IP Library Granted Patent US 10,981,302
Granted Patent B2
US 10,981,302 · App. 16/291,283 · Granted Apr 20, 2021

Peroxide cross-linking and high temperature melting

Inventors: Orhun K. Muratoglu (Cambridge, MA); Ebru Oral (Newton, MA)
Assignee: THE GENERAL HOSPITAL CORPORATION
B29C35/0805A61F2/0095B29B7/88B29B11/06B29B11/12B29B13/022B29B13/045B29C35/02B29C35/0866B29C43/006B29C43/10B65B31/00B65B55/08B65B55/10B65B55/16B65B55/18C08J3/203C08J3/24C08J7/12C08J7/123B29B2013/002B29C2035/085B29C2035/0877B29C2071/022B29C2791/001B29C2791/002B29K2023/0683B29K2105/0035B29K2995/0087B29L2009/00B29L2031/7532C08J2323/06
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Quick Facts
Patent No.
US 10,981,302
App. No.
16/291,283
Granted
Apr 20, 2021
Kind
B2
Abstract

Methods of making oxidation and wear resistant polymeric materials using peroxide cross-linking and high temperature melting process are disclosed. A multiple step procedure for enabling the manufacturing of such material without size limitations is also disclosed.

Claims (46)

1. A medical implant comprising a cross-linked polymeric material made by the method comprising the steps of:

a. blending a polymeric material with at least one antioxidant at a concentration that is between 0.05 wt % and 66.0 wt % and at least one cross-linking agent at a concentration that is between 0.5 and 66.5 wt %;

b. consolidating the blended polymeric material;

c. heating the consolidated polymeric material to a temperature that is about 200° C. or more for a period of time, wherein the heating step comprises:

i. heating the consolidated polymeric material to a temperature that is between about 200° C. and about 290° C.,

ii. maintaining the consolidated blended polymeric material at a temperature that is between about 200° C. and about 290° C.,

iii. heating the consolidated polymeric material to a temperature that is between about 290° C. and 350° C., and

iv. maintaining the consolidated blended polymeric material at a temperature that is between about 290° C. and 350° C. for at least 5 hours but no more than 30 hours; and

d. cooling the consolidated polymeric material, wherein the cooling step comprises:

i. permitting the heated consolidated blended polymeric material to cool to a temperature that is between about 135° C. and about 180° C.,

ii. maintaining the consolidated blended polymeric material at a temperature that is between about 135° C. and about 180° C., and

iii. permitting the consolidated blended polymeric material to cool to a temperature that is between about room temperature and 60° C.

2. The medical implant according to claim 1 , wherein at least one antioxidant is vitamin E or Tetrakis[methylene(3,5-di-tertbutylhydroxyhydrocinnamate)] methane.

3. The medical implant according to claim 1 , wherein at least one cross-linking agent is a peroxide, P130, a carbon-carbon initiator, 2,3-dimethyl-2,3-diphenylbutane, poly-1,4-diisopropylbenzene, or a mixture thereof.

4. The medical implant according to claim 1 , wherein the heating after consolidation is done in inert gas.

5. The medical implant according to claim 1 , wherein the heating after consolidation is done in air.

6. The medical implant according to claim 1 , wherein the consolidation is carried out at a temperature that is between 150° C. and 210° C.

7. The medical implant according to claim 1 , wherein the crosslinked polymeric material is further machined into a medical implant.

8. The medical implant according to claim 1 , wherein the consolidation is done by ram extrusion.

9. The medical implant according to claim 1 , wherein the antioxidant concentration is no more than 1.0 wt %.

10. The medical implant according to claim 1 , wherein the crosslinking agent initiates cross-linking in the polymeric material.

11. An interlocked hybrid material made by the method comprising the steps of:

a. blending a polymeric material with at least one antioxidant at a concentration that is between 0.05 wt % and 66.0 wt % and at least one cross-linking agent at a concentration that is between 0.5 and 66.5 wt %;

b. layering the blended polymeric material and a second material;

c. consolidating the layers, thereby forming an interlocked hybrid material;

d. heating the interlocked hybrid material to a temperature that is above 200° C. for a period of time, wherein the heating step comprises:

i. heating the interlocked hybrid material to a temperature that is between about 200° C. and about 290° C.,

ii. maintaining the interlocked hybrid material at a temperature that is between about 200° C. and about 290° C.,

iii. heating the interlocked hybrid material to a temperature that is between about 290° C. and 350° C. and

iv. maintaining the interlocked hybrid material at a temperature that is between about 290° C. and 350° C. for at least 5 hours but no more than 30 hours; and

e. cooling the interlocked hybrid material, wherein the cooling step comprises:

i. permitting the heated interlocked hybrid material to cool to a temperature that is between about 135° C. and about 180° C.,

ii. maintaining the interlocked hybrid material at a temperature that is between about 135° C. and about 180° C., and

iii. permitting the interlocked hybrid material to cool to a temperature that is between about room temperature and 60° C.

12. The interlocked hybrid material according to claim 11 , wherein the second material is a porous metal.

13. The interlocked hybrid material according to claim 11 , wherein the interlocked hybrid material is consolidated in the form of a medical implant.

14. The interlocked hybrid material according to claim 11 , wherein the interlocked hybrid material is machined into a medical implant.

15. The interlocked hybrid material according to claim 11 , wherein the antioxidant concentration is no more than 1.0 wt %.

16. The interlocked hybrid material according to claim 11 , wherein the crosslinking agent initiates cross-linking in the polymeric material.

17. The interlocked hybrid material according to claim 11 , wherein the consolidation is carried out at a temperature that is between 150° C. and 210° C.

18. The interlocked hybrid material according to claim 11 , wherein at least one antioxidant is vitamin E or Tetrakis[methylene(3,5-di-tertbutylhydroxyhydrocinnamate)] methane.

19. The interlocked hybrid material according to claim 11 , wherein at least one cross-linking agent is a peroxide, P130, a carbon-carbon initiator, 2,3-dimethyl-2,3-diphenylbutane, poly-1,4-diisopropylbenzene, or a mixture thereof.

20. The interlocked hybrid material according to claim 11 , wherein the heating after consolidation is done in inert gas.

21. The interlocked hybrid material according to claim 11 , wherein the heating after consolidation is done in air.

22. The medical implant according to claim 3 , wherein the peroxide is selected from the group consisting: diacyl peroxides, peroxyesters, peoxydicarbonates, dialkyl peroxides, ketone peroxides, peroxyketals, cyclic peroxides, peroxymonocarbonates, hydroperoxides, benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, acetone peroxide, 2,5-Di(tert-butylperoxy)-2,5-dimethyl-3-hexyne, 3,3,5,7,7-pentamethyl-1,2,4 trioxepane, dilauryl peroxide, methyl ether ketone peroxide, t-amyl peroxyacetate, t-butyl hydroperoxide, t-amyl peroxybenzoate, Di-t-amyl peroxide, 2,5-Dimethyl 2,5-Di(t-butylperoxy) hexane, t-butylperoxy isopropyl carbonate, succinic acid peroxide, cumene hydroperoxide, 2,4-pentanedione peroxide, t-butyl perbenzoate, diethyl ether peroxide, acetone peroxide, arachidonic acid 5-hydroperoxide, carbamide peroxide, tert-butyl hydroperoxide, t-butyl peroctoate, t-butyl cumyl peroxide, Di-sec-butylperoxydicarbonate, Di-2-ethyl hexyperoxydicarbonate, 1,1-Di(t-butylperoxy)cyclohexane, 1, 1-Di(tertbutyl peroxy)-3, 3, 5-trimethylcyclohexane, 2, 5-Dimethyl-2, 5-di(tert-butylperoxy)hexane, 3,3,5,7, 7-Pentamethyl-1,2,4-trioxepane, Butyl 4,4-di(tert-butylperoxy)valerate, Di(2,4-dichlorobenzoyl) peroxide, Di(4-methylbenzoyl) peroxide, Di(tert-butylperoxyisopropyl) benzene, tert-Butyl cumyl peroxide, tert-Butyl peroxy-3,5,5-trimethylhexanoate, tert-Butyl peroxybenzoate, and tert-Butylperoxy 2-ethylhexyl carbonate, or mixtures thereof.

23. The interlocked hybrid material according to claim 19 , wherein the peroxide is selected from the group consisting: diacyl peroxides, peroxyesters, peoxydicarbonates, dialkyl peroxides, ketone peroxides, peroxyketals, cyclic peroxides, peroxymonocarbonates, hydroperoxides, benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, acetone peroxide, 2,5-Di(tert-butylperoxy)-2,5-dimethyl-3-hexyne, 3,3,5,7,7-pentamethyl-1,2,4 trioxepane, dilauryl peroxide, methyl ether ketone peroxide, t-amyl peroxyacetate, t-butyl hydroperoxide, t-amyl peroxybenzoate, Di-t-amyl peroxide, 2,5-Dimethyl 2,5-Di(t-butylperoxy) hexane, t-butylperoxy isopropyl carbonate, succinic acid peroxide, cumene hydroperoxide, 2,4-pentanedione peroxide, t-butyl perbenzoate, diethyl ether peroxide, acetone peroxide, arachidonic acid 5-hydroperoxide, carbamide peroxide, tert-butyl hydroperoxide, t-butyl peroctoate, t-butyl cumyl peroxide, Di-sec-butylperoxydicarbonate, Di-2-ethyl hexyperoxydicarbonate, 1,1-Di(t-butylperoxy)cyclohexane, 1, 1-Di(tertbutyl peroxy)-3, 3, 5-trimethylcyclohexane, 2, 5-Dimethyl-2, 5-di(tert-butylperoxy)hexane, 3,3,5,7, 7-Pentamethyl-1,2,4-trioxepane, Butyl 4,4-di(tert-butylperoxy)valerate, Di(2,4-dichlorobenzoyl) peroxide, Di(4-methylbenzoyl) peroxide, Di(tert-butylperoxyisopropyl) benzene, tert-Butyl cumyl peroxide, tert-Butyl peroxy-3,5,5-trimethylhexanoate, tert-Butyl peroxybenzoate, and tert-Butylperoxy 2-ethylhexyl carbonate, or mixtures thereof.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 18, 2020
From: MURATOGLU, ORHUN K.; ORAL, EBRU
To: THE GENERAL HOSPITAL CORPORATION
Reel/Frame 052970/0001 →
Continuity (3)
Division 15030206
Provisional Application 61892249 · Oct 17, 2013
Related Publication 20190255744A1 · Aug 22, 2019
Cited By (1)
US 12,350,403