Process for incorporating poorly substantive paper modifying agents into a paper sheet via wet end addition

Abstract

Synthetic co-polymers having moieties capable of forming hydrogen bonds, ionic bonds, or covalent bonds with cellulose fibers and paper modifying moieties capable of modifying a paper sheet are disclosed. These synthetic co-polymers are derived from the reaction of an aldehyde functional polymer and an aldehyde reactive paper modifying agent containing a non-hydroxyl aldehyde reactive functional group.

We claim:  
     
         1 . A synthetic co-polymer derived from the reaction of an aldehyde functional polymer and an aldehyde reactive paper modifying agent containing a non-hydroxyl aldehyde reactive functional group, said synthetic co-polymer having the following structure:  
       
         
           
           
               
               
           
         
       
       wherein: 
 f>0;  
 a, c, e≧0;  
 w≧1;  
 Q 1 =a monomer unit or a block or graft copolymer prepared from the polymerization of one or more ethylenically unsaturated compounds containing a pendant group capable of forming hydrogen bonds with cellulose;  
 R 1 , R 1′ , R 1″  =independently H or C 1-4  alkyl;  
 R 2 =any linear or branched, aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon group containing a pendant aldehyde functionality;  
 R 3 =an aliphatic hydrocarbon, a polysiloxane, an amphiphilic hydrocarbon, a humectant, or other agent capable of modifying a paper sheet;  
 Z 2 =a covalently bonded bridging radical formed by the reaction of an aldehyde functionality with a reactive entity on the aldehyde reactive paper modifying agent; and,  
 Q 3 =a monomer unit or a block or graft copolymer containing a charge functionality wherein the charge functionality is selected from the group consisting of: cationic; anionic; and, amphoteric.  
 
     
     
         2 . The synthetic co-polymer of  claim 1 , wherein the pendant group on Q 1  capable of forming hydrogen bonds is selected from the group consisting of: —CONH 2 ; —COOH; —COO − M + ; —OH; and, mixtures thereof, wherein M +  is a counter ion.  
     
     
         3 . The synthetic co-polymer of  claim 1 , wherein the hydrocarbon group R 2  containing aldehyde functionality is selected from the group consisting of: —CONHCHOHCHO; —CONHCHOH(CH 2 ) 2 CHO; and, mixtures thereof.  
     
     
         4 . The synthetic co-polymer of  claim 1 , wherein the aldehyde functional polymer is selected from the group consisting of: water dispersible anionic aldehyde functional polymers; water dispersible cationic aldehyde functional polymers; water dispersible nonionic aldehyde functional polymers; water-soluble anionic aldehyde functional polymers; water-soluble cationic aldehyde functional polymers; and, water-soluble non-ionic aldehyde functional polymers.  
     
     
         5 . The synthetic co-polymer of  claim 1 , wherein the R 3  moiety is a linear or branched, saturated or unsaturated, aromatic or aliphatic hydrocarbon of C 2  to C 40  chain length.  
     
     
         6 . The synthetic co-polymer of  claim 1 , wherein the synthetic co-polymer is a product of the reaction of the aldehyde functional polymer and the aldehyde reactive paper modifying agent containing wherein the aldehyde reactive paper modifying agent is a polysiloxane and having the following structure:  
       
         
           
           
               
               
           
         
       
       wherein: 
 x, y=integers>0 such that the mole ratio of x to (x+y) is from about 0.001 percent to about 25 percent; and,  
 R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9  moieties are independently any organofunctional group including C 1  to C 30  alkyl groups, ethers, polyethers, polyesters, amines, imines, amides, or other functional groups including the alkyl and alkenyl analogues of such groups,  
 wherein at least one of R 2 , R 5 , and R 10  moieties is an organofunctional moiety containing a non-hydroxyl functional group capable of reacting with an aldehyde group to form a covalent bond.  
 
     
     
         7 . The synthetic co-polymer of  claim 6 , wherein the aldehyde functional polymer is a cationic, anionic, or non-ionic glyoxylated polyacrylamide and the polysiloxane organofunctional moiety capable of reacting with an aldehyde group that is a primary amine, secondary amine, or unsubstituted amide.  
     
     
         8 . The synthetic co-polymer of  claim 1 , wherein the synthetic co-polymer is the product of the reaction of an aldehyde functional polymer and an amphiphilic paper modifying agent containing a non-hydroxyl aldehyde reactive group.  
     
     
         9 . The synthetic co-polymer of  claim 8 , wherein the aldehyde functional polymer is a cationic, anionic, or non-ionic glyoxylated polyacrylamide and the aldehyde reactive functional group on the amphiphilic paper modifying agent is selected from the group consisting of: primary amine; secondary amine; and, unsubstituted amide.  
     
     
         10 . The synthetic co-polymer of  claim 8 , wherein the aldehyde reactive paper modifying agent is selected from the group consisting of: 1-amino-2-propanol; 2-amino-1-propanol; 3-amino-1,2-propanediol; tris(hydroxymethyl) aminomethane; diethanol amine; 1-amino-1-deoxy-D-sorbitol (glucamine); glucosamine; N-methyl glucamine; 2-aminoethyl hydrogen sulfate; 2-amino-2-ethyl-1,3-propanediol; 2-amino-1phenyl-1,3-propanediol; 2-amino-1,3-propanediol; 3-amino-1-propanol; ethanolamine; 3-amino-2-hydroxy propionic acid; 1-amino-2,3,4-trihydroxybutane; 4-amino-2-hydroxybutyric acid; aspartic acid; 2-amino-2-methyl-1,3-propanediol; 2-amino-1,3-propanediol; 3-mercapto-1,2-propanediol; mercaptosuccinic acid; and, mixtures thereof.  
     
     
         11 . The synthetic co-polymer of  claim 8 , wherein the aldehyde reactive paper modifying agent is a derivative of a polyalkyleneoxy functional compound.  
     
     
         12 . The synthetic co-polymer of  claim 8 , wherein the aldehyde reactive paper modifying agent is a polyalkyleneoxy amine, diamine, thiol, dithiol, unsubstituted amide, or unsubstituted diamide.  
     
     
         13 . The synthetic co-polymer of  claim 8 , wherein the aldehyde reactive paper modifying agent is selected from the group consisting of: polyalkyleneoxy amine; diamine; thiol; and, dithiol, and having the following structure:  
       
         
           
           
               
               
           
         
       
       wherein: 
 Z 4 =a non-hydroxyl aldehyde reactive functionality selected from the group consisting of: primary amine; secondary amine; thiol; or, unsubstituted amide;  
 a, b, c=integers greater≧0 such that a+b+c≧2;  
 n=an integer≧2 and≦6; and,  
 R═H; C 1 -C 30  linear or branched, substituted or non-substituted, aliphatic or aromatic, saturated or unsaturated hydrocarbon; —[CH 2 CHCH 3 ]-Z 4 ; or, [(CH 2 ) n ]-Z 4 .  
 
     
     
         14 . The synthetic co-polymer of  claim 8 , wherein the aldehyde reactive paper modifying agent is an amino acid.  
     
     
         15 . The synthetic co-polymer of  claim 1 , wherein the Z 2  moiety is selected from the group consisting of: —CONHCHOHCHOHNH—; —CONHCHOHCH═N—; —CONHCHOHCH(NH—) 2 ; and, mixtures thereof.  
     
     
         16 . The synthetic co-polymer of  claim 1 , wherein Q 3  is  
       
         
           
           
               
               
           
         
       
     
     
         17 . The synthetic co-polymer of  claim 1 , wherein Q 3  is a radical of the form —CHR 1 CR 0 R 1′ — wherein: 
 R 0 =a pendant group of the form Z 1 -R 10 —W, where Z 1  is a radical bonding the R 10  group to the synthetic co-polymer;  
 R 1 , R 1 ′=independently H or a C 1-4  alkyl group;  
 R 10 =any linear or branched, aliphatic or aromatic hydrocarbon of at least a C 2  chain length; and,  
 W═N + R 11 , R 12 , R 13  where R 11 , R 12 , and R 13  are each independently a C 1-4  alkyl group.  
 
     
     
         18 . The synthetic co-polymer of  claim 1 , wherein the pendant group on Q 1  capable of forming hydrogen bonds is —CONH 2 .  
     
     
         19 . The synthetic co-polymer of  claim 1 , wherein Q 1  has —CONH 2  and -Z 5 R′ pendant groups wherein Z 5  is a bridging radical bonding the R′ group to the synthetic co-polymer and R′ is a C, to C 30  aliphatic hydrocarbon.  
     
     
         20 . A paper sheet comprising a synthetic co-polymer derived from the reaction of an aldehyde functional polymer and an aldehyde reactive paper modifying agent containing an aldehyde reactive functional group, said synthetic co-polymer having the following structure:  
       
         
           
           
               
               
           
         
       
       wherein: 
 f>0;  
 a, c, e≧0;  
 w≧1;  
 Q 1 =a monomer unit or a block or graft copolymer prepared from the polymerization of one or more ethylenically unsaturated compounds containing a pendant group capable of forming hydrogen bonds with cellulose;  
 R 1 , R 1′ , R 1″ =independently H or C 1-4  alkyl;  
 R 2 =any linear or branched, aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon group containing a pendant aldehyde functionality;  
 R 3 =an aliphatic hydrocarbon, a polysiloxane, an amphiphilic hydrocarbon, a humectant, or other agent capable of modifying a paper sheet;  
 Z 2 =a covalently bonded bridging radical formed by the reaction of an aldehyde functionality with a reactive entity on the aldehyde reactive paper modifying agent; and,  
 Q 3 =a monomer unit or a block or graft copolymer containing a charge functionality wherein the charge functionality is selected from the group consisting of: cationic; anionic; and, amphoteric.  
 
     
     
         21 . The paper sheet of  claim 20 , wherein the pendant group on Q 1  capable of forming hydrogen bonds is selected from the group consisting of: —CONH 2 ; —COOH; —COO − M + ; —OH; and, mixtures thereof, wherein M +  is a counter ion.  
     
     
         22 . The paper sheet of  claim 20 , wherein the hydrocarbon group R 2  containing aldehyde functionality is selected from the group consisting of: —CONHCHOHCHO; —CONHCHOH(CH 2 ) 2 CHO; and, mixtures thereof.  
     
     
         23 . The paper sheet of  claim 20 , wherein the aldehyde functional polymer is selected from the group consisting of: water dispersible anionic aldehyde functional polymers; 
 water dispersible cationic aldehyde functional polymers; water dispersible non-ionic aldehyde functional polymers; water-soluble anionic aldehyde functional polymers; water-soluble cationic aldehyde functional polymers; and, water-soluble non-ionic aldehyde functional polymers.    
     
     
         24 . The paper sheet of  claim 20 , wherein the R 3  moiety is a linear or branched, saturated or unsaturated, aromatic or aliphatic hydrocarbon of at least a C 2  to C 40  chain length.  
     
     
         25 . The paper sheet  claim 20 , wherein the synthetic co-polymer is a product of the reaction of the aldehyde functional polymer and the aldehyde reactive paper modifying agent wherein the aldehyde reactive paper modifying agent is a polysiloxane and having the following structure:  
       
         
           
           
               
               
           
         
       
       wherein: 
 x, y=integers≧0 such that the mole ratio of x to (x+y) is from about 0.001 percent to about 25 percent; and,  
 R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9  moieties are independently any organofunctional group including C, to C 3-0  alkyl groups, ethers, polyethers, polyesters, amines, imines, amides, or other functional groups including the alkyl and alkenyl analogues of such groups,  
  wherein at least one of R 2 , R 5 , and R 10  moieties is an organofunctional moiety containing a non-hydroxyl functional group capable of reacting with an aldehyde group to form a covalent bond.  
 
     
     
         26 . The paper sheet of  claim 25 , wherein the aldehyde functional polymer is a cationic, anionic, or non-ionic glyoxylated polyacrylamide and the polysiloxane organofunctional moiety capable of reacting with an aldehyde group is a primary amine, secondary amine, or unsubstituted amide.  
     
     
         27 . The paper sheet of  claim 20 , wherein the synthetic co-polymer is the product of the reaction of an aldehyde functional polymer and an amphiphilic hydrocarbon paper modifying agent containing a non-hydroxyl aldehyde reactive group.  
     
     
         28 . The paper sheet of  claim 27 , wherein the aldehyde functional polymer is a cationic, anionic, or non-ionic glyoxylated polyacrylamide and the aldehyde reactive functional group on the amphiphilic paper modifying agent is selected from the group consisting of: primary amine; secondary amine; and, unsubstituted amide.  
     
     
         29 . The paper sheet of  claim 27 , wherein the aldehyde reactive paper modifying agent is selected from the group consisting of: 1-amino-2-propanol; 2-amino-1-propanol; 3-amino-1,2-propanediol; tris(hydroxymethyl) aminomethane; diethanol amine; 1-amino-1-deoxy-D-sorbitol (glucamine); glucosamine; N-methyl glucamine; 2-aminoethyl hydrogen sulfate; 2-amino-2-ethyl-1,3-propanediol; 2-amino-1 phenyl-1,3-propanediol; 2-amino-1,3-propanediol; 3-amino-1-propanol; ethanolamine; 3-amino-2-hydroxy propionic acid; 
 1-amino-2,3,4-trihydroxybutane; 4-amino-2-hydroxybutyric acid; aspartic acid; 2-amino-2-methyl-1,3 propanediol; 2-amino-1,3-propanediol; 3-mercapto-1,2-propanediol; mercaptosuccinic acid; and, mixtures thereof.    
     
     
         30 . The paper sheet of  claim 27 , wherein the aldehyde reactive paper modifying agent is a derivative of a polyalkyleneoxy functional compound.  
     
     
         31 . The paper sheet of  claim 27 , wherein the aldehyde reactive paper modifying agent is a polyalkyleneoxy amine, diamine, thiol, dithiol, unsubstituted amide, or unsubstituted diamide.  
     
     
         32 . The paper sheet of  claim 27 , wherein the aldehyde reactive agent is a polyalkyleneoxy compound of the following structure:  
       
         
           
           
               
               
           
         
       
       Wherein: 
 Z 4 =a non-hydroxyl aldehyde reactive functionality selected from the group consisting of: primary amine; secondary amine; thiol; or, unsubstituted amide;  
 a, b, c=integers greater≧0 such that a+b+c≧2;  
 n=an integer≧2 and≧6; and,  
 R═H; C 1 -C 30  linear or branched, substituted or non-substituted, aliphatic or aromatic, saturated or unsaturated hydrocarbon; —[CH 2 CHCH 3 ]-Z 4 ; or, [(CH 2 ) n ]-Z 4 .  
 
     
     
         33 . The paper sheet of  claim 27 , wherein the aldehyde reactive paper modifying agent is an amino acid.  
     
     
         34 . The paper sheet of  claim 20 , wherein the Z 2  moiety is selected from the group consisting of: —CONHCHOHCHOHNH—; —CONHCHOHCH═N—; —CONHCHOHCH(NH—) 2 ; and, mixtures thereof.  
     
     
         35 . The paper sheet of  claim 20 , wherein Q 3  is  
       
         
           
           
               
               
           
         
       
     
     
         36 . The paper sheet of  claim 20 , wherein Q 3  is a radical of the form —CHR 1 CR 0 R 1′  wherein: 
 R 0 =a pendant group of the form Z 1 -R 10 —W, where Z 1  is a radical bonding the R 10  group to the synthetic co-polymer;  
 R 1 , R 1 ′=independently H or a C 1-4  alkyl group;  
 R 10 =any linear or branched, aliphatic or aromatic hydrocarbon of at least a C 2  chain length; and,  
 W≡N+R 11 , R 12 , R 13  where R 11 , R 12 , and R 13  are each independently a C 1-4  alkyl group.  
 
     
     
         37 . The paper sheet of  claim 20 , wherein the pendant group on Q 1  capable of forming hydrogen bonds is —CONH 2 .  
     
     
         38 . The paper sheet of  claim 20 , wherein Q 1  has —CONH 2  and -Z 5 R′ pendant groups wherein Z 5  is a bridging radical bonding the R group to the synthetic co-polymer and R′ is a C 1 -C 30  aliphatic hydrocarbon.  
     
     
         39 . A method of making a paper sheet comprising: (a) forming an aqueous suspension of papermaking fibers; (b) contacting prior to web formation a paper modifying agent having a non-hydroxyl aldehyde reactive functional group and a water soluble or water dispersible aldehyde functional ionic polymer according to the following reaction:  
       
         
           
           
               
               
           
         
       
       (c) applying the aldehyde functional ionic polymer reacted with derivatized paper modifying agent to the aqueous suspension of papermaking fibers; (d) depositing the aqueous suspension of papermaking fibers onto a forming fabric to form a web; and, (e) dewatering and drying the web to form a paper sheet, 
 wherein: 
 b, c, f>0;  
 a, e≧0;  
 e+f=b;  
 w≧1;  
 
 Q 1 =a monomer unit or a block or graft copolymer prepared from the polymerization of one or more ethylenically unsaturated compounds and containing a pendant group capable of forming hydrogen bonds with cellulose;  
 R 1 , R 1′ , R 1″ =independently H or C 1-4  alkyl;  
 R 2 =any linear or branched, aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon group containing a pendant aldehyde functionality;  
 R 3 =an aliphatic hydrocarbon, a polysiloxane, an amphiphilic hydrocarbon, humectant or other agent capable of modifying the paper sheet;  
 Z 3 =a reactive group capable of reacting with an aldehyde in an aqueous environment to form a covalent bond which is stable in an aqueous solution;  
 Z 2 =the covalently bonded bridging radical formed by the reaction of the aldehyde functionality with Z 1  functional moiety; and,  
 Q 3 =a monomer unit or a block or graft copolymer containing a charge functionality wherein the charge functionality is selected from the group consisting of: cationic;  
 anionic; and, amphoteric.  
 
     
     
         40 . The method of  claim 39 , wherein the pendant group on Q 1  capable of forming hydrogen bonds is selected from the group consisting of: —CONH 2 ; —COOH; —COO − M + ; OH; and, mixtures thereof, wherein M+is a counter ion.  
     
     
         41 . The method of  claim 39 , wherein M +  is a counter ion selected from the group consisting of: Na + ; K + ; Ca + ; and, mixtures thereof.  
     
     
         42 . The method of  claim 39 , wherein R 2  is Z 4 -R 2′ -Z 3′  wherein Z 4  is any bridging radical capable of incorporating the aldehyde functional group into the synthetic co-polymer and Z 3  is the aldehyde functional group selected from the group consisting of: —CHO; —CH(OH) 2 ; and, mixtures thereof.  
     
     
         43 . The method of  claim 39 , wherein Z 3  is selected from the group consisting of: primary amines —NH 2 ; secondary amines —NH—; amides —CONH 2 ; thiols —SH; sulfinic acids —SO 2 OH; sulfonamides —SO 2 NH 2 ; and, mixtures thereof.  
     
     
         44 . The method of  claim 39 , wherein the hydrocarbon group R 2  containing aldehyde functionality is selected from the group consisting of: —CONHCHOHCHO; —CONHCHOH(CH 2 ) 2 CHO; and, mixtures thereof.  
     
     
         45 . The method of  claim 39 , wherein the aldehyde functional polymer is selected from the group consisting of: water dispersible anionic aldehyde functional polymers; water dispersible cationic aldehyde functional polymers; water dispersible non-ionic aldehyde functional polymers; water-soluble anionic aldehyde functional polymers; water-soluble cationic aldehyde functional polymers; and, water-soluble non-ionic aldehyde functional polymers.  
     
     
         46 . The method of  claim 39 , wherein the R 3  moiety is a linear or branched, saturated or unsaturated, aromatic or aliphatic hydrocarbon of C 2  to C 40  chain length.  
     
     
         47 . The method of  claim 39 , wherein the paper modifying agent is a polysiloxane of the structure:  
       
         
           
           
               
               
           
         
       
       wherein: 
 x, y=integers>0 such that the mole ratio of x to (x+y) is from about 0.001 percent to about 25 percent; and,  
 R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9  moieties are independently any organofunctional group including C 1  to C 30  alkyl groups, ethers, polyethers, polyesters, amines, imines, amides, or other functional groups including the alkyl and alkenyl analogues of such groups,  
  wherein at least one of R 2 , R 5 , and R 10  moieties is an organofunctional moiety containing a non-hydroxyl functional group capable of reacting with an aldehyde group to form a covalent bond.  
 
     
     
         48 . The method of  claim 47 , wherein the aldehyde functional polymer is a cationic, anionic, or non-ionic glyoxylated polyacrylamide and the polysiloxane organofunctional moiety capable of reacting with an aldehyde group is a primary amine, secondary amine, or unsubstituted amide.  
     
     
         49 . The method of  claim 39 , wherein the aldehyde reactive paper modifying agent is an amphiphilic hydrocarbon, polyether, or polyhydroxy compound containing a non-hydroxyl aldehyde reactive group.  
     
     
         50 . The method of  claim 49 , wherein the aldehyde functional polymer is a cationic, anionic, or non-ionic glyoxylated polyacrylamide and the non-hydroxyl aldehyde reactive functional group of the aldehyde reactive paper modifying agent is a primary amine, secondary amine or unsubstituted amide.  
     
     
         51 . The method of  claim 49 , wherein the aldehyde reactive paper modifying agent is selected from the group consisting of: 1-amino-2-propanol; 2-amino-1-propanol; 3-amino-1,2-propanediol; tris(hydroxymethyl)aminomethane; diethanol amine; 1-amino-1-deoxy-D-sorbitol (glucamine); glucosamine; N-methyl glucamine; 2-aminoethyl hydrogen sulfate; 2-amino-2-ethyl-1,3-propanediol; 2-amino-1 phenyl-1,3-propanediol; 2-amino-1,3-propanediol; 3-amino-1-propanol; ethanolamine; 3-amino-2-hydroxy propionic acid; 1-amino-2,3,4-trihydroxybutane; 4-amino-2-hydroxybutyric acid; aspartic acid; 2-amino-2-methyl-1,3-propanediol; 2-amino-1,3-propanediol; 3-mercapto-1,2-propanediol; mercaptosuccinic acid; and, mixtures thereof.  
     
     
         52 . The method of  claim 49 , wherein the aldehyde reactive paper modifying agent is a derivative of a polyalkyleneoxy functional compound.  
     
     
         53 . The method of  claim 49 , wherein the aldehyde reactive paper modifying agent is a polyalkyleneoxy amine, diamine, thiol, dithiol, unsubstituted amide, or unsubstituted diamide.  
     
     
         54 . The method of  claim 49 , wherein the aldehyde reactive paper modifying agent is a polyalkyleneoxy compound having the following structure:  
       
         
           
           
               
               
           
         
       
       wherein: 
 Z 4 =a non-hydroxyl aldehyde reactive functionality selected from the group consisting of: primary amine; secondary amine; thiol; or, unsubstituted amide;  
 a, b, c=integers greater≧0 such that a+b+c>2;  
 n=an integer≧2 and≦6; and,  
 R═H; C 1 -C 30  linear or branched, substituted or non-substituted, aliphatic or aromatic, saturated or unsaturated hydrocarbon; —[CH 2 CHCH 3 ]-Z 4 ; or, [(CH 2 ) n ]-Z 4 .  
 
     
     
         55 . The method of  claim 49 , wherein the aldehyde reactive paper modifying agent is an amino acid.  
     
     
         56 . The method of  claim 39 , wherein the Z 2  moiety is selected from the group consisting of: —CONHCHOHCHOHNH—; —CONHCHOHCH═N—; —CONHCHOHCH(NH—) 2 ; and, mixtures thereof.  
     
     
         57 . The method of  claim 39 , wherein Q 3  is  
       
         
           
           
               
               
           
         
       
     
     
         58 . The method of  claim 39 , wherein Q 3  is a radical of the form —CHR 1 CR 0 R 1′  wherein: 
 R 0 =a pendant group of the form Z 1 -R 10 —W, where Z is a radical bonding the R 10  group to the synthetic co-polymer;  
 R 1 , R 1 ′=independently H or a C 1-4 alkyl group;  
 R 10 =any linear or branched, aliphatic or aromatic hydrocarbon of at least a C 2  chain length; and,  
 W≡N + R 11 , R 12 , R 13  where R 11 , R 12 , and R 13  are each independently a C 1-14  alkyl group.  
 
     
     
         59 . The method of  claim 39 , wherein the pendant group on Q 1  capable of forming hydrogen bonds is —CONH 2 .  
     
     
         60 . The method of  claim 39 , wherein Q 1  has —CONH 2  and -Z 5 R′ pendant groups wherein Z 5  is a bridging radical bonding the R′ group to the synthetic co-polymer and R′ is a C 1 -C 30  aliphatic hydrocarbon.  
     
     
         61 . The method of  claim 39 , wherein the aldehyde functional polymer is first added to the papermaking fibers prior to the addition of the aldehyde reactive paper modifying agent having a non-hydroxyl aldehyde reactive group.  
     
     
         62 . The method of  claim 39 , further comprising filtering and washing the papermaking fibers containing the aldehyde functional ionic polymer reacted with derivatized paper modifying agent.  
     
     
         63 . The method of  claim 62 , further comprising resuspending the papermaking fibers.  
     
     
         64 . The method of  claim 39 , wherein e=0.  
     
     
         65 . The method of  claim 39 , wherein e>0.  
     
     
         66 . The method of  claim 39 , further comprising adding a molar excess of the derivatized paper modifying agent having a non-hydroxyl aldehyde reactive functional group relative to the number of available aldehyde groups on the aldehyde functional ionic polymer.  
     
     
         67 . The method of  claim 66 , further comprising filtering and washing the papermaking fibers thereby removing excess of the paper modifying agent having a non-hydroxyl aldehyde reactive functional group.