Perfluoroalkyl-substituted amines, acids, amino acids and...

Details Perfluoroalkyl-substituted amines, acids, amino acids and... Perfluoroalkyl-substituted amines, acids, amino acids and...

2002-07-24

2004-03-16

Davis, Brian (Department: 1621)

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

Organic compounds

Amino nitrogen containing

C564S298000, C564S485000, C564S506000, C562S107000, C562S556000, C562S567000, C562S574000, C252S003000, C252S183110

Reexamination Certificate

active

06706923

ABSTRACT:

This invention relates to perfluoroalkyl-substituted amines, acids, amino acids and thioether acids and their salts that are useful as surfactants in a wide variety of applications.
BACKGROUND OF THE INVENTION
Perfluoroalkyl (═R
F
) substituted water soluble compounds are used primarily as specialty surfactants which can lower the surface energy of aqueous media to well below 20 dynes/cm, as compared to 25 dynes/cm for silicone based surfactants and 30 dynes/cm for conventional hydrocarbon surfactants. They are therefore useful in applications where conventional hydrocarbon and silicone-based surfactants fail, such as in coating of low free-energy surfaces such as polyolefins and oil-contaminated surfaces. R
F
-surfactants also allow the formulation of aqueous fire-fighting systems that can be used against organic solvent fires, such as those involving burning gasoline or alcohols. Such surfactant formulations are described in U.S. Pat. Nos. 4,460,480 and 5,218,021.
While fluorosurfactants as a general rule contain only one R
F
group per molecule, compounds with 2 or more R
F
groups are useful for grease-proofing paper products used, for example in the fast food industry. Typical compounds are described in U.S. Pat. Nos. 4,419,298; 4,536,254; and 5,091,550. Typical di-R
F
-compounds derived from amino acids, allyl glycidyl ether (AGE) and perfiuoroalkyl iodides are described in U.S. Pat. No. 5,491,261.
Canadian Patent 983,929 describes mono R
F
-substituted cationic surfactants made by reaction of an R
F
-iodide with, first, allyl glycidyl ether (AGE), secondly, with amines and alkanolamines. No carboxylic acids or sulfonic acids are described therein.
U.S. Pat. No. 4,038,195 describes R
F
-surfactants useful for aqueous fire fighting foams that are derived from glycine and N-methylglycine (sarcosine) by reaction with an R
F
-oxirane prepared from allyl glycidyl ether and an R
F
-iodide and followed by dehydrohalogenation. In this patent it is taught that the ensuing double bond improves the linearity of the molecule and its performance.
It has now been discovered that a large variety of 3-perfluoroalkyl-(2,3-ene or 2-iodo) propyl-substituted amino acids as well as thioether acids and their salts, which can be made by reaction of amines or amino acids, or of thio acids with allyl glycidyl ether, followed by reaction with a perfluoroalkyl iodide and partial or complete dehydrohalogenation and, optionally, quaternization, are excellent surfactants. They can be prepared in high yields and are useful as aqueous surfactants in a variety of applications where low surface tensions are required, including coating formulations for glass, wood, metal, cement, paper and textile materials, as active ingredients in hard surface (glass, plastic, metal, stone, laminates, etc.) cleaning products, as well as additives to dye baths, liquid laundry detergents and cosmetic products for the hair and skin, as foam control agents in polyurethane foams and especially as components in aqueous fire-fighting formulations.
The presence of the more hydrophobic 3-perfluoroalkyl-2-iodopropyl intermediate resulting from partial dehydrohalogenation may actually benefit the overall surface tension. According to Jarvis (J. Phys. Chem. 64, 150 (1960), the solubility of a fluorochemical has a significant effect on surface activity. An increase in the organophobic part of the molecule decreases the surface tension while the solubility of the molecule also decreases. Eventually, inadequate solubility of the molecule limits the minimum surface tension that can be achieved.
BRIEF SUMMARY OF THE INVENTION
The present invention provides 3-perfluoroalkyl-(2,3-ene and/or 2-iodo) propyl-substituted amines, amino carboxylic and sulfonic acids, and thioether carboxylic, phosphoric, sulfonic and sulfuric acids, and salts and quaternized derivatives thereof, which are prepared from the corresponding amines, amino and thioether acids by reaction with allyl glycidyl ether and perfluoroalkyl iodides, followed by partial or complete dehydrohalogenation.
Another aspect of this invention relates to a substrate which contains, or has been treated with, 0.01 to 10% by weight of a fluorine-containing composition, at least part of said fluorine being provided by one of the compounds according to the present invention.
Another aspect of this invention relates to fluorine-containing aqueous fire-fighting compositions, at least part of said fluorine being provided by one of the compounds according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The novel perfluoroalkyl amines, amino acids and thioether acids of the present invention are of the formula:
Q
F
—NR
1
R
2
  (Ia),
Q
F
—N(→O)R
1
R
2
  (Ib),
Q
F
—N
+
R
1
R
2
R
3
A
−
  (Ic),
Q
F
—S—R
4
—COOM  (IIa),
Q
F
—S(O)
2
—R
4
—COOM  (IIb),
Q
F
—SO
3
M  (IIIa),
Q
F
—NR
1
—(PO
3
)
3
M  (IIIb)
or
Q
F
—NR
1
—SO
3
M  (IIIc),
in which
R
1
is an aliphatic, aromatic or cyclo-aliphatic hydrocarbon residue with one to 20 carbon atoms, optionally interrupted by one or more oxygens and/or substituted by hydroxy groups, or is R
2
;
R
2
is R
1
or an aliphatic, aromatic or cyclo-aliphatic hydrocarbon residue with 1 to 20 carbon atoms, substituted by one or two carboxy groups or a sulfate or a sulfonate group, and which is optionally further substituted by amino or hydroxy groups and/or interrupted by tertiary amino groups, sulfur or oxygen, with the proviso that when R
2
is R
1
, the compound is of structure (1b) or (1c), and when R
2
is —CH
2
—COOH, Q
F
is Q
F1
;
R
3
is C
1
-C
5
alkyl or benzyl, or is a C
1
-C
5
alkylene group which is substituted by a carboxy or sulfonate group;
R
4
is C
1
-C
5
alkylene or phenylene;
A
−
is an ionically or covalently bound anion;
M is hydrogen, an alkali metal cation, ammonium, or ammonium that is mono-, di-, tri- or tetra-substituted by C
1
-C
4
alkyl, C
1
-C
4
-hydroxyalkyl, or a mixture thereof; and
Q
F
is 0 to 50% by weight Q
F1
and 50 to 100% by weight Q
F2
, wherein
Q
F1
is R
F
CH
2
CHI—CH
2
—O—CH
2
CH(OH)CH
2
— and
Q
F2
is R
F
CH═CH—CH
2
—O—CH
2
CH(OH)CH
2
—,
in which
R
F
is a monovalent, perfluorinated, alkyl or alkenyl, linear, branched or cyclic organic radical having three to twenty fully fluorinated carbon atoms, which organic radical is optionally interrupted by divalent oxygen or sulfur atoms,
with the proviso that the compound of the formula
is excluded.
A
−
as an anion is for example an acetate, a halide such as a chloride, bromide or iodide, or is a covalently bound carboxyl or sulfonate group. A
−
is in particular a chloride or a covalently bound carboxyl group.
M as an alkali metal cation is, for example, a cation of sodium, lithium or potassium. M as an alkali metal cation is especially a cation of sodium.
When M is ammonium that is monosubstituted by C
1
-C
4
alkyl, it is, for example methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl- or tert.-butylammonium.
When M is ammonium that is disubstituted by C
1
-C
4
alkyl, it is, for example dimethyl-, diethyl-, di-n-propyl-, diisopropyl-, or di-n-butylammonium.
When M is ammonium that is trisubstituted by C
1
-C
4
alkyl, it is, for example trimethyl- or triethylammonium.
When M is ammonium that is tetrasubstituted by C
1
-C
4
alkyl, it is preferably tetramethyl-, tetraethyl-, methyltributyl- or tetrabutylammonium.
When M is ammonium that is mono-, di-, tri- or tetra-substituted by C
1
-C
4
hydroxyalkyl, it is, for example diethanol-, disopropanol- or triethanolammonium, with diethanol- or triethanolammonium being particularly preferred.
M as a mixture of C
1
-C
4
alkyl and C
1
-C
4
-hydroxyalkyl is, for example methylethanolammonium.
M is in particular an ammonium or sodium cation.
The perfluoroalkyl moiety R
F
may be a single perfluoroalkyl group, for example perfluorohexyl, or a mixture of such groups, for example a mixture of C
4
F
9
—, C
6
F
13
—, C
8
F
17
—, C
10
F
21
—, C
12
F
25
— and C
14
F
29
— groups.
Preferred compounds according to the p

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