Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acids and salts thereof
Reexamination Certificate
2001-10-15
2003-02-04
Davis, Brian J. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acids and salts thereof
C564S138000, C564S142000, C564S152000, C564S153000, C008S194000, C008S128100, C008S115620, C427S430100
Reexamination Certificate
active
06515175
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to perfluoroalkyl-substituted mono-, di- and poly-amides derived from a perfluoroalkyl iodide, an unsaturated acid and a mono-, di-or polyamine. More particularly it relates to novel compounds which are the reaction products of a mono-, di- or polyamine of 60 to 2000 molecular weight with a perfluoroalkyl-substituted unsaturated acid or its corresponding lower alkyl ester and optionally a non-fluorinated amino-reactive compound such as an acid, ester, anhydride, epichlorohydrin, isocyanate or urea. These R
F
-amides are useful as internally or externally applied paper sizes to impart oil and grease resistance to paper, and as oil proofing coatings on textiles, wood, masonry and the like, or as high-performance surface active agents.
BACKGROUND OF THE INVENTION
The use of perfluoroalkyl-substituted polymers to impart oil and water repellency to a variety of substrates, textiles especially, has long been known. The vast majority of these polymers are perfluoroalkyl-substituted methacrylate copolymers. Several patents also describe R
F
-substituted polyurethanes, where R
F
stands for a perfluoroalkyl moiety. Polyamide-amino polymers derived from polyethyleneimine by reaction with esters of perfluoroalkyl-substituted carboxylic acids are described in U.S. Pat. Nos. 3,769,307 and 3,567,500. These polymers contain a mixture of R
F
-substituted amide and secondary amino groups. These polymers are used to impart oleophobicity yet hydrophlilicity to textile substrates. Di-R
F
amido monocarboxylic acids prepared from 1 equivalent of diethylenetriamine, 2 equivalents of an R
F
-acid and 1 equivalent of an anhydride are taught for use as textile finishes in U.S. Pat. No. 3,754,026. Similar R
F
-amide-substituted polyethyleneimines useful as chemically resistant surfactants are described in U.S. Pat. No. 3,271,430. They are obtained by reaction of a perfluorinated alkanoic acid with a large excess of ethyleneimine. Reaction products of R
F
-substituted acids with polymers bearing pendent primary amino groups attached to a carbon-carbon backbone by a linking group are claimed in U.S. Pat. No. 4,606,973 as low surface energy coatings on flat substrates.
U.S. Pat. No. 5,643,864 describes the synthesis of anionic surfactants by reaction of, for example, triethylenetetramine with first, two equivalents of a long-chain carboxylic acid, and secondly with chloroacetic acid. R
F
-substituted acids are claimed as reactants but not described.
U.S. Pat. No. 5,750,043 and U.S. patent application Ser. No. 09/234,251 now U.S. Pat. No. 6,156,222 describe water-soluble R
F
-substituted carboxylic acids that are amides of polyamines of 100 to 100,000 molecular weight which are used as foam stabilizers for aqueous fire fighting foams
It has now been discovered that unsaturated alkenoic acids, preferably &ohgr;perfluoroalkyl substituted 10-undecenoic acid and tetrahydrophthalic acid, can be converted by reaction with a large variety of amines into mono-, di- and polyamides, which can be further reacted with non-fluorinated amino-reactive compounds such as acids, acid chlorides, esters, anhydrides, epichlorohydrin, isocyanates or urea to form monomeric and polymeric amides, amino-ethers, and ureas which are uniquely suitable—depending on their specific structure—as specialty surfactants or as oil and water repellents when applied to paper, textiles, wood, glass or masonry.
Perfluoroalkyl substituents which are attached to a long-chain hydrocarbon moiety, such as an undecenoic group, exhibit improved surface activity and improved effectiveness as oil repellents, possibly because such long-chain hydrocarbyl groups, by their inter-chain interactions, aid in the orientation of the very poorly interacting R
F
-groups.
&ohgr;-Perfluoroalkyl-substituted 10-undecenoic acid and its use as an oil repellent paper size is disclosed in U.S. Pat. No. 5,491,261. Due to its relatively low molecular weight, this compound however shows substantial weight loss at the temperatures required for many paper product applications. This shortcoming has been overcome with the amide compounds of the present invention, which incorporate hydrogen-bonding amide groups and preferably contain more than one perfluoroalkyl-substituted undecenoic group.
DETAILED DISCLOSURE
The compounds of the present invention are mono-, di- or polyamides of the formulae
(Q)
z
—A—NHC(═O)—(W—R
F
)
x
(I) or
A—(Q
1
—A—NHC(═O)—(W—R
F
)
x
)
y
—NHC(═O)—(W—R
F
)
x
(II),
wherein
A is the hydrocarbon residue of an aliphatic, cycloaliphatic or aromatic mono-, di- or polyamine of 60 to 2000 molecular weight, which is optionally substituted by hydroxy- and/or carboxyl groups and whose carbon chain is optionally interrupted by one or more ether, amide or amino groups, which amino groups are optionally substituted by substituents of the formula —Q— or —Q
1
—, in which
Q is a monovalent radical connected to a nitrogen atom of (A) and is derived from an acid, acid chloride or lower alkyl ester, an anhydride, a halogenated carboxylic acids an alkyl or alkenyl halide, an oxirane compound or chloroacetamide, and which is optionally substituted by one or more hydroxy-, tert. amino or carboxyl groups, or is optionally interrupted by one or more ether or thioether linkages, and optionally contains one or more unsaturated groups and can be substituted by an R
F
group, or is —P(═O)(OH)
2
; —SO
3
H; or —C(═O)—NH
2
;
Q
1
is a difunctional linking group attached to the nitrogen atoms of two A groups and is derived from a diacid, diacid chloride or -lower alkyl ester, a dianhydride, a diisocyanate, epichlorohydrin, or is —C(═O)—, or is a trifunctional group derived from cyanuric acid,
each R
F
is independently a monovalent perfluorinated alkyl or alkenyl, linear or branched organic radical having four to twenty fully fluorinated carbon atoms,
W is —(CH
2
)
p
CH═CH— in which p is 1 to 20, or is a C
6
-C
10
cycloaliphatic hydrocarbyl group connecting an R
F
group to an amide carbonyl,
z is zero to 50,
y is zero to 50 and
x is 1 to 10.
The compounds of the present invention preferably have a number average molecular weight of 1,000 to 10,000.
Preferably W is of the formula —(CH
2
)
p
CH═CH— in which p is 5 to 12 and is derived from a terminally unsaturated alkenoic acid, or is derived from tetrahydrophthalic anhydride or (methyl)-norbornene anhydride; R
F
is saturated and contains 4-14 carbon atoms, is fully fluorinated and contains at least one terminal perfluoromethyl group.
Most preferably W is of the formula —(CH
2
)
p
CH═CH— in which p is 8, and R
F
is saturated and contains 6-12 fully fluorinated carbon atoms.
When A is the hydrocarbon residue of an optionally substituted and/or interrupted monoamine, the amine is preferably an amino acid such as glycine, p-aminosulfonic acid or taurine, or an amino alcohol such as 2-hydroxyethanolamine or is a tert. amino-substituted amine residue of the formula —(CH
2
)
j
—N—(R
1
)
2
wherein j is 2 to 6 and each R
1
is independently C
1
-C
4
alkyl, such as N,N-dimethylpropane-1,3-diamine. Especially preferred is a compound of the formula (II) wherein A is a tert. amino-substituted amine residue of the formula —(CH
2
)
j
—N—(R
1
)
2
wherein j is 2 to 6 and each R
1
is independently C
1
-C
4
alkyl, W is of the formula —(CH
2
)
p
CH═CH— in which p is 8, and R
F
is saturated and contains 6-12 fully fluorinated carbon atoms.
When A is the hydrocarbon residue of an optionally substituted and/or interrupted diamine, the diamine is preferably of the formula H
2
N—(CH
2
)
n
—NH
2
wherein n is 2-6, or is p-phenylenediamine, lysine, or a diamine of the formula
H
2
N—(CH
2
)
3
—O—(CH
2
—CH
2
—O)
m
—(CH
2
—CHCH
3
—O)
l
—(CH
2
)
3
—NH
2
, wherein m and l are independently 0 to 50 and m plus l is ≧1.
When A is the hydrocarbon residue of an optionally substituted and/or interrupted polyamine, the amine is preferably a polyalkyleneamine of the formula
H
2
N—(CH
2
CHR—NH)
n
—CH
2
CHR—NH
2
, wherein n is 1 to 5 and R is hydrogen or
Bochnik Michael
Haniff Marlon
Jennings John
Kantamneni Shobha
Mueller Karl F.
Ciba Specialty Chemicals Corporation
Davis Brian J.
Mansfield Kevin T.
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