Biocompatible crosslinked coating and crosslinkable coating polymer composition for forming such a coating

• US RE40,816 E1
• Filed: 11/01/1996
• Issued: 06/30/2009
• Est. Priority Date: 11/01/1995
• Status: Expired due to Term

• Current Assignee: Biocompatibles Incorporated (Boston Scientific Corporation)
• Original Assignee: Biocompatibles Incorporated (Boston Scientific Corporation)
• Inventors: Yianni, Yiannakis Petrou, Woodroffe, Matthew John, Taylor, Alistair Stewart, Stratford, Peter William, Rowan, Lee
• Primary Examiner(s): TESKIN, FRED M
• Application Number:
  US10/946,604
• Time in Patent Office: 4,624 Days
• Field of Search: 526/277, 526/287, 526/288, 526/319, 623/23.7, 623/1.11, 623/23.57
• US Class Current: 623/1.46
• CPC Class Codes: A61F 2/0077 Special surfaces of prostheses, e.g. for improving ingrowth A61F2/30767 takes precedence
• CPC Class Codes: A61F 2/90 characterised by a net-like or mesh-like structure
• CPC Class Codes: A61F 2/95 Instruments specially adapted for placement or removal of stents or stent-grafts
• CPC Class Codes: A61F 2/966 with relative longitudinal movement between outer sleeve and prosthesis, e.g. using a push rod
• CPC Class Codes: A61F 2002/9665 with additional retaining means
• CPC Class Codes: A61F 2210/0019 operated at only one temperature whilst inside or touching the human body, e.g. constrained in a non-operative shape during surgery, another temperature only occurring before the operation
• CPC Class Codes: A61F 2220/0058 soldered or brazed or welded
• CPC Class Codes: A61F 2220/0075 sutured, ligatured or stitched, retained or tied with a rope, string, thread, wire or cable
• CPC Class Codes: B21F 45/00 Wire-working in the manufacture of other particular articles of pins, needles, nails, hairpins B21G; of chains B21L ; for semiconductor devices H01L24/42
• CPC Class Codes: B21F 45/008 of medical instruments, e.g. stents, corneal rings medical science A61
• CPC Class Codes: D04C 1/02 made from particular materials
• CPC Class Codes: D10B 2401/046 Shape recovering or form memory
• CPC Class Codes: D10B 2509/06 Vascular grafts; stents

Abstract

A braided stent (1) for transluminal implantation in body lumens is self-expanding and has a radial expanded configuration in which the angle α between filaments is acute. Some or all of filaments (6,7) are welded together in pairs at each end (4,5) of the stent to provide beads (8), thereby strengthening the stent and assisting its deployment from a delivery device. The stent is preferably completely coated using a biocompatible polymeric coating, said polymer preferably having pendant phosphoryl choline groups. A method of making the stent by braiding and welding is described as well as a delivery device for deploying the device.The present invention provides a biocompatible crosslinked coating and a crosslinkable coating polymer composition for forming such a coating. The biocompatible crosslinked coating may be formed by curing a polymer of 23 mole % (methacryloyloxy ethyl)-2-(trimethylammonium ethyl) phosphate inner salt, 47 mole % lauryl methacrylate, 5 mole % γtrimethoxysilyl propyl methacrylate and 25 mole % of hydroxy propyl methacrylate. The crosslinkable coating polymer may include 23 mole % (methacryloyloxy ethyl)-2-(trimethylammonium ethyl) phosphate inner salt, 47 mole % lauryl methacrylate, 5 mole % γtrimethoxysilyl propyl methacrylate and 25 mole % of hydroxy propyl methacrylate.

Claims

1. A radially self-expanding stent adapted for implantation in a body passage comprises first and second sets of mutually counter-rotating metallic filaments which are braided together and define a tubular stent body having two ends which is biased towards a first radially expanded configuration in which it is unconstrained by external applied forces and can be retained in a second radially compressed configuration, in which in the said first configuration the angle α

between the filaments at a crossover point at the mid point of the stent is less than 90° and

in which some or all of the filaments at the ends of the body are fixed together in pairs each consisting of counter-rotating filaments such that the angle at which the filaments are fixed is within the range α

−

10 to α

+10, and in which the filaments are joined at a bead which has a diameter of at least 1.2 times the diameter of the filament.

2. The stent according to claim 1 wherein α

is in the range of 60°

to 90°

.

3. The stent according to claim 2 wherein the angle at which the filament ends are fixed is in the range of α

−

5 to α

.

4. The stent according to claim 1, further comprising a polymeric biocompatible coating comprising a zwitterionic pendant group coating the surfaces of the filaments.

5. The stent according to claim 1, wherein the filaments are free to slide over each other at the crossover points.

6. The stent according to claim 1, wherein each beed bead has a diameter of more than twice the mean diameter of each filament.

7. The stent according to claim 1, wherein the filaments are formed of a shape memory alloy having a transition temperature and in which the stent adopts the said first radially expanded configuration below the transition temperature of the alloy and, when the stent is subjected to a temperature above the transition temperature of the alloy the stent adopts a maximally radially expanded configuration in which one or both of the diameter and resistance of the stent to radial compression is increased.

8. A method of making a stent according to claim 1, which comprises braiding filaments over a first mandrel to make an elongate precursor, severing a pre-selected length from the precursor, placing the severed portion onto a second mandrel which has a diameter which is within the range (0.8 to 1.25)×

d (where d is the diameter of the stent in its radially expanded condition) such that one end of the braided portion extends beyond the end of the second mandrel and in the method the protruding ends of at least some of the filaments are joined to each other in counter-rotating pairs whereby each pair of counter-rotating filaments is joined by a beed bead of metal having a diameter of at least 1.2 times the mean diameter of the individual filaments.

9. The method according to claim 8, which comprises joining the filament ends together by welding.

10. The method according to claim 9, which comprises annealing the stent before or after the welding step.

11. The method according to claim 8, which comprises joining all the filaments required to be welded at one end of the stent in their respective pairs simultaneously and, in a separate step, joining all the filaments required to be welded at the other end in their respective pairs.

12. The method according to claim 8, which comprises subsequently coating the stent with a liquid coating composition and drying the coating to form an adherent coating of a biocompatible polymer.

13. The method according to claim 12, wherein the polymer comprises zwitterionic pendant groups.

14. The method according to claim 12, which comprises drying the coating by directing a flow of gas through the stent in an axial direction.

15. A graft comprising at least one stent according to claim 1 surrounded by a sleeve formed of an elastomeric material.

16. A combination of a stent according to claim 1, the stent being in the radially compressed configuration, and a delivery device, in which the delivery device comprises an internal pusher tube comprising an inner guidewire lumen for receiving a guidewire, and an external sleeve, the sleeve and pusher defining there between an annular space, wherein the stent is surrounded along substantially its entire axial length by the sleeve and at least one end of the stent is retained in the annular space between the sleeve and pusher.

17. The stent according to claim 1, wherein α

is in the range of 65°

to 85°

.

18. The stent according to claim 1, wherein α

is in the range of 70°

to 80°

.

19. The stent according to claim 4, wherein the polymeric biocompatible coating comprises an ammonium phosphate ester group.

20. A cross-linkable coating polymer of 23 mole % (methacryloyloxy ethyl)-2-(trimethylammonium ethyl) phosphate inner salt, 47 mole % lauryl methacrylate, 5 mole % γ

trimethoxysilyl propyl methacrylate and 25 mole % of hydroxy propyl methacrylate.

21. A biocompatible crosslinked coating formed by curing a polymer of 23 mole % (methacryloyloxy ethyl)-2-(trimethylammonium ethyl) phosphate inner salt, 47 mole % lauryl methacrylate, 5 mole % γ

trimethoxysilyl propyl methacrylate and 25 mole % of hydroxy propyl methacrylate.