Zwitterion-functionalized block copolymer membranes and associated block copolymer composition
A membrane including a block copolymer is presented. The block copolymer includes at least one block A including structural units having a formula (I), and at least one block B including structural units having a formula (II). A hollow-fiber membrane for hemodialysis or hemofiltration, and associated block copolymer are also presented.
1. A block copolymer, comprising at least one block A comprising structural units having a formula (I), and at least one block B comprising structural units having a formula (II):
(II)
wherein “a” and “b” are independently at each occurrence 0, 1, 2, 3, or 4;
“n”, “p”, “q” and “r” are independently 0 or 1;
R 1 and R 2 are independently at each occurrence a halogen atom, a nitro group, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical;
R 3 is a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical;
R 4 is a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical;
Y is independently at each occurrence a bond, an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, a phenylphosphine group, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical;
Q is a bond, an oxygen atom, a sulfur atom, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical; and
Z is a zwitterion functional group.
2. The block copolymer of claim 1 , wherein the block copolymer comprises structural units having a formula (VI):
wherein “a” and “b” are independently at each occurrence 0, 1, 2, 3, or 4;
“n”, “p”, “q” and “r” are independently 0 or 1;
“x” is an integer in a range from about 20 to about 200;
“y” is an integer in a range from about 1 to about 25;
Y is independently at each occurrence a bond, an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, a phenylphosphine group, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical;
Q is a bond, an oxygen atom, a sulfur atom, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical;
W is independently at each occurrence a radical having a formula (VII) or (VIII):
with the proviso that at least one of W in the block copolymer is a radical having the formula (VIII);
R 1 and R 2 are independently at each occurrence a halogen atom, a nitro group, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical;
R 3 , R 5 , and R 7 are independently at each occurrence a hydrogen atom, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical; and
R 4 and R 6 are independently a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical.
3. The block copolymer of claim 1 , wherein the block copolymer comprises structural units having a formula (IX):
wherein “a” and “b” are independently at each occurrence 0, 1, 2, 3, or 4;
“n”, “p”, “q” and “r” are independently 0 or 1;
“x” is an integer in a range from about 20 to about 200;
“y” is an integer in a range from about 1 to about 25;
Y is independently at each occurrence a bond, an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, a phenylphosphine group, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical;
Q is a bond, an oxygen atom, a sulfur atom, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical;
W is independently at each occurrence a radical having a formula (VII) or (VIII):
with the proviso that at least one W in the block copolymer is a radical having the formula (VIII);
R 1 and R 2 are independently at each occurrence a halogen atom, a nitro group, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical;
R 3 , R 5 , and R 7 are independently at each occurrence a hydrogen atom, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical; and
R 4 and R 6 are independently a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical.
4. The block copolymer of claim 1 , wherein the block B comprises structural units having a formula (III):
wherein “a” and “b” are independently at each occurrence 0, 1, 2, 3, or 4;
“n”, “p”, “q” and “r” are independently 0 or 1;
Q is a bond, an oxygen atom, a sulfur atom, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical; and
R 1 and R 2 are independently at each occurrence a halogen atom, a nitro group, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical.
5. The block copolymer of claim 1 , wherein the zwitterion functional group comprises sulfobetaine, carboxybetaine, phosphorylcholine, or combinations thereof.
6. The block copolymer of claim 1 , wherein the block A comprises structural units having a formula (IV):
wherein R 3 and R 5 are independently at each occurrence a hydrogen atom, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical; and
R 4 and R 6 are independently a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical.
7. The block copolymer of claim 1 , wherein the block A further comprises structural units having a formula (V):
R 3 and R 5 are independently at each occurrence a hydrogen atom, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical; and
R 4 is a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical.
8. The block copolymer of claim 1 , wherein a mole fraction of the zwitterion functional group in the block A is in a range from about 5 percent to about 100 percent.
9. The block copolymer of claim 1 , wherein a mole fraction of the zwitterion functional group in the block A is in a range from about 35 percent to about 70 percent.
10. The block copolymer of claim 1 , wherein the number of repeat units in the block B is in a range from about 20 to about 200.
11. The block copolymer of claim 1 , wherein the number of repeat units in the block A is in a range from about 1 to about 25.