Crosslinked polymers including one or more antioxidants, methods for making same and methods for selecting antioxidants

Patent metadata

Field	Value
Publication number	US-9707316-B2
Application number	US-201615149583-A
Country	US
Kind code	B2
Filing date	May 9, 2016
Priority date	Dec 6, 2010
Publication date	Jul 18, 2017
Grant date	Jul 18, 2017

Abstract

Polymer compositions having one or more antioxidants providing high crosslink density and improved oxidation resistance to the polymer composition and methods for making same. Such polymer compositions can be used to make orthopedic implants.

First claim

The invention claimed is:

1. An orthopedic implant, comprising:
a consolidated and crosslinked UHMWPE blend, the UHMWPE blend comprising:
a homogeneous blend of UHMWPE resin,
6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid, and
a primary antioxidant chosen from lauryl gallate, octyl gallate, propyl gallate, curcumin, resveratrol, rutin, vitamin E, gamma-tocopherol, 2,2,5,7,8-penta-methyl-6-chromamol, catechin, chlorogenic acid, tannic acid, gallic acid, ellagic acid, bilberry, hesperidin, naringin, E-4-hydroxy nonenal, vitamin C, 2,6-dimethyl-2,4,6-octratriene, and pentaerythritol tetrakis (3-(3,5-di-tert-4-hydroxyphenyl)propionate),

wherein a combined concentration of the 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid and the primary antioxidant prior to crosslinking is about 0.05% to about 5% by weight of the UHMWPE blend.

2. The orthopedic implant of claim 1 , wherein the consolidated and crosslinked UHMWPE blend has a crosslink density, an oxidation index rate, and an oxidation induction time measure by the offset method, and the product of the crosslink density and oxidation induction time is greater than 1.5.

3. The orthopedic implant of claim 1 , wherein the product of the crosslink density and the inverse of the oxidation index rate of the consolidated and crosslinked UHMWPE blend is greater than 2500.

4. The orthopedic implant of claim 1 , wherein the consolidated and crosslinked UHMWPE blend has an oxidation induction time as measured by the offset method of greater than 15 minutes.

5. The orthopedic implant of claim 1 , wherein the consolidated and crosslinked UHMWPE blend has an oxidation index rate of less than 0.006 OI/week.

6. The orthopedic implant of claim 1 , wherein the primary antioxidant is sufficient to react directly with free peroxy radicals (—OO.) at a higher rate than directly with hydroperoxides (—OOH).

7. The orthopedic implant of claim 1 , wherein the 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid is sufficient to react directly with hydroperoxides (—OOH) at a higher rate than directly with free peroxy radicals (—OO.).

8. The orthopedic implant of claim 1 , wherein the combined concentration of the primary antioxidant and the 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid prior to cross linking the UHMWPE blend is about 0.05% to about 2% by weight of UHMWPE blend.

9. The orthopedic implant of claim 1 , wherein the combined concentration of the primary antioxidant and the 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid prior to cross linking the UHMWPE blend is about 0.05% to about 1% by weight of the UHMWPE blend.

10. The orthopedic implant of claim 1 , wherein the primary antioxidant is vitamin E, gamma-tocopherol, or 2,2,5,7,8-penta-methyl-6-chromanol.

11. The orthopedic implant of claim 1 , wherein the primary antioxidant is vitamin E.

12. A method of making the orthopedic implant of claim 1 , the method comprising:
mixing UHMWPE resin with a primary antioxidant and a 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid to obtain a homogeneous blend, wherein the primary antioxidant is chosen from lauryl gallate, octyl gallate, octyl gallate, propyl gallate, curcumin, resveratrol, rutin, vitamin E, gamma-tocopheol, 2,2,5,7,8-penta-methyl-6-chromamol, catechin, chlorogenic acid, tannic acid, gallic acid, ellagic acid, bilberry, hesperidin, naringin, E-4-hydroxy nonenal, vitamin C, 2,6-dimethyl-2,4,6-octratriene, and pentaerythritol tetrakis (3(3,5-di-tert-4-hydroxyphenyl)propionate), wherein the combined concentration of the primary antioxidant and the 6-hydroxy-2,5,7,8-etramethylchroman-2-carboxylic acid prior to the crosslinking of the UHMWPE blend is about 0.05% to about 5% by weight of the UHMWPE blend;
consolidating the blend; and
irradiating the consolidated blend to crosslink the consolidated blend.

13. The method of claim 12 , wherein the mixing comprises
mixing the UHMWPE resin with the primary antioxidant, and
mixing the UHMWPE resin with the 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid.

14. The method of claim 12 , wherein the mixing comprises mixing the UHMWPE resin with vitamin E and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid.

15. The method of claim 12 , wherein the irradiating the consolidated blend to crosslink the consolidated blend comprises irradiating the consolidated blend with at least one of electron beam radiation, gamma radiation, and x-ray radiation.

16. The method of claim 15 , wherein a total crosslinking irradiation dose is substantially between about 50 kGy and about 1000 kGy.

17. The method of claim 12 , wherein the irradiation treatment is provided by e-beam radiation at a dose rate of at least 1 MegaGrey per hour.

18. The method of claim 12 , wherein the irradiation treatment is provided by e-beam radiation at a dose rate of at least 18 MegaGrey per hour.

19. The method of claim 12 , wherein the method further includes preheating the consolidated blend to a preheat temperature below the melting point of the consolidated blend.

20. A method of making an orthopedic implant, the method comprising:
mixing UHMWPE resin with 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid and a primary antioxidant chosen from lauryl gallate, octyl gallate, propyl gallate, curcumin, resveratrol, rutin, vitamin E, gamma-tocopherol, 2,2,5,7,8-penta-methyl-6-chromamol, catechin, chlorogenic acid, tannic acid, gallic acid, ellagic acid, bilberry, hesperidin, naringin, E-4-hydroxy nonenal, vitamin C, 2,6-dimethyl-2,4,6-octratriene, and 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid to obtain a homogeneous blend, wherein the combined concentration of the primary antioxidant and the 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid prior to the crosslinking of the UHMWPE blend is about 0.05% to about 5% by weight of the UHMWPE blend;
consolidating the blend; and
irradiating the consolidated blend to crosslink the consolidated blend;
wherein the orthopedic implant comprises the crosslinked consolidated blend, the crosslinked consolidated blend comprising
a homogeneous blend of UHMWPE resin,
the 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid, and
the primary antioxidant.

Assignees

• Zimmer Inc

Inventors

• Thomas Brian H
• Acker Dean M
• Gsell Ray
• Stark Norman

Classifications

• A61L27/505

  Stabilizers · CPC title

• A61L27/50

  Materials characterised by their function or physical properties {, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials} · CPC title

• C08L23/06

  Polyethylene · CPC title

• A61L2/16

  using chemical substances · CPC title

• A61L27/16 Primary

  obtained by reactions only involving carbon-to-carbon unsaturated bonds · CPC title