Poly(oxazoline-co-ethyleneimine)-epichlorohydrin copolymers and uses thereof
View Patent ↗The invention is related to poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymers and chemically-modified derivatives thereof as well as their uses in formation of non-silicone hydrogel coatings on silicone hydrogel contact lenses.
1. A poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer, comprising:
(1) Hydrophobic N-acyl-iminoethylene monomeric units in an amount (designated as M1) of from about 2% to about 95% by mole, wherein the N-acyl-iminoethylene monomer units have a formula of
where R1 is a monovalent radical R1b which is C 6 -C 18 alkyl, C 1 -C 4 alkyl-substituted phenyl, C 1 -C 4 alkoxy-substituted phenyl, or C 6 -C 18 aryl radical; and a monovalent radical R1a which is hydrogen, methyl, ethyl, propyl, isopropyl, N-pyrrolidonyl-C 1 -C 4 alkyl, or a monovalent radical of-alk-(OC 2 H 4 ) m3 —OR″ in which alk is C 1 -C 6 alkyl diradical, R″ is C 1 -C 4 alkyl, and m3 is an integer from 1 to 10;
(2) azetidinium monomeric units in an amount (designated as M2) of from about 0.5% to about 95% by mole, wherein the azetidinium monomeric units have a formula of
(3) ethyleneimine monomeric units in an amount (designated as M3) of from 0 to about 60% by mole, wherein the ethyleneimine monomeric units have a formula of *—NH—CH2—CH2—* and
(4) crosslink units in an amount (designated as M4) of from 0 to about 5% by mole, wherein the crosslink units have a formula of
provided that (M1+M2+M3+M4) is about 100%.
2. The poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer of claim 1 , wherein the poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer comprises hydrophilic N-acyl-iminoethylene monomeric units of formula
in which R 1a is hydrogen, methyl, ethyl, propyl, isopropyl, N-pyrrolidonyl-C 1 -C 4 alkyl, or a monovalent radical of -alk-(OC 2 H 4 ) m3 —OR″ in which alk is C 1 -C 6 alkyl diradical, R″ is C 1 -C 4 alkyl, and m3 is an integer from 1 to 10.
3. The poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer of claim 1 , wherein the poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer comprises hydrophobic N-acyl-iminoethylene monomeric units of formula
in which R 1b is C 6 -C 18 alkyl, C 1 -C 4 alkyl-substituted phenyl, C 1 -C 4 -alkoxy-substituted phenyl, or C 6 -C 18 aryl radical.
4. The poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer of claim 1 , wherein the poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer comprises: (1) from about 10% to about 85% by mole of N-acyl-iminoethylene monomeric units; (2) from about 2.5% to about 75% by mole of azetidinium monomeric units; (3) from 0% to about 60% by mole of ethyleneimine monomeric units; and (4) from 0 to about 5% by mole of crosslink units.
5. The poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer of claim 4 , having a weight average molecular weight Mw of at least about 500 Daltons.
6. The poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer of claim 2 , wherein R 1a is hydrogen or methyl.
7. The poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer of claim 2 , wherein R 1a is ethyl, propyl, or isopropyl.
8. The poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer of claim 2 , wherein R 1a is N-pyrrolidonyl-C 1 -C 4 alkyl.
9. The poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer of claim 2 , wherein R 1a is a monovalent radical of -alk-(OC 2 H 4 ) m3 —OR″ in which alk is C 1 -C 6 alkyl diradical, R″ is C 1 -C 4 alkyl, and m3 is an integer from 1 to 10.
10. The poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer of claim 2 , wherein the poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer comprises: (1) from about 10% to about 85% by mole of N-acyl-iminoethylene monomeric units; (2) from about 2.5% to about 75% by mole of azetidinium monomeric units; (3) from 0% to about 60% by mole of ethyleneimine monomeric units; and (4) from 0 to about 5% by mole of crosslink units.
11. The poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer of claim 10 , having a weight average molecular weight Mw of at least about 500 Daltons.
12. The poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer of claim 6 , wherein the poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer comprises: (1) from about 10% to about 85% by mole of N-acyl-iminoethylene monomeric units; (2) from about 2.5% to about 75% by mole of azetidinium monomeric units; (3) from 0% to about 60% by mole of ethyleneimine monomeric units; and (4) from 0 to about 5% by mole of crosslink units.
13. The poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer of claim 12 , having a weight average molecular weight Mw of at least about 500 Daltons.
14. The poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer of claim 7 , wherein the poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer comprises: (1) from about 10% to about 85% by mole of N-acyl-iminoethylene monomeric units; (2) from about 2.5% to about 75% by mole of azetidinium monomeric units; (3) from 0% to about 60% by mole of ethyleneimine monomeric units; and (4) from 0 to about 5% by mole of crosslink units.
15. The poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer of claim 14 , having a weight average molecular weight Mw of at least about 500 Daltons.
16. The poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer of claim 8 , wherein the poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer comprises: (1) from about 10% to about 85% by mole of N-acyl-iminoethylene monomeric units; (2) from about 2.5% to about 75% by mole of azetidinium monomeric units; (3) from 0% to about 60% by mole of ethyleneimine monomeric units; and (4) from 0 to about 5% by mole of crosslink units.
17. The poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer of claim 16 , having a weight average molecular weight Mw of at least about 500 Daltons.
18. The poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer of claim 9 , wherein the poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer comprises: (1) from about 10% to about 85% by mole of N-acyl-iminoethylene monomeric units; (2) from about 2.5% to about 75% by mole of azetidinium monomeric units; (3) from 0% to about 60% by mole of ethyleneimine monomeric units; and (4) from 0 to about 5% by mole of crosslink units.
19. The poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin copolymer of claim 18 , having a weight average molecular weight Mw of at least about 500 Daltons.