Ligand functionalized polymers
View Patent ↗Ligand functionalized substrates, methods of making ligand functionalized substrates, and methods of using functionalized substrates are disclosed.
1. A guanidinyl functional copolymer of the formula:
-(M Lig ) y -(M Hydrophil ) x -(M hydrophob ) z -(M CO ) w *-,
where
-(M CO ) w * are carbonyl functional monomer units having “w*” polymerized monomer units,
-(M Hydrophil ) x - are positively charged hydrophilic ionic monomer units having “x” polymerized monomer units; said hydrophilic ionic monomers selected from positively charged amino (meth)acrylates, amino (meth)acrylamides dialkylaminoalkylamine adducts of alkenylazlactones, 3-(dimethylamino)propylamine adducts of vinyldimethylazlactone) and diallylamine monomers,
-(M hydrophob ) z - are hydrophobic monomer units having “z” polymerized monomer units;
(M Lig ) y are guanidinyl ligand functional monomer units having “y” polymerized monomer units wherein the pendent guanidinyl groups of the guanidinyl ligand functional monomer units are of the of the formula:
R 9 is C 2 to C 12 alkylene or C 5 -C 12 (hetero)arylene,
each R 3 is independently H, —OH, C 1 -C 12 alkyl, or C 5 -C 12 (hetero)aryl, preferably H or C 1 -C 4 alkyl,
R 4 is H, C 1 -C 12 alkyl, C 5 -C 12 (hetero)aryl, or —N(R 3 ) 2 , preferably H, or C 1 -C 4 alkyl,
where y is 10 to less than 100 wt. % of the monomer units;
x is 1 wt. % to 90 wt. % of the monomer units; and
w* may be comprise 0 to 90 wt. % of the monomer units, and
z is 0 to 20 wt. %, based on 100 wt. % total monomers.
2. The copolymer of claim 1 wherein x is at least 5 wt. %.
3. The copolymer of claim 1 wherein the pendent guanidinyl groups of the guanidinyl ligand functional monomer units are of the formula:
wherein
R 1 is H, C 1 -C 12 alkyl, or C 5 -C 12 (hetero)aryl,
R 2 is a covalent bond, a C 2 to C 12 alkylene, or a C 5 -C 12 (hetero)arylene,
R 9 is C 2 to C 12 alkylene or C 5 -C 12 (hetero)arylene,
each R 3 is independently H, —OH, C 1 -C 12 alkyl, or C 5 -C 12 (hetero)aryl,
each R 4 is H, C 1 -C 12 alkyl, C 5 -C 12 (hetero)aryl, or —N(R 3 ) 2 .
4. The copolymer of claim 1 derived from a carbonyl-functional (co)polymer selected from the group consisting of; acrolein, vinyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone, diacetone (meth)acrylamide, acetonyl acrylate, carbon monoxide copolymer, and diacetone (meth)acrylate(co)polymers.
5. The copolymer of claim 1 wherein the ionic monomers are positively charged monomers derived from compounds of the formula
where X is —O— or —NR 3 —;
R 7 is independently H or CH 3 ,
R 6 is a C 2 to C 10 alkylene, preferably C 2 -C 6 ,
each R 8 is independently hydrogen, alkyl, or hydroxyalkyl.
6. The copolymer of claim 1 further comprising monomers selected from acrylic acid; methacrylic acid; 2-acrylamido-2-methyl-1-propanesulfonic acid.
7. The copolymer of claim 1 further comprising a neutral hydrophilic monomer.
8. The copolymer of claim 7 wherein the neutral hydrophilic monomer is of the formula:
R 3 —O—(CH(R 3 )—CH 2 —O) n —C(O)—C(R 3 )═CH 2 ,
wherein each R 3 is independently H or C 1 -C 4 alkyl, and n is at least 2.
9. The copolymer of claim 1 further comprising a hydrophobic monomer.
10. The copolymer of claim 1 wherein the copolymer comprises 1 to 20 wt. % of hydrophobic monomer units based on 100 wt. % total monomer.
11. The copolymer of claim 1 prepared by condensation of a carbonyl functional (co)polymer with a ligand compound of Formula I:
wherein
R 2 is a covalent bond, a C 2 to C 12 alkylene, a C 5 -C 12 (hetero)arylene,
R 9 is C 2 to C 12 alkylene or C 5 -C 12 (hetero)arylene,
each R 3 is independently H, —OH, C 1 -C 12 alkyl, or C 5 -C 12 (hetero)aryl, preferably H or C 1 -C 4 alkyl,
R 4 is H, C 1 -C 12 alkyl, C 5 -C 12 (hetero)aryl, or —N(R 3 ) 2 , preferably H, or C 1 -C 4 alkyl.
12. The copolymer of claim 1 prepared by copolymerizing a monomer of the formula:
wherein
R 1 is H, C 1 -C 12 alkyl, or C 5 -C 12 (hetero)aryl,
R 2 is a covalent bond, a C 2 to C 12 alkylene, a C 5 -C 12 (hetero)arylene,
R 9 is C 2 to C 12 alkylene or C 5 -C 12 (hetero)arylene,
each R 3 is independently H, —OH, C 1 -C 12 alkyl, or C 5 -C 12 (hetero)aryl, preferably H or C 1 -C 4 alkyl,
R 4 is H, C 1 -C 12 alkyl, C 5 -C 12 (hetero)aryl, or —N(R 3 ) 2 , preferably H, or C 1 -C 4 alkyl,
X is —O— or —NR 3 —
R 6 is a C 2 to C 12 alkylene, and
R 7 is H or CH 3 ;
with an ionic hydrophilic monomer.
13. The copolymer of claim 1 prepared by copolymerizing a monomer of the formula:
wherein
R 1 is H, C 1 -C 12 alkyl, or C 5 -C 12 (hetero)aryl,
R 2 is a covalent bond, a C 2 to C 12 alkylene, a C 5 -C 12 (hetero)arylene,
R 9 is C 1 to C 12 alkylene or C 5 -C 12 (hetero)arylene,
each R 3 is independently H, —OH, C 1 -C 12 alkyl, or C 5 -C 12 (hetero)aryl,
R 4 is H, C 1 -C 12 alkyl, C 5 -C 12 (hetero)aryl, or —N(R 3 ) 2 ,
with an ionic hydrophilic monomer.