Non-oxidizing polymeric medical implant

• US 6,664,308 B2
• Filed: 01/08/2002
• Issued: 12/16/2003
• Est. Priority Date: 06/01/1993
• Status: Expired due to Fees

• Current Assignee: Howmedica Osteonics Corp. (Stryker Corporation)
• Original Assignee: Stryker Technologies Corporation
• Inventors: Sun, Deh-Chuan, Stark, Casper F.
• Primary Examiner(s): Berman, Susan W.
• Application Number:
  US10/041,118
• Publication Number:
  US 20020107299A1
• Time in Patent Office: 707 Days
• Field of Search: 522/161, 522/157, 522/158, 522/159, 522/160, 522/111, 522/112, 523/105, 523/113, 523/115, 525/937, 525/333.7, 264/496, 264/488, 264/345, 264/346, 264/347, 264/348, 264/331.17, 623/16.11, 623/13.12, 623/18.11, 623/19.11, 623/20.11, 623/20.14, 623/22.1, 623/22.21, 623/23.39
• US Class Current: 522/161
• CPC Class Codes: A61L 15/60 Liquid-swellable gel-forming materials, e.g. super-absorbents
• CPC Class Codes: A61L 2/08 Radiation
• CPC Class Codes: A61L 2/081 Gamma radiation
• CPC Class Codes: A61L 2/082 X-rays
• CPC Class Codes: A61L 2/087 Particle radiation, e.g. electron-beam, alpha or beta radiation
• CPC Class Codes: A61L 27/16 obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 29/041 obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 31/048 obtained by reactions only involving carbon-to-carbon unsaturated bonds A61L31/041 takes precedence
• CPC Class Codes: B29C 2035/085 using gamma-ray
• CPC Class Codes: B29C 35/0805 using electromagnetic radiation
• CPC Class Codes: B29C 43/00 Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor by liberation of internal stresses B29C61/006
• CPC Class Codes: B29C 43/16 Forging
• CPC Class Codes: B29K 2023/0683 UHMWPE, i.e. ultra high molecular weight polyethylene
• CPC Class Codes: B29K 2105/253 Preform
• CPC Class Codes: B29K 2995/0087 Wear resistance
• CPC Class Codes: B29K 2995/0089 Impact strength or toughness
• CPC Class Codes: B29L 2031/7532 Artificial members, protheses
• CPC Class Codes: C08L 23/04 Homopolymers or copolymers of ethene
• CPC Class Codes: C08L 23/06 Polyethene
• CPC Class Codes: Y10S 522/915 involving inert gas, steam, nitrogen gas, or carbon dioxide
• CPC Class Codes: Y10S 525/937 : Utility as body contact e.g. implant, contact lens or I.U.D.
• CPC Class Codes: Y10S 623/901 : Method of manufacturing prosthetic device

Abstract

A medical implant made of polymeric material having an increased oxidation resistance is formed by a method including the steps of placing a resin powder in a sealed container. A substantial portion of the oxygen is removed from the sealed contained by either a vacuum, an oxygen absorbent or by flushing with inert gas. The container is then repressurized with a gas such as nitrogen, argon, helium or neon so that long term storage may be possible. On use, the resin in transferred to a forming device which both melts and forms the resin in an oxygen reduced atmosphere to produce a polymeric raw material such as a rod or bar stock. The medical implant is then formed from this raw material annealed and sealed in an airtight package in an oxygen reduced atmosphere. The implant is then radiation sterilized and thereafter annealed in the package for a predetermined time and temperature sufficient to form cross-links between any free radicals in neighboring polymeric chains.

Claims

1. A method of treatment for the ultra-high molecular weight polyethylene material forming a medical implant, said material having a weight-average molecular weight greater than 400,000, the method comprising:

preventing said ultra-high molecular weight polyethylene material forming the implant from contact with oxygen in a concentration greater than 1% volume by volume;

irradiating the polyethylene material forming said implant to create free radicals while said ultra-high molecular weight polyethylene material is prevented from contact with oxygen in a concentration greater than 1% volume by volume; and

heating the polyethylene material forming the implant to form cross-links between said free radicals for a temperature and time at least equivalent to 50°

C. for 144 hours as defined by Arrhennius'"'"' equation (14) while said ultra-high molecular weight polyethylene material is prevented from contact with oxygen in a concentration greater than 1% volume by volume.

2. The method as set forth in claim 1, wherein the contact with oxygen is prevented by sealing the polyethylene within an oxygen impermeable barrier.

3. The method as set forth in claim 2, wherein the oxygen impermeable barrier is a packaging material.

4. The method as set forth in claim 3, wherein the irradiating and heating are applied to a fully formed implant sealed within said packaging material.

5. The method as set forth in claim 1, wherein the temperature is greater than 25°

C.

6. The method as set forth in claim 5, wherein the heating takes place for at least about four hours.

7. The method as set forth in claim 1, wherein the polyethylene material has a solubility of less than 80.9% in solvent after treatment.

8. The method as set forth in claim 1, wherein after treatment the polyethylene material has an oxidation index of 0.01 or less after oven aging in air at 80°

C.

9. The method as set forth in claim 1, wherein the polyethylene material is heated to a temperature of between 25°

C. and the melting point of said polymer.

10. The method as set forth in claim 1, wherein the polyethylene implant material is surrounded by a layer of material whose function is to prevent said polyethylene material from contact with oxygen, said layer of material is heated while surrounded by an oxygen containing atmosphere.

11. The method as set forth in claim 1, wherein the material forming the implant has less than 1.0×

10¹⁷ residual free radicals per grams after said treatment to form cross-links.

12. A method for processing ultra-high molecular weight polyethylene having a weight-average molecular weight greater than 400,000 comprising:

creating free radicals in the polymer chain by irradiating the ultra-high molecular weight polyethylene;

preventing oxygen from bonding with said created free radicals by preventing them from coming into contact with oxygen in a concentration greater than 1% volume by volume; and

heating the polymer to create cross-links between free radicals prior to exposing the free radicals to oxygen above said concentration, said heating for a time and temperature at least equivalent to heating said polyethylene at 50°

C. for 144 hours as defined by Arrhennius'"'"' equation (14).

13. The method as set forth in claim 12, wherein the contact with oxygen is prevented by sealing the polyethylene within an oxygen impermeable barrier.

14. The method as set forth in claim 12, wherein the oxygen impermeable barrier is a packaging material.

15. The method as set forth in claim 14, wherein the irradiating and heating are applied to a fully formed implant sealed within said packaging material.

16. The method as set forth in claim 12, wherein the temperature is greater than 25°

C.

17. The method as set forth in claim 12, wherein the heating takes place for at least about four hours.

18. The method as set forth in claim 12, wherein the polyethylene material has a solubility of less than 80.9% in solvent after cross-linking.

19. The method as set forth in claim 12, wherein after cross-linking the polyethylene material has an oxidation index which does not increase with oven aging in air at 80°

C. for up to 11 days.

20. The method as set forth in claim 12, wherein the polyethylene material is heated to a temperature between 25°

C. and the melting point of said polymer.

21. The method as set forth in claim 12, wherein the polyethylene is surrounded by a layer of material whose function is to prevent said polyethylene material from said contact with oxygen, said layer of material is heated while surrounded by an oxygen containing atmosphere.

22. The method as set forth in claim 12, wherein the polyethylene has less than 1.0×

10¹⁷ residual free radicals per grams after said cross-linking.

23. An orthopedic implant comprising material processed according to the method of claim 12.

24. A medical implant comprising:

an ultra-high molecular weight polyethylene having a weight average molecular weight greater than 400,000, said material being free of free radical generation catalysts and having a level of cross-linking between free radicals which is at least equal to that resulting from heating an ultra-high molecular weight polyethylene material having a weight average molecular weight greater than 400,000 which has been irradiated to create free radicals in the absence of a free radical generation catalyst while out of contact with oxygen in a concentration greater than 1% volume by volume and then heated while out of contact with oxygen in a concentration greater than 1% volume by volume at a temperature of greater than 25°

C. for a sufficient time to create a level of cross-links between free radicals wherein the temperature and time are selected to be at least equivalent to heating said irradiated material at 50°

C. for 144 hours as defined by the Arrhennius'"'"' equation (14).