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US-12616777-B2 - Silicone polyurea block copolymer coating compositions and methods

US12616777B2US 12616777 B2US12616777 B2US 12616777B2US-12616777-B2

Abstract

Silicone polyurea block copolymers are prepared by copolymerizing: (a) a diamine composition that includes a polyethylene glycol diamine, and optionally, a dipiperidyl alkane; (b) a monofunctional silicone isocyanate; and (c) a diisocyanate. Compositions useful as passivating coatings comprising the block copolymer are also provided, and substrates coated with the compositions. Methods of preparing and using the compositions are also described.

Inventors

  • Kristin Taton
  • Patrick Guire
  • Charles Leir

Assignees

  • INNOVATIVE SURFACE TECHNOLOGIES, INC.

Dates

Publication Date
20260505
Application Date
20230411

Claims (20)

  1. 1 . A non-implanted medical device having a surface containing a passivating coating, the passivating coating comprising a silicone polyurea copolymer having a polymer backbone and comprising a reaction product of: (a) a diamine composition comprising a polyethylene glycol diamine compound having a formula (I), (II), or a combination of (I) and (II): wherein y is an integer in the range of 2 to 40, and x+z is an integer in the range of 1 to 8; or wherein n is an integer in the range of 1 to 100; (b) a monofunctional silicone isocyanate compound having a formula: wherein D is an alkyl radical having 1 to 6 carbon atoms, G is a bivalent alkyl radical having 1 to 6 carbon atoms, each R is independently selected from a monovalent alkyl radical having about 1 to about 12 carbon atoms, a substituted alkyl radical having about 1 to about 12 carbon atoms, a phenyl radical and a substituted phenyl radical, and m is an integer in the range of 15 to 300; and (c) a diisocyanate compound, wherein the silicone polyurea copolymer comprises total isocyanate groups to total amine groups in a molar ratio of 1.5:1 to 1.05:1.
  2. 2 . The non-implanted medical device of claim 1 selected from laboratory plates, tubes, trays, capillaries, and containers; diagnostic slides; chromatographic support materials; cell culture ware; biosensors; and microfluidic devices.
  3. 3 . The non-implanted medical device of claim 1 selected from transdermal drug delivery devices, dialysis devices and dialysis tubing, catheters, membranes and grafts, autotransfusion devices, intraaortic balloon pumps, intracardiac suction devices, blood pumps, blood oxygenator devices, blood filters, blood temperature monitors, hemoperfusion units, plasmapheresis units, transition sheaths, dialators, intrauterine pressure devices, breathing circuit connectors, stylets, guidewires, dialators, surgical instruments, endoscopic devices, hearing aids, blood storage bags, umbilical tape, membranes, wound dressings, wound management devices, needles, percutaneous closure devices, transducer protectors, uterine bleeding patches, clamps, cannulae.
  4. 4 . The non-implanted medical device of claim 1 wherein the polyethylene glycol diamine compound has a molecular weight of 100 to 4,434.
  5. 5 . The non-implanted medical device of claim 1 wherein the diamine composition of (a) further comprises a dipiperidyl alkane, and wherein the diamine composition comprises 20 to 99.9 molar percent of the polyethylene glycol and 0.1 to 80 molar percent of the dipiperidyl alkane.
  6. 6 . The non-implanted medical device of claim 5 wherein the dipiperidyl alkane has a formula: where A is a C0 to C 8 bivalent radical.
  7. 7 . The non-implanted medical device of claim 6 wherein the dipiperidyl alkane comprises dipiperidyl propane.
  8. 8 . The non-implanted medical device of claim 1 wherein the silicone isocyanate has a molecular weight in a range of 1,000 to 20,000.
  9. 9 . The non-implanted medical device of claim 1 wherein the diisocyanate has a formula: OCN—B—NCO (VII) where B is a bivalent alkyl radical having 2 to 20 carbon atoms.
  10. 10 . The non-implanted medical device of claim 9 , wherein the diisocyanate is selected from hexane diisocyanate and isophorone diisocyanate.
  11. 11 . The non-implanted medical device of claim 1 wherein the copolymer comprises polyethylene glycol in amount of 25 to 95 weight percent, based on total weight of the silicone polyurea copolymer.
  12. 12 . The non-implanted medical device of claim 1 wherein the silicone polyurea copolymer has a Hardness Value of 30 D or less.
  13. 13 . The non-implanted medical device of claim 1 wherein the silicone polyurea copolymer has an average molecular weight of 100,000 or less.
  14. 14 . The non-implanted medical device of claim 1 wherein the silicone polyurea copolymer further comprises one or more latent reactive groups selected from a photoreactive group, a thermally reactive group, a chemically reactive group, or a combination of any two or more of these.
  15. 15 . A medical device fabricated of a material selected from silicone, polystyrene, polyethylene terephthalate, polyethylene, polyvinyl chloride, polypropylene, polyurethane, polytetrafluoroethylene, polyamide, polyolefin, or copolymers or combinations thereof, the device having a surface containing a dry lubricious coating, the dry lubricious coating comprising a silicone polyurea copolymer having a polymer backbone and comprising a reaction product of: (a) a diamine composition comprising a polyethylene glycol diamine compound having a formula (I), (II), or a combination of (I) and (II): wherein y is an integer in the range of 2 to 40, and x+z is an integer in the range of 1 to 8; or wherein n is an integer in the range of 1 to 100; (b) a monofunctional silicone isocyanate compound having a formula: wherein D is an alkyl radical having 1 to 6 carbon atoms, G is a bivalent alkyl radical having 1 to 6 carbon atoms, each R is independently selected from a monovalent alkyl radical having about 1 to about 12 carbon atoms, a substituted alkyl radical having about 1 to about 12 carbon atoms, a phenyl radical and a substituted phenyl radical, and m is an integer in the range of 15 to 300; and (c) a diisocyanate compound, wherein the silicone polyurea copolymer comprises total isocyanate groups to total amine groups in a molar ratio of 1.5:1 to 1.05:1, wherein the dry lubricous coating provides the medical device with reduced frictional resistance against an uncoated substrate as compared to an uncoated medical device or medical article.
  16. 16 . The medical device of claim 15 wherein the dry lubricous coating provides frictional resistance that is at least 50% less than frictional resistance of an uncoated medical device or medical article.
  17. 17 . The medical device of claim 15 wherein the diamine composition of (a) further comprises a dipiperidyl alkane, and wherein the diamine composition comprises 20 to 99.9 molar percent of the polyethylene glycol and 0.1 to 80 molar percent of the dipiperidyl alkane.
  18. 18 . The medical device of claim 17 wherein the dipiperidyl alkane comprises dipiperidyl propane.
  19. 19 . The medical device of claim 15 wherein the diisocyanate has a formula: OCN—B—NCO (VII) where B is a bivalent alkyl radical having 2 to 20 carbon atoms.
  20. 20 . The medical device of claim 19 , wherein the diisocyanate is selected from hexane diisocyanate and isophorone diisocyanate.

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation of U.S. application Ser. No. 16/771,380, filed Jun. 10, 2020, which is a U.S. National Stage under 35 U.S.C. 371 of PCT Application No. PCT/US2018/064988, filed Dec. 11, 2018, which claims benefit under 35 U.S.C. 119(e) to U.S. Provisional Patent Application Ser. No. 62/597,168, entitled, “Silicone Polyurea Block Copolymer Coating Compositions and Methods,” and filed Dec. 11, 2017, the contents of which are incorporated herein in their entirety for all purposes. FIELD OF THE INVENTION Block copolymers having an A-B-A structure, with A being a silicone segment linked to the B segment through a urea linkage. The B segment is comprised of a random copolymer block of C-D repeating monomers linked through a urea group, where C is a hydrocarbon having 2 to 20 carbon atoms, and D is a polyethylene glycol/polypropylene glycol copolymer or dipiperidyl propane. The block copolymers are prepared by reacting monofunctional silicone isocyanate with diamines and diisocyanates. The silicone polyurea block copolymers thus formed can be utilized in coating compositions for application to surfaces, particularly surfaces that come in contact with aqueous environments and/or biological fluids, such as medical devices and diagnostics. The silicone polyurea copolymers can provide advantageous features to a surface. Articles are also described that include the coating compositions on a surface, as well as methods to coat surfaces. BACKGROUND Silicone rubber surfaces are known for excellent biocompatibility and reduced non-specific protein and cell adhesion over other surfaces, when such surfaces are exposed to biological fluids (for example, when emplaced, either temporarily, for extended periods of time, or permanently, in a patient's body). However, silicone is not suitable for the bulk material of many devices utilized in the medical field, for example, implantable devices, devices for in vitro diagnostics, and/or devices that come in contact with biological fluids outside a patient's body or temporarily emplaced within a patient's body. This unsuitability is due in large part to the material's high elasticity. Medical devices and diagnostic products are frequently made from temperature sensitive materials that can be easily damaged by many solvents. Ideally, therefore, a coating to be applied to such devices and diagnostic products would be soluble in water, or in a less aggressive solvent such as an alcohol. One solvent used when applying coatings to medical devices and diagnostics is isopropanol, and this solvent is generally accepted by the industry. BRIEF SUMMARY OF THE INVENTION Silicone polyurea block copolymers, coating compositions including these block copolymers, methods of synthesizing the block copolymers, methods of providing a passivating or a lubricious surface using the block copolymers, and coated surfaces are described herein. Silicone polyurea copolymers include siloxane, alkyl, and polyethylene glycol/polypropylene glycol copolymer or dipiperidyl propane repeating units separated by urea linkages. In some implementations, the total isocyanate (“total isocyanate” as used herein to include mono- and diisocyanate) is present in a molar ratio with total diamines in a range of 1.5:1 to 1.05:1, or in a range of 1:1.05 to 1:1, or in a range of 1.3:1 to 1.2:1, or in a range of 1:1.2 to 1:1.3. In some implementations, total isocyanate is present in an amount that is equal to, or greater than, the amount of total diamines in the silicone polyurea block copolymer. Inventive silicone polyurea copolymers can provide a wide variety of properties to a surface. In some implementations, inventive silicone polyurea copolymers provide passivating surfaces or lubricious surfaces to medical devices and diagnostics. The silicone polyurea copolymers can exhibit improved properties as compared to other polymers used to modify surface properties of a device. In particular, inventive silicone polyurea copolymers can be synthesized under relatively simple reaction conditions, and the resulting block copolymers can be soluble in mild solvents (e.g., water, alcohol, alcohol-water mixtures, or buffer solutions), can be easily applied to a wide variety of surfaces, and are customizable for particular applications. In some aspects, inventive polyurea copolymers can provide antifouling coating compositions that are suitable for use as coatings on articles immersed in or exposed to an aquatic environment (referred to herein as “aquatic articles). Aquatic environments encompass natural or artificial systems such as lakes, rivers, fountains, ponds (e.g., fish ponds), canals, aquariums, aquaculture systems, water holding or conveying systems, water reservoirs, open drinking water systems, brackish water environments, waste water and oceans. In these aspects, inventive polyurea copolymers can be used in connection with man-made structures such as docks, ship and boat hu