[(CF
3
)
2
CF][(CF
3
)
2
CRf]C═C(CF
3
)Rf (4)
in the formula, each Rf is the same to or different from each other and represents a straight or branched perfluoroalkyl group having 1 to 16 carbon atoms, or, a highly branched perfluoroolefin (C) represented by the following general formula (5):
[(CF
Nishida Masakazu
Okazaki Masaharu
Ono Taizo
Shimizu Tetsuo
Toriyama Kazumi
National Institute of Advanced Industrial Science and Technology
Nazario-Gonzalez Porfirio
Price Elvis O.
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