Fluorophosphate surfactants
View Patent ↗This invention is directed to a composition capable of imparting surface effects to a liquid by contacting the liquid with a partially fluorinated phosphate with an ammonium cation (NH 2 R 1 R 2 ) + wherein R 1 and R 2 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.
1. A composition comprising formula I, formula II, or formula
wherein
R f is a C 1 to C 6 linear or branched perfluoroalkyl optionally interrupted by one, two or three ether oxygen atoms;
x is 1 to 2;
A is (CH 2 ) k , (CH 2 CF) m (CH 2 ) n , (CH 2 )OSO 2 N(CH 3 )(CH 2 ) p , O(CF 2 ) 2 (CH 2 ) r , or OCHFCF 2 OE;
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 2 to C20 linear or branched alkyl group optionally interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a C 6 to C 10 aryl group;
R is a C 2 to C 60 linear or branched alkyl group optionally interrupted by hetero atoms selected from the group consisting of an oxygen, sulfur, or nitrogen atom; a cyclic alkyl; or a C 6 to C 10 aryl; provided that when R is greater than 8 carbons, the ratio of hetero atoms to carbon atoms is at least 1:2; and
M is an ammonium cation (NH 2 R 1 R 2 ) + wherein R 1 and R 2 are linear or branched organic groups which, collectively as R 1 R 2 , contain at least one carboxylate moiety and one amino moiety, said linear or branched organic groups being optionally substituted, interrupted, or both with sulfur-containing moieties, nitrogen-containing moieties, cyclic alkyl moieties, or aryl moieties, where said cyclic alkyl or aryl moieties contain up to 10 carbon atoms.
2. A composition of claim 1 , wherein R f is a C 4 to C 6 linear perfluoroalkyl, A is (CH 2 ) k , and k is 2.
3. A composition of claim 1 , wherein R f is a C 4 to C 6 linear perfluoroalkyl, A is (CH 2 CF 2 ) m (CH 2 ) n , m is 1, and n is 2.
4. A composition of claim 1 , wherein R f is a C 3 linear perfluoroalkyl A is O(CF 2 ) 2 (CH 2 ) r , and r is 2.
5. A composition of claim 1 , wherein M is an ammonium cation (NH 2 R 1 R 2 ) + wherein R 1 and R 2 are unsubstituted and uninterrupted linear or branched organic groups which, collectively as R 1 R 2 , contain at least one carboxylate moiety and one amino moiety.
6. A composition comprising formula I, formula II, or formula III
wherein
R f is a C 1 to C 6 linear or branched perfluoroalkyl optionally interrupted by one, two or three ether oxygen atoms;
x is 1 to 2;
A is (CH 2 ) k , (CH 2 CF 2 ) m (CH 2 ) n , (CH 2 )OSO 2 N(CH 3 )(CH 2 ) p , O(CF 2 ) 2 (CH 2 ) r , or OCHFCF 2 OE;
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 2 to C 20 linear or branched alkyl group optionally interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a C 6 to C 10 aryl group;
R is a C 2 to C 10 linear or branched alkyl group optionally interrupted by hetero atoms selected from the group consisting of an oxygen, sulfur, or nitrogen atom; a cyclic alkyl; or a C 6 to C 10 aryl; provided that when R is greater than 8 carbons, the ratio of hetero atoms to carbon atoms is at least 1:2; and
wherein M is
7. A composition comprising formula I, formula II, or formula III
wherein
R f is a C 1 to C 6 linear or branched perfluoroalkyl optionally interrupted by one, two or three ether oxygen atoms;
x is 1 to 2;
A is (CH 2 ) k , (CH 2 CF 2 ) m (CH 2 ) n , (CH 2 )OSO 2 N(CH 3 )(CH 2 ) p , O(CF 2 ) 2 (CH 2 ) r , or OCHFCF 2 OE;
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 2 to C 20 linear or branched alkyl group optionally interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a C 6 to C 10 aryl group;
R is a C 2 to C 10 linear or branched alkyl group optionally interrupted by hetero atoms selected from the group consisting of an oxygen, sulfur, or nitrogen atom: a cyclic alkyl; or a C 6 to C 10 aryl; provided that when R is greater than 8 carbons, the ratio of hetero atoms to carbon atoms is at least 1:2; and
where M is an ammonium cation (NH 3 R) 4 wherein R is linear or branched organic group containing at least one carboxylate moiety and one amino moiety, said linear or branched organic groups being optionally substituted, interrupted, or both with sulfur-containing moieties, nitrogen-containing moieties, cyclic alkyl moieties, or aryl moieties, where said cyclic alkyl or aryl moieties contain up to 10 carbon atoms.
8. A composition of claim 7 , wherein M is
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
wherein
R f is a C 1 to C 6 linear or branched perfluoroalkyl optionally interrupted by one, two or three ether oxygen atoms;
x is 1 to 2;
A is (CH 2 ) k , (CH 2 CF 2 ) m (CH 2 ) n , (CH 2 )OSO 2 N(CH 3 )(CH 2 ) p , O(CF 2 ) 2 (CH 2 ) r , or OCHFCF 2 OE;
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 2 to C 20 linear or branched alkyl group optionally interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a C 6 to C 10 aryl group;
R is a C 2 to C 60 linear or branched alkyl group optionally interrupted by hetero atoms selected from the group consisting of an oxygen, sulfur, or nitrogen atom; a cyclic alkyl; or a C 6 to C 10 aryl; provided that when R is greater than 8 carbons, the ratio of hetero atoms to carbon atoms is at least 1:2; and
M is an ammonium cation (NH 2 R 1 R 2 ) + wherein R 1 and R 2 are linear or branched organic groups which, collectively as R 1 R 2 , contain at least one carboxylate moiety and one amino moiety, said linear or branched organic groups being optionally substituted, interrupted, or both with sulfur-containing moieties, nitrogen-containing moieties, cyclic alkyl moieties, or aryl moieties, where said cyclic alkyl or aryl moieties contain up to 10 carbon atoms.
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 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.
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 by contacting the liquid with a phosphate composition comprising formula I, formula II, or formula III
wherein
R f is a C 1 to C 6 linear or branched perfluoroalkyl optionally interrupted by one, two or three ether oxygen atoms;
x is 1 to 2;
A is (CH 2 ) k , (CH 2 CF 2 ) m (CH 2 ) n , (CH 2 )OSO 2 N(CH 3 )(CH 2 ) p , O(CF 2 ) 2 (CH 2 ) r , or OCHFCF 2 OE;
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 2 to C 20 linear or branched alkyl group optionally interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a C 6 to C 10 aryl group;
R is a C 2 to C 60 linear or branched alkyl group optionally interrupted by hetero atoms selected from the group consisting of an oxygen, sulfur, or nitrogen atom; a cyclic alkyl; or a C 6 to C 10 aryl; provided that when R is greater than 8 carbons, the ratio of hetero atoms to carbon atoms is at least 1:2; and
M is an ammonium cation (NH 2 R 1 R 2 ) + wherein R 1 and R 2 are linear or branched organic groups which, collectively as R 1 R 2 , contain at least one carboxylate moiety and one amino moiety, said linear or branched organic groups being optionally substituted, interrupted, or both with sulfur-containing moieties, nitrogen-containing moieties, cyclic alkyl moieties, or aryl moieties, where said cyclic alkyl or aryl moieties contain up to 10 carbon atoms.
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
wherein
R f is a C 1 to C 6 linear or branched perfluoroalkyl optionally interrupted by one, two or three ether oxygen atoms;
x is 1 to 2;
A is (CH 2 ) k , (CH 2 CF 2 ) m (CH 2 ) n , (CH 2 )OSO 2 N(CH 3 )(CH 2 ) p , O(CF 2 ) 2 (CH 2 ) r , or OCHFCF 2 OE;
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 2 to C 20 linear or branched alkyl group optionally interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a C 6 to C 10 aryl group;
R is a C 2 to C 60 linear or branched alkyl group optionally interrupted by hetero atoms selected from the group consisting of an oxygen, sulfur, or nitrogen atom; a cyclic alkyl; or a C 6 to C 10 aryl; provided that when R is greater than 8 carbons, the ratio of hetero atoms to carbon atoms is at least 1:2; and
M is an ammonium cation (NH 2 R 1 R 2 ) + wherein R 1 and R 2 are linear or branched organic groups which, collectively as R 1 R 2 , contain at least one carboxylate moiety and one amino moiety, said linear or branched organic groups being optionally substituted, interrupted, or both with sulfur-containing moieties, nitrogen-containing moieties, cyclic alkyl moieties, or aryl moieties, where said cyclic alkyl or aryl moieties contain up to 10 carbon atoms.
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 water-dispersed coating.
15. A method of claim 13 , wherein the surface effects are lowering surface tension, water repellency, oil repellency, stain resistance, soil resistance, and resistance to blocking, increased contact angle, wetting and leveling.