NZ622972B2 - Fluorophosphate surfactants - Google Patents
Fluorophosphate surfactants Download PDFInfo
- Publication number
- NZ622972B2 NZ622972B2 NZ622972A NZ62297212A NZ622972B2 NZ 622972 B2 NZ622972 B2 NZ 622972B2 NZ 622972 A NZ622972 A NZ 622972A NZ 62297212 A NZ62297212 A NZ 62297212A NZ 622972 B2 NZ622972 B2 NZ 622972B2
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- New Zealand
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- 239000004094 surface-active agent Substances 0.000 title abstract description 25
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 title abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 90
- 238000000576 coating method Methods 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 26
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 18
- 239000011593 sulfur Chemical group 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 150000007942 carboxylates Chemical group 0.000 claims abstract description 13
- 125000000962 organic group Chemical group 0.000 claims abstract description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 37
- 230000000903 blocking effect Effects 0.000 claims description 30
- 239000008199 coating composition Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- 239000003921 oil Substances 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 229920000180 alkyd Polymers 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000004816 latex Substances 0.000 claims description 11
- 229920000126 latex Polymers 0.000 claims description 11
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 10
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 10
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 10
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
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- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 20
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- XAHQYEAIJGTPET-JEDNCBNOSA-N [(1s)-5-amino-1-carboxypentyl]azanium;dihydrogen phosphate Chemical class OP(O)([O-])=O.NCCCC[C@H]([NH3+])C(O)=O XAHQYEAIJGTPET-JEDNCBNOSA-N 0.000 description 9
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- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 6
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- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 4
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
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- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- OJTDGPLHRSZIAV-UHFFFAOYSA-N propane-1,2-diol Chemical compound CC(O)CO.CC(O)CO OJTDGPLHRSZIAV-UHFFFAOYSA-N 0.000 description 1
- KOPQZJAYZFAPBC-UHFFFAOYSA-N propanoyl propaneperoxoate Chemical compound CCC(=O)OOC(=O)CC KOPQZJAYZFAPBC-UHFFFAOYSA-N 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 description 1
- RBBWNXJFTBCLKT-UHFFFAOYSA-M sodium;ethanethioate Chemical compound [Na+].CC([S-])=O RBBWNXJFTBCLKT-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- WPLOVIFNBMNBPD-ATHMIXSHSA-N subtilin Chemical compound CC1SCC(NC2=O)C(=O)NC(CC(N)=O)C(=O)NC(C(=O)NC(CCCCN)C(=O)NC(C(C)CC)C(=O)NC(=C)C(=O)NC(CCCCN)C(O)=O)CSC(C)C2NC(=O)C(CC(C)C)NC(=O)C1NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C1NC(=O)C(=C/C)/NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)CNC(=O)C(NC(=O)C(NC(=O)C2NC(=O)CNC(=O)C3CCCN3C(=O)C(NC(=O)C3NC(=O)C(CC(C)C)NC(=O)C(=C)NC(=O)C(CCC(O)=O)NC(=O)C(NC(=O)C(CCCCN)NC(=O)C(N)CC=4C5=CC=CC=C5NC=4)CSC3)C(C)SC2)C(C)C)C(C)SC1)CC1=CC=CC=C1 WPLOVIFNBMNBPD-ATHMIXSHSA-N 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/004—Surface-active compounds containing F
- C11D1/006—Surface-active compounds containing fluorine and phosphorus
Abstract
This disclosure is directed to fluorophosphate compositions and their use as surfactants, additives for coatings or treating agent to impart water and oil repellency to substrates coated with such compositions. The fluorophosphate is a partially fluorinated phosphate with an ammonium cation (NH2R1R2)+ wherein R1 and R2 are independently linear or branched organic groups containing at least one carboxylate moiety and one amino moiety, and optionally be substituted, interrupted, or both with oxygen, sulfur, or nitrogen-containing moieties, or with cyclic alkyl or aryl moieties containing up to 10 carbon atoms. )+ wherein R1 and R2 are independently linear or branched organic groups containing at least one carboxylate moiety and one amino moiety, and optionally be substituted, interrupted, or both with oxygen, sulfur, or nitrogen-containing moieties, or with cyclic alkyl or aryl moieties containing up to 10 carbon atoms.
Description
TITLE
FLUOROPHOSPHATE SURFACTANTS
FIELD OF INVENTION
The field of invention is related to fluorophosphates and their use as
surfactants, additives for coatings or treating agents to impart water, oil,
and oil repellency to substrates coated with such compositions.
BACKGROUND OF INVENTION
Commonly fluoroalkyl phosphate surfactants and surface treatment
agents contain multiple fluorochemical chains, containing a higher
percentage of fluorine at a given concentration and are typically used
because they are thought to provide better performance. However, the
fluorinated starting materials are more expensive and in short supply.
Reduction of the amount of the fluorinated starting material in these
surfactants while maintaining the same or better performance is desirable.
Reducing the amount of the fluorinated starting component needed would
not only reduce the cost, but also shorten the cycle time as fewer steps
are needed in the production of the surfactants and less energy is
required. Reducing the fluorine content would reduce the cost, but it is
necessary to maintain product performance.
Brace and Mackenzie, in U.S. Patent 3,083,224, describe mixed
fluoroalkyl phosphates having the formula [C F C H O] PO( O M)
m 2m+1 n 2n y 3-
where m is 4 to 12, n is 1 to 16, and y is averaged to be 1.0 to 2.5.
Brace and Mackenze describe their use as an oil repellent, particularly
when y is 2.
Phosphate surfactants having ammonium as a counter ion can
potentially release ammonia into the environment. Alternate counter ions
need to be able to provide a stable surfactant, while also providing no
adverse effects to the surfactant performance.
It is desirable to improve surfactant performance, in particular
lowering of surface tension in coating compositions while using less
fluorinated starting materials and a counter ion other than simple
ammonium compounds. It is also desirable to impart improved surface
effects to coated surfaces. The present invention provides a method to
increase surfactant performance and to impart improved surface effects to
a coated surface while utilizing less fluorinated starting material.
SUMMARY OF THE INVENTION
The present invention comprises a composition comprising formula
I, formula II, or formula III
(R -A-Z)
(O M )
(Fo rmula I)
R -A-Z-CH
R -A-Z-CH M
(Fo rmula II)
R -A-Z
OROH
(Fo rmula III)
wherein
R is a C to C linear or branched perfluoroalkyl optionally
f 1 6
interrupted by one, two or three ether oxygen atoms;
x is 1 to 2;
A is (C H ) , (C H CF ) (C H ) , ( C H ) SO N(C H )( C H ) ,
2 k 2 2 m 2 n 2 o 2 3 2 p
O(C F ) ( C H ) , or OCHFCF OE;
2 2 2 r 2
Z is O or S;
m is 1 to 4;
k, n, o, p, and r are each independently 1 to 20;
E is a C to C linear or branched alkyl group optionally
2 20
interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a
C to C aryl group;
6 10
R is a C to C linear or branched alkyl group optionally
2 60
interrupted by hetero atoms selected from the group consisting of an
oxygen, sulfur, or nitrogen atom; a cyclic alkyl; or a C to C aryl;
6 10
provided that when R is greater than 8 carbons, the ratio of hetero atoms
to carbon atoms is at least 1:2; and
1 2 + 1 2
M is an ammonium cation (N H R R ) wherein R and R are
independently hydrogen, linear or branched organic groups containing at
least one carboxylate moiety and one amino moiety, and optionally be
substituted, interrupted, or both with oxygen, sulfur, or nitrogen-containing
moieties, or with cyclic alkyl or aryl moieties containing up to 10 carbon
atoms,
with the proviso that at least one of R and R is a linear or
branched organic groups containing at least one carboxylate moiety and
one amino moiety.
Another aspect of the invention is a method of providing lowering
surface tension, water repellency, oil repellency and stain resistance to a
substrate comprising contacting the substrate with a composition
comprising one or more compounds of formula ( I ), (I I) or (I II).
Another aspect of the invention is a method of providing resistance
to blocking, open time extension and oil repellency to a substrate having
deposited thereon a coating composition comprising adding to the coating
composition, prior to deposition on the substrate, a composition
comprising one or more compounds of formula (I ), (I I) or ( I II).
Another embodiment of the invention is a substrate to which has
been applied a composition of comprising one or more compounds of
formula (I ), (I I) or ( I II).
DETAILED DESCRIPTION OF INVENTION
Hereinafter trademarks are designated by upper case.
The present invention comprises a composition comprising formula
I, formula II, or formula III
(R -A-Z)
(O M )
(Fo rmula I)
R -A-Z-CH
R -A-Z-CH M
(Fo rmula II)
R -A-Z
OROH
(Fo rmula III)
wherein
R is a C to C linear or branched perfluoroalkyl optionally
f 1 6
interrupted by one, two or three ether oxygen atoms;
x is 1 to 2;
A is (C H ) , (C H CF ) (C H ) , ( C H ) SO N(C H ) ( C H ) ,
2 k 2 2 m 2 n 2 o 2 3 2 p
O(C F ) (C H ) , or OCHFCF OE;
2 2 2 r 2
Z is O or S;
m is 1 to 4;
k, n, o, p, and r are each independently 1 to 20;
E is a C to C linear or branched alkyl group optionally
2 20
interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a
C to C aryl group;
6 10
R is a C to C linear or branched alkyl group optionally
2 60
interrupted by hetero atoms selected from the group consisting of an
oxygen, sulfur, or nitrogen atom; a cyclic alkyl; or a C to C aryl;
6 10
provided that when R is greater than 8 carbons, the ratio of hetero atoms
to carbon atoms is at least 1:2; and
1 2 + 1 2
M is an ammonium cation (N H R R ) wherein R and R are
independently linear or branched organic groups containing at least one
carboxylate moiety and one amino moiety, and optionally be substituted,
interrupted, or both with oxygen, sulfur, or nitrogen-containing moieties, or
with cyclic alkyl or aryl moieties containing up to 10 carbon atoms.
Fluorinated compounds of formula (I ) , (I I) , and (I II) described above
useful in various embodiments of the invention are available by synthesis.
The fluoroalkylphosphates of formula ( I ) and (I I) are prepared
according to the method described by Longoria et al in US Patent
6,271,289, and Brace and Mackenzie, in U.S. Patent 3,083,224, each
herein incorporated by reference. Typically, either phosphorus pentoxide
(P O ) or phosphorus oxychloride (P OCl ) is reacted with the fluoroalkyl
2 5 3
alcohol or fluoroalkyl thiol to give mixtures of the mono- and
bis(f luoroalkyl) p hosphoric acids. Neutralization with an amino acid, such
as L-arginine and L-lysine, for instance, provides the corresponding
phosphates. Reacting an excess of fluoroalkyl alcohol or fluoroalkyl thiol
with P O followed by neutralization provides a mixture of
mono(f luoroalkyl)p hosphate and bis(f luoroalkyl)p hosphate. Higher ratios
of bis(f luoroalkyl)p hosphate to mono(f luoroalkyl)p hosphate are obtained
by using the method of Hayashi and Kawakami in U.S. Patent 4,145,382.
The phosphite and phosphinate compositions are prepared in a similar
manner.
The resulting composition is then diluted with water, mixture of
water and solvent, or further dispersed or dissolved in a solvent selected
from the groups comprising simple alcohols, glycol ethers, and ketones
that are suitable as the solvent for final application to substrates
(h ereinafter the “application solvent”). Alternatively, an aqueous
dispersion, made by conventional methods with surfactants, is prepared
by removing solvents by evaporation and the use of emulsification or
homogenization procedures known to those skilled in the art. Such
solvent-free emulsions may be preferred to minimize flammability and
volatile organic compounds (V OC) concerns. The final product for
application to a substrate can be a dispersion, if water based, or a
solution.
The fluoroalkylphosphates of formula (I II) are prepared by reacting
either phosphorus pentoxide (P O ) or phosphorus oxychloride (P OCl )
2 5 3
with fluorinated alcohol, followed by the addition of hydrocarbon diol or
poly(g lycol). Typically the phosphorus pentoxide or phosphorus
oxychloride is added to the fluorinated alcohol in an amount that is
approximately equivalent mol percent. For example, when phosphorus
pentoxide is used from about 0.4 to about 1.6 mole equivalent of
fluorinated alcohol to P O is added. The mixture is heated to a
temperature of from about 70ºC to about 120º C, preferably to from about
100ºC to about 110ºC, and maintained for several hours, preferably from
about 3 to about 15 hours. A diol or poly(g lycol) is then added to the
reaction mixture with continued heating at the above temperature for an
additional time of from about 3 to about 15 hours. The mole ratio of diol or
poly(g lycol) to P O is from about 1.4 to about 2.6. This is followed by the
optional addition of a surfactant in from about 1% to about 3% by weight.
Any of a variety of surfactants can be employed, such as TERGITOL
available from Sigma Aldrich, St. Louis, MO. After about 1 to about 2
hours, ammonia is added with mixing, followed by water, to provide the
phosphate of Formula 1.
Diols useful in the synthesis of compounds of Formula (I II) include
C to C straight and branched chain alcohols optionally having one or
2 60
two double bonds. Examples include 1,3-propanediol; propylene glycol
(1 ,2-propanediol); di( e thylene glycol); tri(e thylene glycol); tetra(e thylene
glycol); poly(e thylene glycol)s [PEG(O H) ], preferably having from about 4
to about 20 repeat units, and more preferably from about 5 to about 15
repeat units; poly(e thylene glycol)-polypropylene glycol-poly(e thylene
glycol) triblock polymers [PEG-PPG-PEG-(O H) ]; and random copolymers
of ethylene oxide and propylene oxide, preferably with a molecular weight
M of from about 200 to about 1250. Poly(1 .3-propanediol)s are available
from E. I. du Pont de Nemours and Company, Wilmington, DE.
Polyethylene glycols with nominal molecular weights of 200 to 2000 are
available from Aldrich Chemical Company, St. Louis, MO. Tri-block
copolymers of polyethylene oxide and polypropylene oxide ( P EG-PPG-
PEG) are available from BASF, Mount Olive, NJ.
It will be apparent to one skilled in the art that many changes to any
or all of the procedures described above may also be used to optimize the
reaction conditions for obtaining maximum yield, productivity or product
quality.
The fluoroalkyl alcohol used as a reactant in the preparation of
composition comprising formula (I ), ( I I), or (I II) are described below for
various embodiments.
One embodiment of the present invention is a composition
comprising formula (I ) , (I I), or (I II), where A is (C H ) . Fluorinated alkyl
iodides of formula R -I can be treated with ethylene by procedures
described in U.S. Patent 3,979,469, (C iba-Geigy, 1976) to provide the
telomer ethylene iodides wherein k is 2 to 6, or higher. The telomer
ethylene iodides can be treated with oleum and hydrolyzed to provide the
corresponding telomer alcohols according to procedures disclosed in WO
95/11877 ( E lf Atochem S.A.) . Fluorinated alcohols C F CH CH OH
6 13 2 2
and C F CH CH OH are available from E. I. du Pont de Nemours and
4 9 2 2
Company, Wilmington, DE. The higher homologs of telomer ethylene
iodides are available with excess ethylene at high pressure. The telomer
ethylene iodides can be treated with a variety of reagents to provide the
corresponding thiols according to procedures described in J. Fluorine
Chemistry, 104, 2 173-183 (2 000) . One example is the reaction of the
telomer ethylene iodides with sodium thioacetate, followed by hydrolysis.
One embodiment of the present invention is a composition
comprising formula (I ), (I I), or (I II), wherein A is (C H CF ) (C H ) .
2 2 m 2 n
The telomerization of vinylidene fluoride ( V DF) with linear or
branched perfluoroalkyl iodides is well known, and produces compounds
of the structure R ( C H CF ) I, wherein, m is 1 to 3 or more and R is a
f 2 2 m f
C to C linear or branched perfluoroalkyl group. For example, see
Balague, et al, “Synthesis of fluorinated telomers, Part 1, Telomerization of
vinylidene fluoride with perfluoroalkyl iodides”, J. Flour Chem. (1 995),
70(2 ), 215-23. The specific telomer iodides of formula R (C H CF ) I are
f 2 2 p
isolated by fractional distillation and can be treated with ethylene, as
described above, to produce compounds of formula
R ( C H CF ) (C H2) I. The compounds of formula R (C H CF ) ( C H2) I
f 2 2 m n f 2 2 m n
can be treated as described above to produce alcohols and thiols.
One embodiment of the present invention is a compound
composition comprising formula (I ), (I I), or (I II), A is
(C H ) SO N( C H ) ( C H ) -. Preferred compositions of formula (I ), (I I), or
2 o 2 3 2 p
(I I), include those wherein o and p are each 2. The fluoroalkyl alcohol
used to prepare compounds of R ( C H ) SO N(C H ) ( C H ) -OH is
f 2 o 2 3 2 p
available from E. I. du Pont de Nemours and Company, Wilmington DE.
Alternatively the fluoroalkyl alcohol R (C H ) SO N(C H )( C H ) -OH,
f 2 o 2 3 2 p
wherein o and p are defined above in Formula (1 ), is prepared by the
reaction of a fluoroalkyl ethylene iodide with potassium thiocyanate in
water. The product R (C H ) SCN is distilled as a colorless liquid, which
f 2 o
then is converted to fluorinated sulfonyl chloride having the formula
R ( C H ) SO Cl by a reaction with chlorine and acetic acid over several
f 2 o 2
hours at about 45~50˚C in an autoclave. The sulfonyl chloride is then
reacted with an amine, for example, such as N-methylethanolamine, to
produce the fluorinated alcohol of the formula
R (C H ) SO N( C H )( CH ) -OH.
f 2 o 2 3 2 p
One embodiment of the present invention is a composition
comprising formula (I ) , (I I), or (I II), A is O(C F ) (C H ) . Preferred
2 q 2 r
compositions of formula (I ) or (I I) are those wherein A is O(C F ) (C H ) , q
2 q 2 r
and r are each 2, R is C F . Preferred compositions of formula (I II) are
f 3 7
those wherein A is O(C F ) ( C H ) , q and r are each 2, and R is C F R is
2 q 2 r f 3 7
CH CH .
The fluoroalcohols used as starting materials to make the
compositions of compositions wherein A is O(C F ) (C H ) are available
2 q 2 r
by synthesis.
The starting perfluoroalkyl ether iodides of formula R OCF CF I
f 2 2
can be made by the procedure described in US Patent 5,481,028, in
Example 8, which discloses the preparation of perfluoroalkyl ether iodides
from perfluoro-n-propyl vinyl ether. Perfluoroalkyl ether iodide is then
reacted with an excess of ethylene at an elevated temperature and
pressure. While the addition of ethylene can be carried out thermally, the
use of a suitable initiator is preferred. Preferably the initiator is a peroxide
such as benzoyl peroxide, isobutyryl peroxide, propionyl peroxide, or
acetyl peroxide. More preferably the peroxide is benzoyl peroxide. The
temperature of the reaction is not limited, but a temperature in the range of
110°C to 130°C is preferred. The reaction time can vary with the initiator
and reaction conditions, but 24 hours is usually adequate. The product is
purified by any means that separates unreacted starting material from the
final product, but distillation is preferred. Satisfactory yields up to 80% of
theory have been obtained using about 2.7 mols of ethylene per mole of
perfluoalkyl ether iodide, a temperature of 110°C and autogenous
pressure, a reaction time of 24 hours, and purifying the product by
distillation.
The perfluoroalkylether ethylene iodides of formula
R O(C F ) (C H ) I, where R and r are as defined above, are treated with
f 2 2 2 r f
oleum and hydrolyzed to provide the corresponding alcohols according to
procedures disclosed in WO 95/11877 ( E lf Atochem S.A.). Alternatively,
the perfluoroalkylether ethyl iodides can be treated with N-methyl
formamide followed by ethyl alcohol/acid hydrolysis. A temperature of
about 130° to 160°C is preferred. The higher homologs (r is >2) are
available with excess ethylene at high pressure. The fluorinated alkyl
ether ethylene iodides of formula R O(C F ) ( C H ) I are treated with a
f 2 2 2 r
variety of reagents to provide the corresponding thiols according to
procedures described in J. Fluorine Chemistry, 104, 2 173-183 (2 000).
The fluorinated alkyl ether ethylene iodides can also be treated to provide
the corresponding thioethanols or thioethylamines by conventional
methods.
One embodiment of the present invention is a composition
comprising formula (I ), (I I), or ( I II), A is OCHFCF OE. The fluoroalcohols
used as starting materials to make the compositions of Formula 5 are
prepared by reacting a dioxane with a diol in the presence of an alkali
metal compound. For example a dioxane and a perfluoroalkyl ether of
formula R OCF=CF are reacted with a diol such as HO( C H ) OH in the
f 2 2 2
presence of an alkali metal, such as KOH, typically in a sealed stainless
steel reaction vessel at about 70ºC for about 8 hours. The diol is used at
about 1 to about 15 mols per mol of ether, preferably from about 1 to
about 5 mols per mol of ether. Suitable alkali metal compounds include an
alkali metal, alkali earth metal, alkali hydroxide, alkali hydride, or an alkali
amide. Preferred are alkali metals such as Na, K or Cs, or alkali hydrides
such as NaH or KH. The reaction is conducted at a temperature of from
about 40ºC to about 120ºC. The reaction can be conducted in an optional
solvent, such as ether or nitrile.
The present invention comprises fluorinated aqueous mixtures
comprising a mixture of an anionic aqueous fluoroalkyl phosphate,
phosphite or phosphonite acid solution neutralized with an amino acid,
preferably L-arginine and L-lysine. The composition is neutralized to a pH
of about 5 to about 10, preferably about 6 to about 9 and most preferably,
from about 6 to about 8.
One embodiment of the present invention is a method of lowering
the surface tension of a liquid comprising contacting a liquid to a
composition comprising formula I, formula II, or formula III
( R -A-Z)
(O M )
(Fo rmula I)
R -A-Z-CH
f 2 O O
R -A-Z-CH M
(Fo rmula II)
R -A-Z
OROH
(Fo rmula III)
wherein R , x, A, Z, M, k, n, o, p, r, E, R, and M are as defined above.
The liquids where the present invention is useful to lower the
surface tension include, but not limited to, are water, saline solution, KCl
solution, drill fluids, well fluids, liquid treatment or gas treatment stream for
subterranean formation and well bore areas, hydrocarbon, halocarbon
system, coating composition, latex, polymer, floor finish, floor polish, fire
fighting agent, ink, emulsifying agent, foaming agent, release agent,
repellency agent, flow modifier, film evaporation inhibitor, wetting agent,
penetrating agent, cleaner, grinding agent, electroplating agent, corrosion
inhibitor, etchant solution, soldering agent, dispersion aid, microbial agent,
pulping aid, rinsing aid, polishing agent, personal care composition, drying
agent, antistatic agent, or bonding agent.
Coating compositions are alkyd coatings, a Type I urethane
coatings, an unsaturated polyester coatings, or a water-dispersed
coatings.
The present invention further comprises a method of providing
water repellency, oil repellency, and stain resistance to a substrate
comprising contacting the substrate with a composition of formula (I ) or ( I I)
as defined above, or a mixture thereof. The composition of the present
invention is typically applied by contacting the substrate with the
composition by conventional means, including, but not limited to, brush,
spray, roller, doctor blade, wipe, immersion, dip techniques, foam, liquid
injection, and casting. Optionally, more than one coat can be used,
particularly on porous surfaces.
The compositions of the present invention can be used as an
additive during the manufacture of substrates. They can be added at any
suitable point during manufacture. For example, in the case of paper, they
can be added to the paper pulp in a size press. Preferably, about 0.3
weight % to about 0.5 weight % of the composition of the invention is
added to paper pulp, based on the dry solids of the composition and dry
paper fiber.
When used as a surface treatment for paper, the compositions of
the invention are typically diluted with water to give an application solution
having about 0.01 weight % to about 20 weight %, preferably about 0.1
weight % to about 10 weight %, and most preferably about 0.5 weight % to
about 5 weight %, of the composition based on solids. The coverage as
applied to paper is about 10 g/m to about 200 g/m , and preferably about
g/m to about 100 g/m of the application solution. Preferably the
application results in about 0.1 g/m to about 5.0 g/m of solids being
applied to the paper.
When used on stone, tile and other hard surfaces, the compositions
of the invention are typically diluted with water to give an application
solution having about 0.1 weight% to about 20 weight %, preferably from
about 1.0 weight% to about 10 weight%, and most preferably from about
2.0 weight% to about 5.0 weight%, of the composition based on solids.
The coverage as applied to a substrate is about 100 g of application
solution per sq meter ( g /m ) for semi-porous substrates (e .g. limestone)
and 200 g/m for porous substrates ( e .g. Saltillo) . Preferably the
application results in about 0.1 g/m to about 2.0 g/m of solids being
applied to the surface.
The composition of this invention is applied to or contacted with the
substrate as such, or in combination with one or more other finishes or
surface treating agents. The composition of the present invention
optionally further comprises additional components such as treating
agents or finishes to achieve additional surface effects, or additives
commonly used with such agents or finishes. Such additional components
comprise compounds or compositions that provide surface effects such as
stain repellency, stain release, soil repellency, soil release, water
repellency, oil repellency, antimicrobial protection, and similar effects.
One or more of such treating agents or finishes can be blended with the
composition of the present invention and applied to the substrate.
Other additives commonly used with such treating agents or
finishes can also be present such as surfactants, pH adjusters, leveling
agents, wetting agents, and other additives known by those skilled in the
art. Examples of such finishes or agents include processing aids, foaming
agents, lubricants, anti-stains, and the like. The composition is applied at
a manufacturing facility, retailer location, or prior to installation and use, or
at a consumer location.
The present invention further comprises a method of providing
resistance to blocking, open time extension, and oil repellency to a
substrate having deposited thereon a coating composition comprising
adding to the coating composition prior to deposition on the substrate a
composition of the above formula ( I ) or (I I) or mixtures thereof. Suitable
coating compositions, referred to herein by the term “coating base”,
include a composition, typically a liquid formulation, of an alkyd coating,
Type I urethane coating, unsaturated polyester coating, or water-dispersed
coating, and is applied to a substrate for the purpose of creating a lasting
film on the substrate surface. These are conventional paints, stains, and
similar coating compositions.
By the term "alkyd coating" as used herein is meant a conventional
liquid coating based on alkyd resins, typically a paint, clear coating, or
stain. The alkyd resins are complex branched and cross-linked polyesters
containing unsaturated aliphatic acid residues. Conventional alkyd
coatings utilize, as the binder or film-forming component, a curing or
drying alkyd resin. Alkyd resin coatings contain unsaturated aliphatic acid
residues derived from drying oils. These resins spontaneously polymerize
in the presence of oxygen or air to yield a solid protective film. The
polymerization is termed "drying" or "curing" and occurs as a result of
autoxidation of the unsaturated carbon-carbon bonds in the aliphatic acid
component of the oil by atmospheric oxygen. When applied to a surface
as a thin liquid layer of formulated alkyd coating, the cured films that form
are relatively hard, non-melting, and substantially insoluble in many
organic solvents that act as solvents or thinners for the unoxidized alkyd
resin or drying oil. Such drying oils have been used as raw materials for
oil-based coatings and are described in the literature.
By the term "urethane coating" as used hereinafter is meant a
conventional liquid coating based on Type I urethane resins, typically a
paint, clear coating, or stain. Urethane coatings typically contain the
reaction product of a polyisocyanate, usually toluene diisocyanate, and a
polyhydric alcohol ester of drying oil acids. Urethane coatings are
classified by ASTM D-1 into five categories. Type I urethane coatings
contain a pre-reacted autoxidizable binder as described in Surface
Coatings Vol. 1, previously cited. These are also known as uralkyds,
urethane-modified alkyds, oil-modified urethanes, urethane oils, or
urethane alkyds, are the largest volume category of polyurethane coatings
and include paints, clear coatings, or stains. The cured coating is formed
by air oxidation and polymerization of the unsaturated drying oil residue in
the binder.
By the term "unsaturated polyester coating" as used hereinafter is
meant a conventional liquid coating based on unsaturated polyester
resins, dissolved in monomers and containing initiators and catalysts as
needed, typically as a paint, clear coating, or gel coat formulation.
Unsaturated polyester resins contain as the unsaturated prepolymer the
product obtained from the condensation polymerization of a glycol such as
1,2- propylene glycol or 1,3-butylene glycol with an unsaturated acid such
as maleic (o r of maleic and a saturated acid, e.g., phthalic) in the
anhydride form. The unsaturated prepolymer is a linear polymer
containing unsaturation in the chain. This is dissolved in a suitable
monomer, for instance styrene, to produce the final resin. The film is
produced by copolymerization of the linear polymer and monomer by
means of a free radical mechanism. The free radicals can be generated
by heat, or more usually by addition of a peroxide, such as benzoyl
peroxide, separately packaged and added before use. Such coating
compositions are frequently termed "gel coat" finishes. In order that curing
can take place at room temperature, the decomposition of peroxides into
free radicals is catalyzed by certain metal ions, usually cobalt. The
solutions of peroxide and cobalt compound are added separately to the
mix and well stirred before application. The unsaturated polyester resins
that cure by a free radical mechanism are also suited to irradiation curing
using, for instance, ultraviolet light. This form of cure, in which no heat is
produced, is particularly suited to films on wood or board. Other radiation
sources, for instance electron-beam curing, are also used.
By the term "water-dispersed coatings" as used herein is meant
coatings intended for the decoration or protection of a substrate composed
of water as an essential dispersing component such as an emulsion, latex,
or suspension of a film-forming material dispersed in an aqueous phase.
“Water-dispersed coating” is a general classification that describes a
number of formulations and includes members of the above described
classifications as well as members of other classifications. Water-
dispersed coatings general contain other common coating ingredients.
Water-dispersed coatings are exemplified by, but not limited to, pigmented
coatings such as latex paints, unpigmented coatings such as wood
sealers, stains, and finishes, coatings for masonry and cement, and water-
based asphalt emulsions. A water dispersed coating optionally contains
surfactants, protective colloids and thickeners, pigments and extender
pigments, preservatives, fungicides, freeze-thaw stabilizers, antifoam
agents, agents to control pH, coalescing aids, and other ingredients. For
latex paints the film forming material is a latex polymer of acrylate acrylic,
vinyl-acrylic, vinyl, or a mixture thereof. Such water-dispersed coating
compositions are described by C. R. Martens in "Emulsion and Water-
Soluble Paints and Coatings" (R einhold Publishing Corporation, New York,
NY, 1965) .
By the term "dried coating" as used herein is meant the final
decorative and/or protective film obtained after the coating composition
has dried, set or cured. Such a final film can be achieved by, for non-
limiting example, curing, coalescing, polymerizing, interpenetrating,
radiation curing, UV curing or evaporation. Final films can also be applied
in a dry and final state as in dry coating.
Blocking is the undesirable sticking together of two coated surfaces
when pressed together, or placed in contact with each other for an
extended period of time. When blocking occurs separation of the surfaces
can result in disruption of the coating on one or both surfaces. Thus
improved resistance to blocking is beneficial in many situations where two
coated surfaces need to be in contact, for example on window frames.
The term “open time extension” is used herein to mean the time
during which a layer of liquid coating composition can be blended into an
adjacent layer of liquid coating composition without showing a lap mark,
brush mark, or other application mark. It is also called wet-edge time.
Latex paint containing low boiling, volatile organic chemicals (V OC) has
shorter than desired open-time due to lack of high boiling temperature
VOC solvents. Lack of open time extension will cause surface defects
such as overlapping brush marks or other marks. A longer open time
extension is beneficial when the appearance of the coated surface is
important, as it permits application of the coating without leaving overlap
marks, brush marks, or other application marks at the area of overlap
between one layer of the coating and an adjacent layer of the coating.
When used as additives the compositions of the present invention
are effectively introduced to the coating base or other composition by
thoroughly stirring it in at room or ambient temperature. More elaborate
mixing can be employed such as using a mechanical shaker or providing
heat or other methods. Such methods are not necessary and do not
substantially improve the final composition. When used as an additive to
latex paints, the compositions of the invention generally are added at
about 0.001 weight % to about 5 weight % by dry weight of the
composition of the invention in the wet paint. Preferably about 0.01
weight % to about 1 weight %, and more preferably 0.1 weight % to about
0.5 weight % is used.
The present invention also comprises substrates treated with the
composition of the present invention. Suitable substrates include fibrous
and hard surface substrates. The fibrous substrates include wood, paper,
and leather. The hard surface substrates include porous and non-porous
mineral surfaces, such as glass, stone, masonry, concrete, unglazed tile,
brick, porous clay and various other substrates with surface porosity.
Specific examples of such substrates include unglazed concrete, brick,
tile, stone including granite, limestone and marble, grout, mortar, statuary,
monuments, wood, composite materials such as terrazzo, and wall and
ceiling panels including those fabricated with gypsum board. These are
used in the construction of buildings, roads, parking ramps, driveways,
floorings, fireplaces, fireplace hearths, counter tops, and other decorative
uses in interior and exterior applications.
The compositions of the present invention are useful to provide one
or more of excellent water repellency, oil repellency, and stain resistance
to treated substrates. They also are useful to provide resistance to
blocking, open time extension, and oil repellency to substrates coated with
a coating composition to which the compositions of the present invention
have been added. These properties are obtained using lower fluorine
concentrations compared with conventional perfluorocarbon surface
treatment agents, providing improved “fluorine efficiency” in the protection
of treated surfaces The compositions of the present invention are effective
at fluorine concentrations about one half to one third of the fluorine
concentration for conventional fluorochemical surface protectants. The
compositions of the present invention also allow for the use of shorter
fluoroalkyl groups containing 6 or fewer fluorinated carbon atoms while
conventional commercially available surface treatment products typically
show poor oil repellency and water repellency performance if the
fluoroalkyl groups contain less 8 carbon atoms.
MATERIALS and TEST METHODS
The following materials and test methods were used in the
examples herein.
C F CH CH2OH and C F CH CH OH are commercially
6 13 2 4 9 2 2
available from Sigma Aldrich, St. Louis, MO.
i-C F CF CF CH CH OH is commercially available available
3 7 2 2 2 2
from SynQuest Labs, Inc.
C F CH CF CH CH OH was produced by introducing ethylene
4 9 2 2 2 2
(2 5 g, 0.53 mol) was introduced to an autoclave charged with
C F CH CF I (2 17 g, 0.87 mol) and d-( + ) - limonene ( 1 g), and then the
4 9 2 2
reactor was heated at 240 ºC for 12 hours. Product was obtained via
vacuum distillation 81~91 C at 19~24 mmHg in 62 % yield. Fuming
sulfuric acid (7 0mL) was added slowly to 50 g of C F CH CF CH CH I
4 9 2 2 2 2
and mixture was stirred at 60 ºC for 1.5 h. The reaction was quenched
with ice-cold 1.5 wt% Na SO aqueous solution and heated at 95 ºC for
0.5 h. The bottom layer was separated and washed with 10 wt% aqueous
sodium acetate and distilled to provide compound of formula
C F CH CF CH CH OH: bp 54-57 ºC at 2 mmHg ( 2 67 Pascals).
4 9 2 2 2 2
C F OCF CF CH CH OH was produced by charging
3 7 2 2 2 2
C F OCF CF I ( 1 00 g, 0.24 mol) and benzoyl peroxide (3 g) to a
3 7 2 2
pressure vessel under nitrogen. A series of three vacuum/nitrogen gas
sequences was then executed at –50 °C and ethylene (1 8 g, 0.64 mol)
was introduced. The vessel was heated for 24 hour at 110 °C. The
autoclave was cooled to 0 °C and opened after degassing. Then the
product was collected in a bottle. The product was distilled giving 80 g of
C F OCF CF CH CH I in 80% yield. The boiling point was 56~60 °C at
3 7 2 2 2 2
mm Hg (3 333 Pa). A mixture of C F OCF CF CH CH I ( 3 00 g, 0.68
3 7 2 2 2 2
mol) and N-methyl-formamide (3 00 mL) , was heated to 150 °C for 26 h.
Then the reaction was cooled to 100 °C, followed by the addition of water
to separate the crude ester. Ethyl alcohol (7 7 mL) and p-toluene sulfonic
acid (2 .59 g) were added to the crude ester, and the reaction was stirred
at 70 °C for 15 minutes. Then ethyl formate and ethyl alcohol were
distilled out to give a crude product. The crude product was dissolved in
ether, washed with aqueous sodium sulfite, water, and brine in turn, and
then dried over magnesium sulfate. The product was then distilled to give
199 g of C F OCF CF CH CH OH in 85% yield. The boiling point was
3 7 2 2 2 2
71~73 ºC at 40 mm Hg ( 5 333 Pa).
L-lysine and L- Arginine are commercially available from Sigma
Aldrich, St. Louis, MO.
RHOPLEX 3829, formulation N1, is commercially available from
The Dow Chemical Company, Philadelphia, PA.
MAB paints have an acrylic semi-gloss resin with 84% gloss at 85
degrees and are commercially available from M. A. Bruder and Sons, Inc.,
Broomall, PA.
METHODS
Test Method 1–Surface Tension Measurement
Surface tension was measured according to the American Society
for Testing and Materials ASTM # D1331-56, using the Wilhelmy plate
method on a KRUSS K11 Version 2.501 tensiometer (K RUSS USA, 5
Matthews NC) in accordance with instructions with the equipment. A
vertical plate of known perimeter was attached to a balance, and the force
due to wetting was measured. Each example to be tested was added to a
coating composition by weight based on solids of the additive in deionized
water. Several different concentrations were prepared. Ten replicates
were tested of each dilution, and the following machine settings were
used: Method: Plate Method SFT, interval: 1.0 s, wetted length: 40.2mm,
reading limit: 10, min standard deviation: 2 dynes/cm, and Gr. Acc.:
9.80665 m/s2.
Results were in dynes/cm ( m N/m) with a Standard Deviation of less
than 1 dyne/cm. The tensiometer was used according to the
manufacturer’s recommendations. A stock solution was prepared for the
highest concentration of surfactant in the coating composition to be
analyzed. The concentration of the solution was by mol percent of the
surfactant in a commercially available floor polish (R HOPLEX 3829,
Formulation N1), in deionized water, and in 2% KCl solution in water.
The solutions are stirred overnight (f or approximately 12 hours) to ensure
complete mixing. Lower concentrations of the stock solution for each
example were made by diluting the original stock solution. The floor polish
is used for applications in the consumer, institutional, and industrial
cleaning segments for demonstration of providing surface effects to
substrates. Lower surface tension results indicate superior performance.
Test Method 2-Blocking Resistance of Architectural Latex Paints
The test method described herein is a modification of ASTM
D4946 - 89 — Standard Test Method for Blocking Resistance of
Architectural Paints.
The face-to-face blocking resistance of paints to be tested was
evaluated in this test. Blocking, for the purpose of this test, is defined as
the undesirable sticking together of two painted surfaces when pressed
together or placed in contact with each other for an extended period of
time.
The paint to be tested was cast on a polyester test panel using an
applicator blade. All painted panels were protected from grease, oil,
fingerprints, dust, et cetera, to avoid surface contamination that could
affect blocking resistance results. Typically, results are evaluated at 24
hours after casting the paint. After the panels have been conditioned in
the conditioned room as specified in the ASTM Method referenced above
for the desired period of time, six squares (3 .8 cm x 3.8 cm) were cut out
from the painted test panel. The cut sections (t hree pairs) were placed
with the paint surfaces face-to-face for each of the paints to be tested.
The cut sections (t hree pairs) are placed with the paint surfaces face-to-
face for each of the paints to be tested. The face-to-face specimens were
placed in a 50 °C oven on a marble tray. A no. 8 stopper was placed on
top, with the smaller diameter in contact with the specimens, and then a
1000g weight was placed on top of the stopper. This resulted in a
pressure of 1.8 psi (1 2.4 x 10 Pa) on the specimens. One weight and
stopper was used for each specimen tested. After exactly 30 minutes, the
stoppers and weights were taken off the test specimens which were
removed from the oven and allowed to cool in the conditioned room for 30
minutes before determining resistance to blocking.
After cooling, the specimens were separated by peeling apart with a
slow and steady force. The blocking resistance was rated from 0 to 10,
corresponding to a subjective tack assessment (so und made upon
separation of the painted specimens) or seal (co mplete adhesion of the
two painted surfaces) as determined by the operator of the method. The
specimen was put near the ear to actually hear the degree of tack. The
rating system is described in Table 1. The degree of seal was estimated
from the appearance of the specimens and the fraction of the paint
surfaces that adhere. Paint tearing away from the test panel backing was
an indication of seal. A higher number indicates better resistance to
blocking.
Table 1. Blocking Resistance Numerical Ratings
Blocking Resistance
Description of the Performance
Numerical Ratings
Separation Description
No tack Perfect
9 Trace tack Excellent
8 Very slight tack Very good
7 Slight tack Good/very good
6 Moderate to slight tack Good
Moderate tack Fair
4 Very tacky – no seal Poor to fair
3 5 to 25% seal Poor
2 25 to 50% seal Poor
1 50 to 75% seal Very poor
0 75 to 100% seal Very poor
Test Method 3 – Contact Angle
Contact angles were measured by the Sessile Drop Method, which
is described by A. W. Adamson in The Physical Chemistry of Surfaces,
Fifth Edition, Wiley & Sons, New York, NY, 1990. Additional information on
the equipment and procedure for measuring contact angles is provided by
R. H. Dettre et al. in "Wettability", Ed. by J. C. Berg, Marcel Dekker, New
York, NY, 1993. In the Sessile Drop Method, a Ramè-Hart optical bench
(a vailable from Ramè-Hart Inc., 43 Bloomfield Ave., Mountain Lakes, NJ)
was used to hold the substrate in the horizontal position. The contact
angle was measured at a prescribed temperature with a telescoping
goniometer from the same manufacturer. Each Example to be tested was
added to MAB paint at 0.018% by weight based on solids of the additive in
the paint. A drop of test liquid was placed on a polyester scrub test panel
(L eneta P-121 dull black or equivalent, Leneta Company, Mahwah, NJ)
and the tangent was precisely determined at the point of contact between
the drop and the surface. An advancing angle was determined by
increasing the size of the drop of liquid. The data were presented as
advancing contact angles.
The relationship between organic liquid contact angles, and the
cleanability and dirt retention of surfaces is described by A. W. Adamson,
above. In general, higher hexadecane contact angles indicate that a
surface has greater dirt and soil repellency, and easier surface
cleanability.
Test Method 4-Wetting/Leveling Test
To test the performance of the samples in their wetting and leveling
ability, the samples were added to a floor polish (R HOPLEX 3829,
Formulation N1, available from The Dow Chemical Company,
Philadelphia, PA]) and applied to half of a thoroughly cleaned 12 inch X 12
inch ( 3 0.36 cm X 30.36 cm) vinyl tile (a vailable from Interfuse Vinyl Tiles
by Estrie, Sherbrooke, QC Canada). The tiles are thoroughly cleaned by
wetting the tiles, adding a powdered oxygen bleach cleanser and
scrubbing using a green SCOTCH-BRITE scouring pad, available from 3M
Company, St. Paul MN) . This scrubbing procedure was used to remove
the pre-existing coating on the tiles. The tiles initially have a uniform shiny
finish; a uniform dull finish indicates coating removal. The tiles are then
air-dried overnight. A 1 wt % solution of the surfactant to be tested was
prepared by dilution in deionized water. Following the resin manufacturer
protocols, a 100 g portion of the RHOPLEX 3829, N1 formulation was
prepared, followed by addition of 0.75 g of the 1 wt % surfactant solution,
to provide a test floor polish.
The test floor polish was applied to the tile by placing 3 mL portion
of the test polish in the center of the tile, and spreading from top to bottom
using a cheesecloth applicator, and finally placing a large “X” across the
tile, using the applicator. The “X” subsequently provides visual evidence of
leveling at the rating step. The applicator was prepared from a two-layer
18 x 36 inch (4 6 x 91 cm) sheet of cheesecloth (f rom VWR, West Chester
PA), folded twice into an eight-layer pad. One corner of the pad was then
used as the applicator. The tile was allowed to dry for 30 min. and a total
of 5 coats ( C oating #s 1 - 5) were applied and dried, with the X test
performed after each coating had been dried. After each coat, the tile was
rated on a 1 to 5 scale (1 being the worst, 5 the best) on the surfactant’s
ability to promote wetting and leveling of the polish on the tile surface.
The rating is determined using the Tile Rating Scale below, based on
comparison of a tile treated with the floor polish that contains no added
surfactant.
Table 2. Visual Tile Rating Scale for Leveling
Score Description
1 Uneven surface coverage of the film, significant streaking and
surface defects
2 Numerous surface defects and streaks are evident but,
generally, film coats entire tile surface
3 Visible streaking and surface defects, withdrawal of the film
from the edges of the tile
4 Minor surface imperfections or streaking
No visible surface defects or streaks
Test Method 5 – Blender Foaming Test
The test procedure used to evaluate the foaming of
fluorosurfactants for oilfield (e .g. drilling and stimulation) and cleaning
applications is a modified version of the blender foaming test ASTM
D3519-88 – Standard Test Method for Foam in Aqueous Media (Blender
Test). The ability of the samples to create foam and maintain stable foam
in aqueous solution over a period of time was evaluated in this test. A
blender, graduated cylinder, glass sample bottles and a stop watch were
the only materials required. First, stock solutions of the testing base
solutions were made. These solutions were deionized water and 2% KCl
Samples of 100 mL of the fluorosurfactant to be tested at 0.1 % active
ingredient in the desired base testing solution were prepared and stirred
overnight to ensure complete mixing. The blender was cleaned with
copious amounts of deionized water. Once clean, the blender was
assembled for use. The test fluid sample of 100 mL was poured into the
blender jar. The temperature of the test fluid was measured with a
thermometer and recorded. The blender was then run for 20 seconds at
50-60% power. After 20 seconds, the liquid and foam were immediately
poured into a 500 mL graduated cylinder. The initial liquid and foam height
were measured in mL and a timer was started. This was designated the
maximum total foam height at time zero. The graduated cylinder was
allowed to stand undisturbed. Additional liquid and foam height (i n mL)
measurements were taken 5, 10 and 15 minutes after the stop watch was
started. In addition, the half-life of the foam was also recorded. The half-
life was the time when half of the liquid had drained to the bottom of the
graduated cylinder. During this time, any observations of the foam were
recorded such as dense or thin foam and foam persistency. A larger
height (i n mL) of the foam indicated that the sample foamed more. A
consistently high height (i n mL) of foam demonstrated persistent foam.
The blender foaming test was used as an indicator of the amount of foam
that a sample produced and also displayed the persistence of that foam.
EXAMPLES
Example 1
Phosphorous pentoxide (5 .24 g, 0.03692 mol) was added to
C F CH CH OH ( 3 0 g, 0.08242 mol) at 80 C and the reaction was
6 13 2 2
heated to 105 C overnight. The reaction mixture was cooled to 60 C and
added to aqueous lysine solution (1 2.77 g lysine in 181 mL water). The
mixture was stirred for 1 hour at 70 C. The resulting product was tested
from surface tension, contact angle, resistance to blocking, and leveling as
described below with results in Tables 3 to 7.
Example 2
Phosphorous pentoxide (1 .23 g, 0.008682 mol) was added to
C F CH CH OH (5 .12 g, 0.01938 mol) at 80 C and the reaction was
4 9 2 2
heated to 105 C overnight. The reaction mixture was cooled to 60 C,
followed by adding aqueous lysine solution (3 g lysine in 37 g water)
addition. This phosphate lysine salt solution was stirred for 1 hour at
70 C. The resulting product was tested from surface tension, contact
angle, resistance to blocking, and leveling as described below with results
in Tables 3 to 7.
Example 3
Phosphorous pentoxide (0 .97 g, 0.00683 mol) was added to
C F CH CF CH CH OH (5 g, 0.01524 mol) at 80 C and the reaction
4 9 2 2 2 2
was heated to 105 C overnight. The reaction mixture was cooled to
60 C, followed by adding aqueous lysine solution (2 .36 g lysine in 33 g
water). This phosphate lysine salt solution was stirred for 1 hour at 70 C.
The resulting product was tested from surface tension, contact angle,
resistance to blocking, and leveling as described below with results in
Tables 3 to 7.
Example 4
Phosphorous pentoxide (0 .96 g, 0.00679 mol) was added to
C F OCF CF CH CH OH (5 g, 0.01515 mol) at 80 C and the reaction
3 7 2 2 2 2
was heated to 105 C overnight. The reaction mixture was cooled to
60 C, followed by adding aqueous lysine solution (2 .34 g lysine in 47 g
water). This phosphate lysine salt solution was stirred for 1 hour at 70 C.
The resulting product was tested from surface tension, contact angle,
resistance to blocking, and leveling as described below with results in
Tables 3 to 7.
Example 5
Phosphorous pentoxide (1 .01 g, 0.00713 mol) was added to i-
C F CF CF CH CH OH ( 5 g, 0.01592 mol) at 80 C and the reaction
3 7 2 2 2 2
was heated to 105 C overnight. The reaction mixture was cooled to
60 C, followed by adding aqueous lysine solution (2 .94 g lysine in 34 g
water). This phosphate lysine salt solution was stirred for 1 hour at 70 C.
The resulting product was tested from surface tension, contact angle,
resistance to blocking, and leveling as described below with results in
Tables 3 to 7.
Example 6
Phosphorous pentoxide (0 .87 g, 0.006154 mol) was added to
C F CH CH OH (5 g, 0.01374 mol) at 80 C and the reaction was
6 13 2 2
heated to 105 C overnight. The reaction mixture was cooled to 60 C,
followed by adding aqueous arginine solution (2 .54 g arginine in 34 g
water) addition. This phosphate lysine salt solution was stirred for 1 hour
at 70 C. The resulting product was tested from surface tension, contact
angle, resistance to blocking, and leveling as described below with results
in Tables 3 to 7.
Example 7
Phosphorous pentoxide (1 .20 g, 0.008485 mol) was added to
C F CH CH OH ( 5 g, 0.01894 mol) at 80 C and the reaction was heated
4 9 2 2
to 105 C overnight. The reaction mixture was cooled to 60 C, followed
by adding aqueous arginine solution (3 .5 g arginine in 39 g water)
addition. This phosphate lysine salt solution was stirred for 1 hour at
70 C. The resulting product was tested from surface tension, contact
angle, resistance to blocking, and leveling as described below with results
in Tables 3 to 7.
Example 8
Phosphorous pentoxide (0 .97 g, 0.00683 mol) was added to
C F CH CF CH CH OH ( 5 g, 0.01524 mol) at 80 C and the reaction
4 9 2 2 2 2
was heated to 105 C overnight. The reaction mixture was cooled to
60 C, followed by adding aqueous arginine solution (2 .81 g arginine in 35
g water) addition. This phosphate lysine salt solution was stirred for 1 hour
at 70 C. The resulting product was tested from surface tension, contact
angle, resistance to blocking, and leveling as described below with results
in Tables 3 to 7.
Example 9
Phosphorous pentoxide (0 .96 g, 0.00679 mol) was added to
C F OCF CF CH CH OH ( 5 g, 0.01515 mol) at 80 C and the reaction
3 7 2 2 2 2
was heated to 105 C overnight. The reaction mixture was cooled to
60 C, followed by adding aqueous arginine solution (2 .8 g arginine in 35 g
water) addition. This phosphate lysine salt solution was stirred for 1 hour
at 70 C. The resulting product was tested from surface tension, contact
angle, resistance to blocking, and leveling as described below with results
in Tables 3 to 7.
Example 10
Phosphorous pentoxide ( 1 .01 g, 0.00713 mol) was added to i-
C F CF CF CH CH OH (5 g, 0.01592 mol) at 80 C and the reaction
3 7 2 2 2 2
was heated to 105 C overnight. The reaction mixture was cooled to
60 C, followed by adding aqueous arginine solution (2 .94 g arginine in 36
g water) addition. This phosphate lysine salt solution was stirred for 1 hour
at 70 C. The resulting product was tested from surface tension, contact
angle, resistance to blocking, and leveling as described below with results
in Tables 3 to 7.
Comparative Example A
Phosphorus pentoxide (1 equivalent) was added to a
perfluoroalkylethyl alcohol mixture of the formula F(C F ) CH CH OH ( 2 .3
2 z 2 2
equivalents). at 80 C. The typical mixture was as follows: 1.6% of z=4,
48.3% of z = 6, 28.7% of z = 8, 13.9% of z = 10, 5.3% of z = 12, 1.7 of z =
14, 0.4% of z = 16 and 0.1% of z = 18. The reaction was heated to 105 C
for 24 hours. Ammonia (3 0% solution in water, 2.6 equivalents) was
added and the reaction was stirred for 10 min. at 70 C. Water was added
and the reaction was stirred at 70 °C for 1 hour to provide a phosphate
product. The resulting product was tested for leveling, surface tension,
contact angle, and resistance to blocking using Test Methods 1 to 4. The
results are listed in Tables 3 to 7.
Table 3. Surface Tension in DI Water (d ynes/cm) at 23 degC.
Example* 0.000% 0.001% 0.010% 0.100% 0.500%
1 72.2 64.1 25.7 23.8 26.9
2 72.1 58.4 44.7 27.4 16.4
3 72.3 46.9 33.4 18.2 16.5
4 72.3 38.7 26.6 18.2 17.1
72.0 47.4 36.5 21.6 19.0
6 72.4 66.4 24.6 21.6 22.0
7 72.6 57.0 42.0 25.1 17.0
8 72.6 46.9 32.2 16.8 17.0
9 72.2 40.7 26.0 20.1 18.0
72.3 40.2 33.0 19.4 17.7
Comparative
72.2 61.8 39.2 34.3 26.3
Example
*Example was added to deionized water by weight based on solids of
the additive in DI water.
*Standard Deviation <1 dynes/cm
Normal surface tension of deionized water is 72 dynes/cm (sh own
in Table 3 as 0.000%). When the compounds of the present invention
were added at a specified rate, the surface tension of each aqueous
solution was reduced significantly. Better performance was obtained at
higher levels.
Table 4. Surface Tension in Rhoplex 3829 (N 1 Formulation) Floor
Finish (d ynes/cm) at 23 °C.
Example* 0.000% 0.001% 0.010% 0.100% 0.500%
1 32.2 31.5 27.8 17.3 16.1
2 32.3 31.6 30.1 24.4 19.5
3 32.3 31.2 30.3 25.3 19.9
4 32.1 31.8 27.4 19.1 16.8
32.2 29.2 29.0 22.7 18.1
6 32.3 31.7 27.8 17.9 16.4
7 32.2 32.1 30.6 24.8 19.5
8 32.0 31.8 29.7 25.8 20.1
9 32.4 31.9 28.2 19.9 16.5
32.5 31.9 29.7 23.6 17.9
Comparative
32.5 31.3 28.2 21.0 20.3
Example
* Concentration of examples in floor finish, % by weight.
* Standard Deviation < 1 dynes/cm
Normal surface tension of the RHOPLEX 3829, formulation N1
coating composition is 32 dynes/cm. When the above examples of the
present invention were added at a specified rate, the surface tension of
each aqueous coating composition solution was significantly reduced.
Better performance (l ower surface tension values) was obtained at higher
levels, which is indicative of improved wetting and leveling properties.
Examples 1-10 performed equal or better with surface tension reduction
than the Comparative Example comprising fluorinated phosphate having
longer perfluorinated alkyl groups and a higher fluorine loading.
Table 5. Resistance to Blocking in Semi-Gloss Latex Paint
Example* Blocking Rating** Fluorine (p pm)
Control 2.7 0
1 8.7 85
2 7.3 71
3 8.3 76
4 8.0 76
8.0 78
6 8.3 81
7 7.3 67
8 7.0 73
9 7.3 72
7.3 74
Comparative 8.2 114
Example
*Example was added to paint at 0.02% based on solids by weight
based on solids of the additive in the paint
**Average of 3 replicates
The data in Table 5 demonstrates that excellent resistance to
blocking was obtained from the present invention compared to the
Comparative Example at much lower fluorine content.
Table 6. Advancing Contact Angle in Semi-Gloss Latex Paint
Example* Hexadecane F ( p pm)
Control 0 0
1 81.3 85
2 84.5 71
3 82.2 76
4 98.8 76
95.8 78
6 81.9 81
7 87.5 67
8 73.6 73
9 92.5 72
83.6 74
Comparative Example 81.4 114
*Example added to paint at 0.02 wt % based on solids of the
additive in the paint
The data in Table 6 show excellent increased hexadecane contact
angle for all examples of the present invention compared to the control.
The increase in the advancing hexadecane contact angle correlates with
improved oil repellency. The present invention also performs equal to or
better than the comparative example at significant lower F loading.
The product was added to floor polish in an amount of 0.75 wt% of
1 wt% the surfactant dilution and tested for leveling using Test Method 3.
Results are shown in Table 7.
Table 7. Leveling in RHOPLEX 3829 (N 1 Formulation) Floor Finish
Examples Reading* F (p pm)
Blank 1.2 0
1 3.3 32
2 3.3 27
3 3.3 29
4 3.1 29
3.1 30
6 3.3 30
7 3.2 25
8 3.1 27
9 3.3 27
3.1 28
Comparative
3.6 43
Example
*Average of 5 coats
The phosphates exhibited excellent wetting ability in a
commercially available floor finish (R HOPLEX 3829 N1 formulation).
They performed equally to the Comparative Example comprising
fluorinated phosphate having longer perfluorinated alkyl groups and a
much higher fluorine loading when tested on vinyl tile.
Table 8. Surface Tension in 2% KCl (d ynes/cm) at 23 degC.
Example* 0.000% 0.001% 0.010% 0.100% 0.500%
1 73.5 - - - -
2 73.3 46.0 24.0 15.8 16.0
3 73.5 48.6 19.9 17.3 17.3
4 72.9 28.3 19.4 18.8 15.1
73.4 29.8 17.9 17.6 16.9
6 73.5 - - - -
7 73.5 43.2 23.0 16.1 14.5
8 74.2 38.5 19.0 18.2 16.1
9 73.5 46.8 20.3 19.5 17.3
73.4 34.2 18.5 17.1 17.5
Comparative
73.6 68.4 50.2 32.9 29.0
Example
- = not tested
Normal surface tension of 2% KCl water is 73.5 dynes/cm (s hown
in Table X as 0.000%). Example 1 and 6 were not stable in 2% KCl.
When the above phosphate was added at a specified rate, the surface
tension of each aqueous solution was reduced significantly. Better
performance was obtained at higher levels. According to the results from
the test, excellent surface tension reduction was seen from the present
invention that outperforms the Comparative Example. Improved surface
tension reduction in brine is desirable for oilfield stimulation and drilling
fluid applications.
Table 9 – Blender Foaming in Deionized Water
Example Foam Volume(m L)
Initial t = 5 min t = 10 min t = 15 min
1 110 5 5 5
2 245 115 100 85
3 220 123 11 110
4 210 120 100 90
200 100 82 75
6 8 7 7 2
7 245 140 110 95
8 210 110 90 81
9 200 100 83 80
185 86 75 71
Comparative 0 0 0 0
Example
Table 10 – Blender Foaming in 2% KCl
Foam Volume( m L)
Example
t = 5 t = 10
Initial t = 15 min
min min
1 - - - -
2 170 31 30 30
3 150 39 34 34
4 130 25 21 18
25 15 15 15
6 - - - -
7 175 29 28 28
8 135 30 30 30
9 125 26 24 19
115 14 122 10
Comparative 14 7 0 0
Example
Examples 1 and 6 were not stable in 2% KCl and thus the blender
foaming test could not be conducted.
- = not tested
The blender foaming results in deionized water and 2% KCl shown
in Tables 9 and 10, respectively, demonstrated improved foaming and
more sustainable foam with time over the Comparative Example.
Foaming properties are desirable for cleaning solutions where the foam is
used to promote adhesion of the active cleaning ingredient on the surface.
In oilfield stimulation and drilling applications surfactant additives that help
boost the foaming properties of the fluids are desirable.
Where the terms “comprise”, “comprises”, “comprised” or
“comprising” are used in this specification, they are to be interpreted as
specifying the presence of the stated features, integers, steps or
components referred to, but not to preclude the presence or addition of
one or more other feature, integer, step, component or group thereof.
Claims (17)
1. A composition comprising formula I, formula II, or formula III ( R -A-Z) (O M ) (Fo rmula I) R -A-Z-CH R -A-Z-CH M ( Fo rmula II) R -A-Z P O M OROH (Fo rmula III) wherein 10 R is a C to C linear or branched perfluoroalkyl optionally f 1 6 interrupted by one, two or three ether oxygen atoms; x is 1 to 2; A is (C H ) , (C H CF ) ( C H ) , (C H ) SO N(C H ) ( C H ) , 2 k 2 2 m 2 n 2 o 2 3 2 p O( C F ) ( C H ) , or OCHFCF OE; 2 2 2 r 2 15 Z is O or S; m is 1 to 4; k, n, o, p, and r are each independently 1 to 20; E is a C to C linear or branched alkyl group optionally 2 20 interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a 20 C to C aryl group; 6 10 R is a C to C linear or branched alkyl group optionally 2 60 interrupted by hetero atoms selected from the group consisting of an oxygen, sulfur, or nitrogen atom; a cyclic alkyl; or a C to C aryl; 6 10 provided that when R is greater than 8 carbons, the ratio of hetero atoms to carbon atoms is at least 1:2; and 1 2 + 1 2 M is an ammonium cation (N H R R ) wherein R and R are independently hydrogen, linear or branched organic groups containing at 5 least one carboxylate moiety and one amino moiety, and optionally be substituted, interrupted, or both with oxygen, sulfur, or nitrogen-containing moieties, or with cyclic alkyl or aryl moieties containing up to 10 carbon atoms, with the proviso that at least one of R and R is a linear or 10 branched organic group containing at least one carboxylate moiety and one amino moiety.
2. A composition of Claim 1, wherein R is a C to C linear f 4 6 perfluoroalkyl, A is ( C H ) , and k is 2.
3. A composition of Claim 1, wherein R is a C to C linear f 4 6 15 perfluoroalkyl, A is (C H CF ) ( C H ) , m is 1, and n is 2. 2 2 m 2 n
4. A composition of Claim 1, wherein R is a C linear perfluoroalkyl A is O(C F ) ( C H ) , and r is 2. 2 2 2 r
5. A composition of Claim 1, wherein M is an ammonium cation 1 2 + 1 2 (N H R R ) wherein R and R are independently hydrogen, linear or 20 branched organic groups containing at least one carboxylate moiety and one amino moiety.
6. A composition of Claim 5, wherein M is
7. A composition of Claim 1, where M is an ammonium cation 25 (N H R) wherein R is a linear or branched organic group containing at least one carboxylate moiety and one amino moiety, and optionally be substituted, interrupted, or both with oxygen, sulfur, or nitrogen-containing moieties, or with cyclic alkyl or aryl moieties containing up to 10 carbon atoms.
8. A composition of Claim 7, wherein M is NH O H N NH O
9. A method of lowering the surface tension of a liquid comprising contacting a liquid to a composition comprising formula I, formula II, or formula III (R -A-Z) P (O M ) 10 (Fo rmula I) R -A-Z-CH R -A-Z-CH M (Fo rmula II) R -A-Z P O M OROH ( Fo rmula III) 15 wherein R is a C to C linear or branched perfluoroalkyl optionally f 1 6 interrupted by one, two or three ether oxygen atoms; x is 1 to 2; A is (C H ) , ( C H CF ) ( C H ) , ( C H ) SO N(C H )( C H ) , 2 k 2 2 m 2 n 2 o 2 3 2 p 20 O(C F ) (C H ) , or OCHFCF OE; 2 2 2 r 2 Z is O or S; m is 1 to 4; k, n, o, p, and r are each independently 1 to 20; E is a C to C linear or branched alkyl group optionally 2 20 interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a 5 C to C aryl group; 6 10 R is a C to C linear or branched alkyl group optionally 2 60 interrupted by hetero atoms selected from the group consisting of an oxygen, sulfur, or nitrogen atom; a cyclic alkyl; or a C to C aryl; 6 10 provided that when R is greater than 8 carbons, the ratio of hetero atoms
10 to carbon atoms is at least 1:2; and 1 2 + 1 2 M is an ammonium cation (N H R R ) wherein R and R are independently hydrogen, linear or branched organic groups containing at least one carboxylate moiety and one amino moiety, and optionally be substituted, interrupted, or both with oxygen, sulfur, or nitrogen-containing 15 moieties, or with cyclic alkyl or aryl moieties containing up to 10 carbon atoms, with the proviso that at least one of R and R is a linear or branched organic group containing at least one carboxylate moiety and one amino moiety. 20 10. The method of claim 9, wherein the liquid is selected from the group consisting of wherein the medium is water, saline solution, KCl solution, drill fluids, well fluids, liquid treatment or gas treatment stream for subterranean formation and well bore areas, hydrocarbon, halocarbon system, coating composition, latex, polymer, floor finish, floor polish, fire 25 fighting agent, ink, emulsifying agent, foaming agent, release agent, repellency agent, flow modifier, film evaporation inhibitor, wetting agent, penetrating agent, cleaner, grinding agent, electroplating agent, corrosion inhibitor, etchant solution, soldering agent, dispersion aid, microbial agent, pulping aid, rinsing aid, polishing agent, personal care composition, drying 30 agent, antistatic agent, or bonding agent.
11. The method of claim 10, wherein the coating composition is an alkyd coating, a Type I urethane coating, an unsaturated polyester coating, or a water-dispersed coating.
12. A composition comprising a liquid treated in accordance of Claim 9. 5 13. A method of imparting surface effects to a substrate comprising contacting at least a portion of a surface of the substrate with a coating composition containing a composition comprising formula I, formula II, or formula III (R -A-Z) P ( O M ) 10 (Fo rmula I) R -A-Z-CH R -A-Z-CH M (Fo rmula II) R -A-Z P O M OROH (Fo rmula III) 15 wherein R is a C to C linear or branched perfluoroalkyl optionally f 1 6 interrupted by one, two or three ether oxygen atoms; x is 1 to 2;
A is ( C H ) , (C H CF ) (C H ) , ( C H ) SO N( C H )( C H ) , 2 k 2 2 m 2 n 2 o 2 3 2 p 20 O(C F ) (C H ) , or OCHFCF OE; 2 2 2 r 2 Z is O or S; m is 1 to 4; k, n, o, p, and r are each independently 1 to 20; E is a C to C linear or branched alkyl group optionally 2 20 interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a C to C aryl group; 6 10 R is a C to C linear or branched alkyl group optionally 2 60 5 interrupted by hetero atoms selected from the group consisting of an oxygen, sulfur, or nitrogen atom; a cyclic alkyl; or a C to C aryl; 6 10 provided that when R is greater than 8 carbons, the ratio of hetero atoms to carbon atoms is at least 1:2; and 1 2 + 1 2 M is an ammonium cation (N H R R ) wherein R and R are 10 independently hydrogen, linear or branched organic groups containing at least one carboxylate moiety and one amino moiety, and optionally be substituted, interrupted, or both with oxygen, sulfur, or nitrogen-containing moieties, or with cyclic alkyl or aryl moieties containing up to 10 carbon atoms, 15 with the proviso that at least one of R and R is a linear or branched organic group containing at least one carboxylate moiety and one amino moiety.
14. A method of Claim 13, wherein the coating composition is an alkyd coating, a Type I urethane coating, an unsaturated polyester coating, or a 20 water-dispersed coating.
15. A method of Claim 14, wherein the coating composition is applied to the substrate prior to contacting with a composition comprising formula I, formula II, or formula III.
16. A method of Claim 13, wherein the surface effects are lowering 25 surface tension, water repellency, oil repellency, stain resistance, soil resistance, and resistance to blocking, increased contact angle, wetting and leveling.
17. A substrate treated in accordance of method of Claim 13.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161556418P | 2011-11-04 | 2011-11-04 | |
US61/556,418 | 2011-11-07 | ||
US13/400,176 US9328317B2 (en) | 2011-11-04 | 2012-02-20 | Fluorophosphate surfactants |
US13/400,176 | 2012-02-20 | ||
PCT/US2012/036916 WO2013066400A1 (en) | 2011-11-04 | 2012-05-08 | Fluorophosphate surfactants |
Publications (2)
Publication Number | Publication Date |
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NZ622972A NZ622972A (en) | 2015-06-26 |
NZ622972B2 true NZ622972B2 (en) | 2015-09-29 |
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