Organic compounds -- part of the class 532-570 series – Organic compounds – Nitrogen attached directly or indirectly to the purine ring...
Reexamination Certificate
1992-12-08
2001-03-13
Raymond, Richard L. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Nitrogen attached directly or indirectly to the purine ring...
C560S150000, C562S106000, C562S556000
Reexamination Certificate
active
06201122
ABSTRACT:
This invention relates to fluoroaliphatic radical-containing sulfonamido compounds, a process for their preparation, and methods for using them as surfactants.
Certain fluoroaliphatic radical-containing compounds, or fluorochemicals, are useful as surfactants for a variety of demanding industrial applications. Their unique combination of properties are due mainly to the properties of the fluoroaliphatic radical: low surface energy, high chemical stability, and oleophobic-hydrophobic character. Because of these properties, fluorochemical surfactants are often useful in applications where conventional hydrocarbon surfactants, that is, relatively fluorine-free surfactants, do not perform adequately. For example, compared with hydrocarbon surfactants, fluorochemical surfactants (1) give much lower surface tension in aqueous systems, (2) are effective at much lower concentration, (3) show better stability in hostile environments (e.g., strong acids or bases, reducing or oxidizing media), and (4) exhibit surface activity in organic solvents systems, e.g., as a leveling agent in organic coatings. See, for example, “Organofluorine Compounds and their Industrial Applications”, R. E. Banks, editor, pages 218-226, Ellis Horwood, Ltd., (1979).
Many fluorochemicals useful as surfactants are described in patents. U.S. Pat. No. 3,536,749 (Groves) describes the preparation of certain adducts from the reaction of certain fluorocarbon amides with an ester of acrylic acid or methacrylic acid. Adducts of the formula R
f
SO
2
N(R)CH
2
CH(R′)CO
2
R″ are disclosed where R
f
is a perfluoroalkyl group containing from 3 to 18 carbon atoms, R′ is hydrogen or methyl, and R″ is an alkyl group containing up to 18 carbon atoms. Specific adducts prepared include C
8
F
17
SO
2
N(C
2
H
5
)CH
2
CH
2
CO
2
C
2
H
5
and C
5
F
11
CONHCH
2
CH
2
CO
2
C
2
H
5
.
U.S. Pat. No. 4,014,926 (Dear et al.) discloses certain compounds said to be useful as surfactants and as leveling agents in floor polish formulations. The invention is directed to fluorinated alkylamido sulfonic acids and salts of the formula [R
f
—R
6
—SCH
2
C(R
1
)HC(O)NH—C(R
2
)(R
3
)—C(R
4
)(R
5
)—SO
3
]
n
M, where R
f
is straight or branched chain perfluoroalkyl of 1 to 18 carbon atoms or perfluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbon atoms, R
1
is hydrogen or lower alkyl and each of R
2
, R
4
and R
5
is individually hydrogen or a hydrocarbon radical, and R
6
is alkylene, alkylenethioalkylene, alkyleneoxyalkylene or alkyleneiminoalkylene with a secondary or tertiary nitrogen atom, R
3
is hydrogen, alkyl, aryl or pyridyl, M is hydrogen, a monovalent alkali metal, an alkaline earth metal, an organic base or ammonium, and n is an integer corresponding to the valency of M. A specific example is C
6
F
13
CH
2
CH
2
SCH
2
CH
2
C(O)NHC(CH
3
)
2
CH
2
SO
3
K.
U.S. Pat. No. 4,069,244 (Mueller) discloses certain fluorinated compounds, said to be useful as surfactants, of the formula R
f
—R
1
—S—(CH
2
)
y
—CH(—COOH)—CH
2
—CO—XQ, where R
f
is a perfluoroalkyl group, R
1
is a branched or straight chain alkylene, alkylenethioalkylene, alkyleneoxyalkylene or alkyleneiminoalkylene group, X is oxygen or —NR, Q is an organic group containing at least one amino group and y is zero or 1. An example of a compound which was prepared is C
8
F
17
CH
2
CH
2
SCH(COO
−
)—CH
2
CONH(CH
2
)
3
N
+
H(CH
3
)
2
.
U.S. Pat. No. 4,102,916 (Falk) discloses certain compounds, said to be useful as surfactants, having the formula R
f
R
1
SCH
2
CH(R
2
)CONN(R
3
)(R
4
)(R
5
) wherein R
f
is a perfluoroalkyl, R
1
is alkylene, oxy or thioalkylene, or alkyleneiminoalkylene; R
2
is hydrogen or alkyl; R
3
and R
4
are alkyl or together with nitrogen form a heterocyclic ring and R
5
is alkyl which may contain hydroxyl or carboxyl groups or an anionic function such as sulfonate, sulfate or carboxylate. A specific compound of the invention has the formula C
6
F
13
CH
2
CH
2
SCH
2
CH(CH
3
)CONN(CH
3
)
2
CH
2
CH(OH)CH
3
.
U.S. Pat. No. 2,759,019 (Brown, et al.) discloses certain perfluoroalkane-sulfonamidopolymethylenedialkylamine compounds and their corresponding quaternary ammonium derivatives. Such derivatives include C
8
F
17
SO
2
NHC
2
H
4
N
+
(C
2
H
5
)
2
(CH
3
) CH
3
SO
4
−
.
U.S. Pat. No. 2,809,990 (Brown) discloses certain fluorocarbon acids and derivatives. In particular, Brown discloses certain perfluoroalkane sulfonamido alkylenemonocarboxylic acids. Certain methods for making these compounds and their derivative are also disclosed. Such compounds include C
8
F
17
SO
2
NHCH
2
CH
2
CO
2
H.
Briefly, in one aspect, this invention provides novel fluoroaliphatic radical-containing sulfonamido compounds each of which comprises a fluoroaliphatic radical-containing sulfonamido group and an ethylenecarbonyl group whose beta ethylene carbon atom is bonded to a sulfur or nitrogen atom bonded to a linking group that is bonded to the nitrogen atom of said sulfonamido group. The carbonyl carbon atom of said ethylenecarbonyl group is bonded to an anionic hydrophilic polar group, comprising at least one atom selected from the group consisting of carbon, sulfur, oxygen, and nitrogen atoms. As used herein, “anionic” means those groups or compounds which can form anions when in aqueous mixtures. The compounds of this invention are useful as anionic surfactants.
Representative fluoroaliphatic radical-containing compounds useful in this invention include:
C
6
F
13
SO
2
NHCH
2
CH
2
NHCH
2
CH
2
CO
2
Na,
C
8
F
17
SO
2
NHC
2
H
4
NHC
2
H
4
CONHC(CH
3
)
2
CH
2
SO
3
K
This invention also provides methods for the preparation of fluoroaliphatic radical-containing sulfonamido compounds by a Michael addition reaction.
And, this invention also provides methods for using the fluoroaliphatic radical-containing sulfonamido compounds of this invention as anionic surfactants in improving or imparting properties to solutions and substrates such as wetting, penetration, spreading, leveling, foam stabilization, flow properties, emulsification, and dispersability.
A class of the fluoroaliphatic radical-containing sulfonamido compounds of this invention can be represented by Formula I,
R
f
SO
2
N(R)WACH(R′)CH(R″)C(O)Y I
where R
f
is a fluoroaliphatic radical; A is S or NR′″; W is a linking group and is alkylene, siloxylene, silylene, arylene, or combinations thereof; R, R′, R″, and R′″ are hydrogen, lower alkyl with, for example, 1 to 6 carbon atoms, aryl such as phenyl, or combinations thereof such as alkaryl, and can be functional groups, e.g., —CH
2
CH
2
OH or —CH
2
CO
2
NH
4
; Y is an anionic hydrophilic polar group which comprises at least one carbon, sulfur, oxygen, or nitrogen atom. In Formula I, A can be a secondary or tertiary, but not a quaternary, nitrogen atom. And, R and R′″, together with the nitrogen atoms to which they are bonded and W, can form a ring, e.g. a substituted piperazine ring.
The fluoroaliphatic radical, R
f
, is a stable, inert, preferably saturated, non-polar, monovalent aliphatic radical. It can be straight chain, branched chain, cyclic, or combinations thereof. It can contain catenary hetero-atoms, bonded only to carbon atoms, such as oxygen, divalent or hexavalent sulfur, or nitrogen. It is preferably a fully-fluorinated radical, but hydrogen or chlorine atoms can be present as substituents if not more than one atom of either is present for every two carbon atoms. The fluoroaliphatic radical has at least 3 carbon atoms, preferably 3 to 20 carbon atoms and most preferably about 4 to about 10 carbon atoms, and preferably contains about 40% to about 78% fluorine by weight, more preferably about 50% to about 78% fluorine by weight. The terminal portion of the fluoroaliphatic radical is a perfluorinated moiety which will preferably contain at least 7 fluorine atoms, e.g., CF
3
CF
2
CF
2
—, (CF
3
)
2
CF—, F
5
SCF
2
—, or the like. The preferred fluoroaliphatic group is fully or substantially fluorinated and is preferably a perfluorinated aliphatic rad
3M Innovative Properties Company
Jordan Robert H.
Raymond Richard L.
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