Sulfonated fluorinated, non-fluorinated or partially fluorinated urethanes

Abstract

The invention relates to a compound prepared by (i) reacting (a) at least one compound selected from diisocyanate, polyisocyanate, or mixture thereof; (b) at least one isocyanate-reactive compound selected from 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(0)R 1 , or mixtures thereof; or mixtures of a fluorinated alcohol and a substituted cyclic or acyclic sugar alcohol; and (c) at least one isocyanate-reactive ethylenically unsaturated compound; 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; and (ii) reacting the reaction product of step (i) with a bisulfate source.

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         10 . A method of preparing a compound comprising:
 (i) reacting (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; and (c) at least one isocyanate-reactive ethylenically unsaturated compound;   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; and   (ii) reacting the reaction product of step (i) with (d) a bisulfate source in the presence of a radical initiator.   
     
     
         11 . The method of  claim 10 , 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 . 
       
     
     
         12 . The method of  claim 10 , 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, or O; and   A is a direct bond or a C 1  to C 6  alkylene group.   
     
     
         13 . The method of  claim 10 , where the isocyanate-reactive ethylenically unsaturated compound (c) is selected from hydroxyalkyl vinyl compounds, allylic or methallylic polyether alcohols, aminoalkyl vinyl compounds, acrylic or methacrylic alkyl alcohols, acrylic or methacrylic polyether alcohols, or acrylic or methacrylic amines. 
     
     
         14 . The method of  claim 10 , where the bisulfate source is a metabisulfite salt, a bisulfite salt, or a mixture of SO 2  and base. 
     
     
         15 . The method of  claim 10 , wherein the diisocyanate or polyisocyanate is selected from formulas (IIIa), (IIIb), (IIIc), (IIId), and (IIIe): 
       
         
           
           
               
               
           
         
       
     
     
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         21 . The method of  claim 10 , where the compound contains about 0% to about 1% of reactive isocyanate groups. 
     
     
         22 . The method of  claim 10 , wherein the reagents of step (i) 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, —C 1  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. 
       
     
     
         23 . The method of  claim 11  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 . 
       
     
     
         24 . The method of  claim 11  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 .