Fluorinated polymers and lubricious coatings
View Patent ↗The invention provides fluorinated polymeric articles formed a composition including a fluoropolymer. The fluoropolymer is formed using a fluorinated monomer that provides the fluoropolymer with most or all of the fluorine atoms not directly covalently attached to an atom of the fluoropolymer backbone. The fluoropolymer can also include a non-fluorinated hydrophilic monomer in a weight amount greater than the fluorinated monomer. The fluoropolymer composition also includes an ultraviolet light (UV)-reactive group capable of covalent bonding to promotes formation of the fluorinated polymeric article. The fluorinated polymeric article can be in the form of a durable lubricious coating on the surface of an implantable medical device. Coatings of the invention exhibit excellent wet/dry lubricity, durability, and controlled swelling.
1. An implantable or insertable medical device comprising a lubricious coating comprising one or more polymers comprising at least one water soluble fluoropolymer;
wherein the fluoropolymer has a polymeric backbone and comprises:
a fluorinated monomer comprising fluorine atoms, wherein the majority or all of the fluorine atoms in the fluorinated monomer are not directly covalently attached to an atom of the polymer backbone;
the coating further comprising a non-fluorinated hydrophilic monomer present in the fluoropolymer, in a second polymer, or both in the fluoropolymer and second polymer; and
an ultraviolet light (UV)-reacted group covalently bonded to a target moiety, the UV-reacted group present in the fluoropolymer, in a second polymer, or in a non-polymeric compound, and wherein the non-fluorinated hydrophilic monomer is present in the coating in an amount by weight greater than the fluorinated monomer.
2. The device of claim 1 , wherein the fluoropolymer has no fluorine atoms directly covalently attached to an atom of the polymer backbone.
3. The device of claim 1 , wherein the fluorinated monomer is present in the fluoropolymer in an amount in the range of from about 1% wt to about 40% wt.
4. The device of claim 3 , wherein the fluorinated monomer is present in the fluoropolymer in an amount in the range of from about 5% wt to about 30% wt.
5. The device of claim 1 , wherein the fluorine atoms that are not directly covalently attached to an atom of the polymer backbone are present in the fluoropolymer in an amount in the range of from about 0.2 mmol/gram to about 11 mmol/gram.
6. The device of claim 5 , wherein the fluorine atoms that are not directly covalently attached to an atom of the polymer backbone are present in the fluoropolymer in an amount in the range of from about 1 mmol/gram to about 6.5 mmol/gram.
7. The device of claim 1 , wherein the fluorinated monomer is of formula I:
wherein R 1 is —H, —F, —CH 3 , or —CH 2 CH 3 ,
R 2 is (a covalent bond), or a non-fluorinated linking group comprising one or more of C, O, N, S, or mixtures thereof and
R 3 is a fluorocarbon group.
8. The device of claim 7 , wherein the fluorinated monomer comprises at least 2 fluorine atoms that are not directly covalently attached to an atom of a polymer backbone.
9. The device of claim 8 , wherein the fluorinated monomer comprises from 2-10 fluorine atoms that are not directly covalently attached to an atom of a polymer backbone.
10. The device of claim 7 where, in formula I, R 2 is selected from the group consisting of —C(O)O—, —C(O)N—, —CH 2 O—, —O—, and —(CH 2 ) z —, wherein z in an integer in the range of 1 to 4.
11. The device of claim 10 where, in formula I, R 2 is —C(O)O—.
12. The device of claim 7 where, in formula I, R 3 is a linear, branched, or cyclic fluorocarbon group having 1-24 carbon atoms, 2-48 fluorine atoms, and 0-48 hydrogen atoms.
13. The device of claim 7 where, in formula I, R 3 is —(CR 4 R 5 ) q CR 6 R 7 R 8 , where R 4 , R 5 , R 6 , R 7 , and R 8 , are independently selected from H and F, provided that at least two of R 4 , R 5 , R 6 , R 7 , and R 8 , are F, and wherein q is in the range of 0 to 20.
14. The device of claim 7 wherein the fluorinated monomer is selected from the group consisting of 2,2,2-trifluoroethyl(meth)acrylate, 2,2,3,3,3-pentafluoropropyl(meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl(meth)acrylate, and 2,2,3,3,4,4,5,5-octafluoropentyl(meth)acrylate.
15. The device of claim 1 , wherein the non-fluorinated hydrophilic monomer is present in the polymeric backbone of the fluoropolymer.
16. The device of claim 15 , wherein the non-fluorinated hydrophilic monomer is present in the fluoropolymer in an amount in the range of 60% wt to 99% wt of the fluoropolymer.
17. The device of claim 16 , wherein the non-fluorinated hydrophilic monomer is present in the fluoropolymer in an amount in the range of from about 70% wt to about 95% wt of the fluoropolymer.
18. The device of claim 1 , wherein the non-fluorinated hydrophilic monomer comprises vinyl pyrrolidone.
19. The device of claim 1 , wherein the UV-reacted group is present as a pendent group on the polymeric backbone of the fluoropolymer.
20. The device of claim 1 , wherein the coating has a thickness in the range of from about 0.5 μm to about 10 μm in a dried state, and in the range of from about 1 μm to about 40 μm in a fully hydrated state.
21. The device of claim 1 comprising a catheter, wherein the coating is present on at least a portion the catheter surface.
22. The device of claim 1 , wherein the fluoropolymer has as solubility in water of 1 mg/mL or greater.