Sulfonated fluorinated, non-fluorinated or partially fluorinated urethanes

1. A compound having 0 to about 1% reactive isocyanate groups comprising the reaction product of reagents comprising:

(a) at least one isocyanate group-containing compound selected from diisocyanate, polyisocyanate, or mixture thereof;

(b) at least one isocyanate-reactive compound selected from the group consisting of a fluorinated alcohol; a cyclic or acyclic sugar alcohol which is substituted with at least one R 1 , —C(O)R 1 , —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 , —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 , or mixtures thereof; and mixtures of a fluorinated alcohol and a cyclic or acyclic sugar alcohol which is substituted with at least one R 1 , —C(O)R 1 , —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 , —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 , or mixtures thereof;

where the cyclic or acyclic sugar alcohol is selected from a saccharide, reduced sugar, aminosaccharide, aldonic acid, or aldonic acid lactone; wherein

each n is independently 0 to 20;

each m is independently 0 to 20;

m+n is greater than 0;

each R 1 is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond;

each R 2 is independently —H, or a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond, or mixtures thereof;

(c) at least one isocyanate-reactive ethylenically unsaturated compound selected from allylic or methallylic polyether alcohols, aminoalkyl vinyl compounds, acrylic or methacrylic alkyl alcohols, acrylic or methacrylic polyether alcohols, or acrylic or methacrylic amines; and

(d) a bisulfate source.

2. The compound of claim 1 , where the isocyanate-reactive compound (b) is selected from formulas (IIa), (IIb), or (IIc):

wherein each R is independently —H; —R 1 ; —C(O)R 1 ;

—(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 ; or

—(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 ;

each n is independently 0 to 20;

each m is independently 0 to 20;

m+n is greater than 0;

r is 1 to 3;

a is 0 or 1;

p is independently 0 to 2;

provided that a is 0 when r is 3;

each R 1 is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond;

each R 2 is independently —H, or a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond;

or a mixtures thereof,

provided when formula (IIa) is chosen, then at least one R is —H and at least one R is a —R 1 ; —C(O)R 1 ; —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 ;

or —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 ;

each R 4 is independently —H, a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond, or combinations thereof; —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 ; or —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 ;

provided when formula (IIb) is chosen, then at least one R or R 4 is —H; and at least one R or R 4 is a linear or branched alkyl group optionally comprising at least 1 unsaturated bond, or combinations thereof; —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 ; or —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 ; and

each R 19 is —H, —C(O)R 1 , or —CH 2 C[CH 2 OR] 3 ,

provided when formula (IIc) is chosen, then at least one R 19 or R is —H; and

at least one R 19 or R is —C(O)R 1 , —(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 ; or

—(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 .

3. The compound of claim 2 wherein the isocyanate-reactive compound (b) is selected from formula (IIa) to be formula (IIa′):

wherein R is further limited to independently —H; —R 1 ; or —C(O)R 1 .

4. The compound of claim 2 wherein the isocyanate-reactive compound (b) is selected from formula (IIa) to be formula (IIa′):

wherein R is further limited to independently —H;

—(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m R 2 ; or

—(CH 2 CH 2 O) n (CH(CH 3 )CH 2 O) m C(O)R 1 .

5. The compound of claim 1 , where the isocyanate-reactive compound (b) is a fluorinated alcohol having formula (I)

R f -A-OH  (I),

where R f is a C 1 to C 20 fluoroalkyl group optionally interrupted by CH 2 , CH 2 CH 2 , SO 2 N, CFH, S, or O; and

A is a direct bond or a C 1 to C 6 alkylene group.

6. The compound of claim 1 , where the bisulfate source (d) is a metabisulfite salt, a bisulfite salt, or a mixture of SO 2 and base.

7. The compound of claim 1 , wherein the diisocyanate or polyisocyanate is selected from formulas (IIIa), (IIIb), (IIIc), (IIId), and (IIIe):

8. The compound of claim 1 , wherein the reagents further comprise at least one additional isocyanate-reactive compound (e) selected from water, organic compounds of formula (IVa)

R 5 -D  (IVa), or

organic compounds of formula (IVb)

R 3 —(OCH 2 CH(OR 3 )CH 2 )z-OR 3   (IVb),

or mixtures thereof, wherein

R 5 is selected from a —C 1 to C 30 linear or branched alkyl optionally comprising at least one unsaturated group, a hydroxy-functional C 1 to C 30 linear or branched alkyl, a hydroxy-functional linear or branched C 1 to C 30 polyether, a hydroxy-functional linear or branched polyester having a polyester polymer backbone, a hydroxy-functional linear or branched organosiloxane, an amine-functional linear or branched organosiloxane, a thiol-functional C 1 to C 30 linear or branched alkyl, an amine-functional C 1 to C 30 linear or branched alkyl,

D is selected from —N(R 12 )H, —OH, —COOH, —SH, —O—(CH 2 CH 2 O) s (CH(CH 3 CH 2 O) t —H, or (C(O)—O—(CH 2 CH 2 O) s (CH(CH 3 )CH 2 O) t H;

R 3 is independently selected from —H; —R 18 ; or —C(O)R 18 , provided that at least one R 3 is —H;

R 12 is —H or a monovalent C 1 to C 6 alkyl group;

R 7 , R 8 , and R 9 are each independently, —H, to C 6 alkyl, or combinations thereof;

R 10 is a divalent alkyl group of 1 to 20 carbons;

R 18 is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond;

z is 1 to 15;

Y is Cl;

s is an integer of 0 to 50;

t is an integer of 0 to 50; and

s+t is greater than 0.

9. An aqueous composition comprising the compound of claim 1 .

10. A method of reducing the surface tension of an aqueous medium comprising contacting the aqueous medium with a compound of claim 1 .

11. A coating composition made by the method of claim 10 , wherein the aqueous medium is an aqueous coating base.

12. A method of providing a surface effect to a fibrous substrate comprising contacting a fibrous substrate with a compound of claim 1 .

13. A fibrous substrate which has been treated by the method of claim 12 .