Ionic polymers, method of manufacture, and uses thereof

1. A polymer comprising units of formula VI

wherein

each b=0 or 1;

each X is independently a hydrogen, 1/z of a metal ion of charge z, a protonated nitrogen base, or a tetrasubstituted organic ammonium compound;

the molar ratio of q:r:s:t=(99.99-0.1):(0-99.9):(0-98):(0-30), wherein s+t is at least 1;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

R 4 , R 5 , R 6 and R 7 are each independently a hydrogen, C 1-4 alkyl or F, wherein F is a functional group that imparts a property to the polymer VI, at least one and no more than two of R 4 , R 5 , R 6 and R 7 are F and F is the same or different in each instance;

G is a single bond or a C 1-30 hydrocarbyl group; and

for each instance of t when t is not zero, c=0-5 and d=0-5, provided that c+d=1-5, and wherein q, r and s as present in c are independent of any other value of q, r and s.

2. The polymer of claim 1 , wherein X is a metal ion having a valence of z and is present in an amount of q/z.

3. The polymer of claim 1 , wherein t is not zero, and G is a single bond or a C 1-12 alkyl substituted with 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 2-12 alkenyl substituted with 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 2-12 alkynyl substituted with 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 3-8 cycloalkyl substituted with 0-4 oxycarbonyl groups, 0-4 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 3-8 heterocycloalkyl substituted with 0-4 oxycarbonyl groups, 0-4 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 6-12 aryl substituted with 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 4-12 heteroaryl substituted with 0-4 oxycarbonyl groups, 0-4 aminocarbonyl groups, or a combination comprising at least one of the foregoing, C 2-24 (C 1-4 alkyloxy) e (C 1-4 -alkyl)) groups wherein e=1-16 substituted with 0-6 oxycarbonyl groups, 0-6 aminocarbonyl groups, or a combination comprising at least one of the foregoing.

4. The polymer of claim 1 , wherein s is not zero and R 4 and R 5 are hydrogen, R 6 is methyl or hydrogen, and R 7 is carboxylic acid.

5. The polymer of claim 1 , wherein t is not zero and c=1-4.

6. The polymer of claim 1 , having a weight average molecular weight of 250-3,000,000 g/mole.

7. The polymer of claim 1 , wherein the polymer is water soluble in an amount of at least 10% of the polymer by weight in water.

8. The polymer of claim 1 , having a water absorption under a load of 3 psi of at least 0.1 gram of water per gram of ionic polymer.

9. The polymer of claim 1 , having a glass transition temperature of greater than 50° C. when dried.

10. The polymer of claim 1 , wherein the molar amount of q is 40-99.9.

11. A crosslinked product of the polymer of claim 1 , comprising at least one further crosslink in any of the q, r, or s units.

12. The polymer of claim 11 , wherein the at least one further crosslink is the crosslink residue of a diol or higher polyol, a diisocyanate or higher isocyanate, a diamine or higher amine, a diacid or higher acid, the C 1-3 alkyl esters thereof, or the acid halide thereof, a diepoxide or higher epoxide, an alcohol-amine, a compound having two or more ethylenic unsaturations, a polyvalent ion, or a combination comprising at least one of the forgoing crosslinkers.

13. The polymer of any of claim 11 , wherein the at least one further crosslink exists through hydroxyl, lactone, or carboxylic acid groups of unit q.

14. The polymer of claim 11 , wherein the at least one further crosslink exists through the F group of unit s.

15. A binder-desiccant comprising

the polymer of claim 1 ; and optionally

a desiccant.

16. A binder-sorptive composition comprising

the polymer of claim 1 .

17. The binder-sorptive composition of claim 16 , further comprising a sorbent.

18. A biological fluid absorptive article comprising the binder-sorptive composition of claim 16 .

19. A method of aggregating a material present in an liquid phase, comprising contacting the material in the liquid phase with an amount of the polymer of claim 1 , to aggregate the one or more materials.

20. The method of claim 19 , wherein the material in the liquid phase is in the form of a solution, suspension, colloid, dispersion, or emulsion.

21. A method of preparing the polymer of claim 1 , the method comprising

contacting a base and a polymer of formula VII under conditions effective to at least partially hydrolyze the lactones,

wherein

each b=0 or 1;

the molar ratio of u:s:t=(99.99-20):(0-50):(0-30), wherein s+t=at least 1 and wherein u and s as present in c are independent of any other value of u and s;

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

G is a single bond or a C 1-30 hydrocarbyl group;

R 4 , R 5 , R 6 and R 7 are each independently a hydrogen, C 1-4 alkyl or F, wherein F is a functional group that imparts a property to the polymer VI, at least one and no more than two of R 4 , R 5 , R 6 and R 7 are F and F is the same or different in each instance; and

for each instance of t when t is not zero, c=0-5 and d=0-5, provided that c+d=1-5; and

optionally contacting the polymer with a crosslinking agent under conditions effective to crosslink the polymer.

22. The method of claim 21 , wherein the molar content of the base is equal to or less than 5 times the moles of monomer units of u in the polymer.

23. The method of claim 21 , wherein the base is an oxide or a hydroxide of a metal ion of Groups IA, IIA, IIIA, IVA, VA, IIB, IVB, VIIB, VIIIB, or a combination comprising at least one of the foregoing groups, or a tetra(C 1-12 alkyl)ammonium salt.

24. The method of claim 23 , wherein the base is sodium hydroxide, calcium hydroxide, or potassium hydroxide, and the contacting is performed at a temperature of 25-200° C.

25. The method of claim 21 further comprising neutralizing the polymer after the contacting to a pH less than 9.0, and optionally drying the polymer thereafter.

26. The method of claim 21 , wherein the crosslinking monomer is a diol or higher polyol, a diisocyanate or higher isocyanate, a diamine or higher amine, a diacid or higher acid, the C 1-3 alkyl esters thereof, or the acid halide thereof, a diepoxide or higher epoxide, an alcohol-amine, a compound having two or more ethylenic unsaturations, a polyvalent ion, or a combination comprising at least one of the forgoing crosslinkers.

27. A polymer comprising units of formula VIa

wherein

each b=0 or 1;

each X is independently a hydrogen, 1/z of a metal ion of charge z, a protonated nitrogen base, or a tetrasubstituted organic ammonium compound;

the molar ratio of q:r:s=(99.99-0.1):(0-99.89):(0.01-99.9); and

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl or F, wherein F is a functional group that imparts a property to the polymer VI, and at least one and no more than two of R 4 , R 5 , R 6 and R 7 are F and F is the same or different in each instance, provided that formula VIa comprises at least one q unit having an ionizable group or at least one s unit having an ionizable group.

28. The polymer of claim 21 , wherein unit s is a polymerization residue of acrylic acid, fumaric acid, itaconic acid, maleic acid, maleic anhydride, itaconic anhydride, styrene, n-butyl acrylate, N,N-dimethyl acrylamide, octadecyl acrylate, p-styrene sulfonate, butadiene, 2-vinylpyridine, 4-vinyl benzoic acid, N-vinyl pyrrolidone, methacrylic acid, butadiene, acrylonitrile, ethylene, or a combination comprising at least one of the foregoing.

29. A cross Inked product of the polymer of claim 27 , comprising at least one further crosslink in any of the q, r, or s units.

30. The polymer of claim 29 , wherein the at least one further crosslink is the crosslink residue of a diol or higher polyol, a diisocyanate or higher isocyanate, a diamine or higher amine, a diacid or higher acid or the C1-3alkyl esters thereof, a diepoxide or higher epoxide, an alcohol-amine, a polyvalent ion, a compound having at least two sited of ethylenic unsaturation, or a combination comprising at least one of the forgoing crosslinkers.

31. The polymer of claim 30 , wherein the at least one further crosslink exists through hydroxyl, lactone, or carboxylic acid groups of unit q.

32. The polymer of claim 30 , wherein the at least one further crosslink exists through the F group of unit s.

33. A method of preparing the polymer of claim 27 , the method comprising

contacting a base and a polymer of formula VIIa under conditions effective to at least partially hydrolyze the lactone,

wherein

each b=0 or 1;

each X is independently a hydrogen, 1/z of a metal ion of charge z, a protonated nitrogen base, or a tetrasubstituted organic ammonium compound;

the molar ratio of r:s=(0.1-99.9):(0.1:99.9); and

R 4 , R 5 , R 6 , and R 7 are each independently a hydrogen, C 1-4 alkyl or F, wherein at least one and no more than two of R 4 , R 5 , R 6 and R 7 are F, F is a functional group that imparts a property to the polymer VI, and F is the same or different in each instance; and

optionally contacting the ionic polymer with a crosslinking agent under conditions effective to crosslink the ionic polymer.

34. The method of claim 33 , wherein the crosslinking agent is a compound having two or more ethylenic unsaturations, a diol or higher polyol, a diisocyanate or higher isocyanate, a diamine or higher amine, a dicarboxylic acid or higher carboxylic acid, the C 1-3 alkyl esters thereof, or the acid halide thereof, a polyvalent ion, an alcohol-amine, or a combination comprising at least one of the forgoing crosslinking agents.

35. A polymer comprising units of formula VIb

wherein

each b=0 or 1;

each X is independently a hydrogen, 1/z of a metal ion of charge z, a protonated nitrogen base, or a tetrasubstituted organic ammonium compound;

the molar ratio of q:r:t=(99.99-0.1):(0-99.89):(0.01-30);

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

G is a single bond or a C 1-30 hydrocarbyl group; and

for each instance of t, c=0-5 and d=0-5, provided that c+d=1-5, and wherein q and r as present in c are independent of any other value of q and r.

36. A crosslinked product of the polymer of claim 35 , comprising at least one further crosslink in any of the q or r units.

37. The polymer of claim 36 , wherein the at least one further crosslink is a residue of a diol or higher polyol, a diisocyanate or higher isocyanate, a diamine or higher amine, a diacid or higher acid or the C 1-3 alkyl esters thereof, a diepoxide or higher epoxide, an alcohol-amine, a polyvalent ion, a compound having at least two sited of ethylenic unsaturation, or a combination comprising at least one of the forgoing crosslinkers.

38. The polymer of claim 36 , wherein the at least one further crosslink exists through hydroxyl, lactone, or carboxylic acid groups of unit q.

39. The polymer of claim 36 , wherein the crosslink exists through the F group of unit s.

40. A method of preparing the polymer of claim 35 , the method comprising

contacting a base and a polymer of formula VIIb

wherein

each b=0 or 1;

each X is independently a hydrogen, 1/z of a metal ion of charge z, a protonated nitrogen base, or a tetrasubstituted organic ammonium compound;

the molar ratio of w:t=(99.99-70):(0.01-30);

R 1 , R 2 , and R 3 are each independently a hydrogen or C 1-4 alkyl;

G is a single bond or a C 1-30 hydrocarbyl group; and

for each instance of t when t is not zero, c=0-5 and d=0-5, provided that c+d=1-5, and wherein q, r and s as present in c are independent of any other value of q, r and s; and

optionally contacting the ionic polymer with a crosslinking agent under conditions effective to crosslink the ionic polymer.

41. The method of claim 33 , wherein the crosslinking agent is a diol or higher polyol, a diisocyanate or higher isocyanate, a diamine or higher amine, a dicarboxylic acid or higher carboxylic acid, the C 1-3 alkyl esters thereof, or the acid halide thereof, a polyvalent ion, an alcohol-amine, or a combination comprising at least one of the forgoing crosslinking agents.