Coating solutions comprising segmented reactive block copolymers

• US 7,942,929 B2
• Filed: 12/15/2008
• Issued: 05/17/2011
• Est. Priority Date: 12/27/2007
• Status: Expired due to Fees

• Current Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Original Assignee: Bausch & Lomb Incorporated (Bausch Health Cos., Inc.)
• Inventors: Shipp, Devon A., Kunzler, Jay F., Linhardt, Jeffrey G.
• Primary Examiner(s): Gulakowski; Randy
• Assistant Examiner(s): Loewe; Robert
• Application Number:
  US12/334,618
• Publication Number:
  US 20090171459A1
• Time in Patent Office: 883 Days
• Field of Search: 523/106, 523/107, 428/420, 428/447, 427/2.24, 623/6.62
• US Class Current: 623/6.62
• CPC Class Codes: A61L 27/34 Macromolecular materials
• CPC Class Codes: A61L 31/10 Macromolecular materials
• CPC Class Codes: A61M 25/0045 multi-layered, e.g. coated coating materials A61L29/08
• CPC Class Codes: C08F 130/08 containing silicon
• CPC Class Codes: C08F 230/00 Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal metal salts, e.g. phenolates or alcoholates, see the parent compounds
• CPC Class Codes: C08F 2438/03 Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• CPC Class Codes: C08J 2343/04 Homopolymers or copolymers of monomers containing silicon
• CPC Class Codes: C08J 2383/00 Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
• CPC Class Codes: C08J 7/056 Forming hydrophilic coatings
• CPC Class Codes: G02B 1/043 Contact lenses
• CPC Class Codes: Y10T 428/31536 Including interfacial reaction product of adjacent layers
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

This invention is directed toward surface treatment of a device. The surface treatment comprises the attachment of reactive segmented block copolymers to the surface of the substrate by means of reactive functionalities of the terminal functionalized surfactant material reacting with complementary surface reactive functionalities in monomeric units along the polymer substrate. The present invention is also directed to a surface modified medical device, examples of which include contact lenses, intraocular lenses, vascular stents, phakic intraocular lenses, aphakic intraocular lenses, corneal implants, catheters, implants, and the like, comprising a surface made by such a method.

Claims

1. A method of forming a surface modified medical device, the method comprising:

providing a medical device having at least one group providing reactive functionality on at least one surface of the medical device;

providing a surface modifying agent comprising a reactive segmented block copolymer comprising a hydrophilic block and a chemical binding unit block having reactivity that is complimentary to the at least one group providing surface functionality of the medical device;

contacting the at least one surface having reactive functionality of the medical device with the surface modifying agent, and;

subjecting the device surface and surface modifying agent to reaction conditions suitable for forming a covalent bond between the device surface and the surface modifying agent to form a surface modified medical device,

wherein the reactive segmented block copolymer is selected from the following formulae (I)-(III);

R1−

[(A)m]p−

[(B)n]q−

X 

 

(I)

wherein R1 is a reactive residue of a moiety capable of acting as an initiator for atom transfer radical polymerization, A is a chemical binding unit block, B is a hydrophilic unit block, m is 1 to 10,000, n is 1 to 10,000, p and q are natural numbers, and X is a halogen capping group of an initiator for atom transfer radical polymerization or a derivatized reaction product,

R1−

[(A)m]p−

[(B)n]q−

R2 

 

(II)

wherein R1 is a radical forming residue of a reverse addition fragmentation transfer agent or free radical initiator, A is a chemical binding unit block, B is a hydrophilic unit block, m is 1 to 10,000, n is 1 to 10,000, p and q are natural numbers, and R2 is a thio carbonyl fragment of a chain transfer agent or a derivatized reaction product, and

R1−

[(B)n]q−

[(A)m]p−

R2−

[(A)m]p−

[(B)n]q−

R1 

 

(III)

wherein R1 is a radical forming residue of a reverse addition fragmentation transfer agent or free radical initiator, A is a chemical binding unit block, B is a hydrophilic unit block, m is 1 to 10,000, n is 1 to 10,000, p and q are natural numbers, and R2 is a thio carbonyl thio group.

2. The method of claim 1 wherein the medical device is prepared from a silicon containing monomer.

3. The method of claim 2 wherein the silicon containing monomer comprises a silicon containing monomer selected from the group consisting of silicon containing vinyl carbonates, silicon containing vinyl carbamates, polyurethane-polysiloxanes having one or more hard-soft-hard blocks and end-capped with a hydrophilic monomer, fumarate containing silicon containing monomers, poly(organosiloxanes) capped with an unsaturated group at two or more ends of the molecule, polyurethane-polysiloxane macromonomers and mixtures thereof.

4. The method of claim 2 wherein the medical device comprises as a bulk monomer mixture to be copolymerized 5 to 50 percent by weight of one or more silicon containing macromonomers, 5 to 75 percent by weight of one or more polysiloxanylalkyl(meth)acrylic monomers, and 10 to 50 percent by weight of a hydrophilic monomer.

5. The method of claim 2 wherein the medical device comprises as a bulk monomer mixture to be copolymerized 10 to 25 percent by weight of one or more silicon containing macromonomers, 30 to 60 percent by weight of one or more polysiloxanylalkyl (meth)acrylic monomers, and 20 to 40 percent by weight of a hydrophilic monomer.

6. The method of claim 1 wherein the medical device comprises hydrogel materials.

7. The method of claim 1 wherein the medical device comprises silicon containing hydrogel materials.

8. The method of claim 1 wherein the medical device comprises vinyl functionalized polydimethylsiloxanes copolymerized with hydrophilic monomers.

9. The method of claim 1 wherein the medical device comprises fluorinated monomers.

10. The method of claim 1 wherein the medical device comprises methacrylate functionalized fluorinated polyethylene oxides copolymerized with hydrophilic monomers.

11. The method of claim 1 wherein the medical device is selected from the group consisting of heart valves, intraocular lenses, intraocular lens inserters, contact lenses, intrauterine devices, vessel substitutes, artificial ureters, vascular stents, phakic intraocular lenses, aphakic intraocular lenses, corneal implants, catheters, implants, and artificial breast tissue.

12. The method of claim 11 wherein the medical device formed is a soft contact lens.

13. The method of claim 12 wherein the medical device is a silicon containing hydrogel contact lens material.

14. The method of claim 1 wherein the medical device has at least one surface functionality selected from the group consisting of epoxides, carboxylic acids, anhydrides, oxazolinones, lactams, lactones, amines, hydroxys, hydrazines, hydrazides, thiols, nucleophilic groups, electrophilic groups, carboxylic esters, imide esters, orthoesters, carbonates, isocyanates, isothiocyanates, aldehydes, ketones, thiones, alkenyls, acrylates, methacrylates, acrylamides, sulfones, maleimides, disulfides, iodos, sulfonates, thiosulfonates, silanes, alkoxysilanes, halosilanes, phosphoramidate and alcohol functionality.

15. The method of claim 14 wherein the surface functionality is selected from the group consisting of aldehyde hydrates, hemiacetals, acetals, ketone hydrates, hemiketals, ketals, thioketals, and thioacetals.

16. The method of claim 14 wherein the surface functionality is selected from the group consisting of succinimidyl carbonate, succinimidyl ester, maleimide, benzotriazole carbonate, glycidyl ether, imidazoyl ester, p-nitrophenyl carbonate, acrylate, tresylate, aldehyde, and orthopyridyl disulfide.

17. The method of claim 1, wherein the reactive segmented block copolymer has a chemical binding unit selected from the group consisting of monomers comprising a functionality selected from the group consisting of epoxides, carboxylic acids, anhydrides, oxazolinones, lactams, lactones, amines, hydroxys, hydrazines, hydrazides, thiols, nucleophilic groups, electrophilic groups, carboxylic esters, imide esters, orthoesters, carbonates, isocyanates, isothiocyanates, aldehydes, ketones, thiones, alkenyls, acrylates, methacrylates, acrylamides, sulfones, maleimides, disulfides, iodos, sulfonates, thiosulfonates, silanes, alkoxysilanes, halosilanes, phosphoramidate and alcohol functionality.

18. The method of claim 1, wherein the reactive segmented block copolymer has a hydrophilic unit monomer selected from the group consisting of 2-hydroxyethyl methacrylate, glycerol methacrylate, methacrylic acid, acrylic acid, methacrylamide, acrylamide, N,N′

-dimethylmethacrylamide, N,N′

-dimethylacrylamide;

ethylenically unsaturated poly(alkylene oxide)s, cyclic lactams, N-vinyl-2-pyrrolidone, hydrophilic vinyl carbonate, hydrophilic vinyl carbamate monomers, 2-hydroxyethyl acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, glyceryl (meth)acrylate, poly(ethylene glycol (meth)acrylate), tetrahydrofurfuryl (meth)acrylate, N-vinyl acetamide, copolymers, derivatives and combinations thereof.

19. The method of claim 1, wherein the reactive segmented block copolymer has a chemical binding unit comprises between 1 and about 1,000 units.

20. The method of claim 1, wherein the reactive segmented block copolymer has a chemical binding unit comprises between 1 and about 100 units.

21. The method of claim 1, wherein the reactive segmented block copolymer has a chemical binding unit comprising between 1 and about 30 units.

22. The method of claim 1, wherein the reactive segmented block copolymer has a hydrophilic block comprising between 1 and about 10,000 units.

23. The method of claim 1, wherein the reactive segmented block copolymer has a hydrophilic block comprising between about 10 and about 1,000 units.

24. The method of claim 1, wherein the reactive segmented block copolymer has a hydrophilic block comprising between about 20 and about 300 units.

25. The method of claim 1 wherein the step of subjecting the device surface and surface modifying agent to reaction conditions suitable for forming a covalent bond between the device surface and the surface modifying agent to form a surface modified medical device occurs under autoclave conditions.

26. The method of claim 25 further comprising the step of applying a lid stock to a package containing the device and the surface modifying agent prior to subjecting the medical device to a step of autoclaving.

27. The method of claim 25 further comprising the steps of removing the surface modifying agent after autoclaving, rinsing the coated device, providing a storage solution and further autoclaving the device to sterilize the device.

28. The method of claim 1 wherein one of the chemical binding unit block or the hydrophilic block is a statistical copolymerization or compositionally heterogeneous block.

29. The method of claim 1 wherein the reactive segmented block copolymer further comprises at least one block selected from the group consisting of nonbinding blocks, nonhydrophilic blocks and combinations thereof.

30. A surface modified medical device comprising:

a medical device having at least one group providing reactive functionality on at least one surface of the medical device; and

a reactive segmented block copolymer comprising a chemical binding unit block and a hydrophilic block applied to the surface of the medical device;

whereby a chemical reaction between the surface functionality of the medical device and the one or more reactive segmented block copolymer comprising a chemical binding unit block and a hydrophilic block forms covalent bonds there between,

wherein the reactive segmented block copolymer is selected from the following formulae (I)-(III);

R1−

[(A)m]p−

[(B)n]q−

X 

 

(I)

wherein R1 is a reactive residue of a moiety capable of acting as an initiator for atom transfer radical polymerization, A is a chemical binding unit block, B is a hydrophilic unit block, m is 1 to 10,000, n is 1 to 10,000, p and q are natural numbers, and X is a halogen capping group of an initiator for atom transfer radical polymerization or a derivatized reaction product,

R1−

[(A)m]p−

[(B)n]q−

R2 

 

(II)

wherein R1 is a radical forming residue of a reverse addition fragmentation transfer agent or free radical initiator, A is a chemical binding unit block, B is a hydrophilic unit block, m is 1 to 10,000, n is 1 to 10,000, p and q are natural numbers, and R2 is a thio carbonyl fragment of the chain transfer agent or a derivatized reaction product, and

R1−

[(B)n]q−

[(A)m]p−

R2−

[(A)m]p−

[(B)n]q−

R1 

 

(III)

wherein R1 is a radical forming residue of a reverse addition fragmentation transfer agent or free radical initiator, A is a chemical binding unit block, B is a hydrophilic unit block, m is 1 to 10,000, n is 1 to 10,000, p and q are natural numbers, and R2 is a thio carbonyl thio group.

31. The surface modified medical device of claim 30 wherein the medical device is selected from the group consisting of heart valves, intraocular lenses, intraocular lens inserters, contact lenses, intrauterine devices, vessel substitutes, artificial ureters, vascular stents, phakic intraocular lenses, aphakic intraocular lenses, corneal implants, catheters, implants, and artificial breast tissue.

32. The surface modified medical device of claim 31 wherein the medical device is a hydrophilic contact lens.

33. The surface modified medical device of claim 31 wherein the medical device is a hydrogel contact lens.