Modification of polymeric surface by graft polymerization

• US 5,229,172 A
• Filed: 01/19/1993
• Issued: 07/20/1993
• Est. Priority Date: 01/19/1993
• Status: Expired due to Term

• Current Assignee: Medtronic Incorporated (Medtronic Plc)
• Original Assignee: Medtronic Incorporated (Medtronic Plc)
• Inventors: Cahalan, Patrick T., Verhoeven, Michel
• Primary Examiner(s): PIANALTO, BERNARD D
• Application Number:
  US08/005,698
• Time in Patent Office: 182 Days
• Field of Search: 427/536, 427/412.3, 427/412.4, 427/412.5, 427/539, 427/551
• US Class Current: 427/536
• CPC Class Codes: A61L 33/0011 Anticoagulant, e.g. heparin, platelet aggregation inhibitor, fibrinolytic agent, other than enzymes, attached to the substrate
• CPC Class Codes: A61L 33/0029 using an intermediate layer of polymer
• CPC Class Codes: A61L 33/0088 by grafting of a monomer onto the substrate
• CPC Class Codes: C08J 7/18 using wave energy or particle radiation

Abstract

A method for modifying the surface characteristics of a polymeric material by irradiating a surface of the polymeric material in the presence of an oxygen and then grafting acrylamide to the irradiated surface by contacting the irradiated surface with an aqueous solution including acrylamide monomer and ceric ion. Grafted polymer surfaces with dense surface coverage are produced without using a deaerated monomer solution. Biofunctional molecules can be ionically or covalently bonded to the grafted surface.

Claims

1. A method for modifying the surface characteristics of a solid polymeric material comprising the steps of;

(a) irradiating a surface of the polymeric material in the presence of an oxygen source such that the bulk properties of the material are not degraded;

(b) applying to the irradiated surface an aqueous solution including acrylamide monomer and ceric ion, whereby the monomer is grafted to the irradiated surface.

2. A method according to claim 1 wherein the polymeric material is selected from the group consisting of polyurethanes, silicones, polyolefins, fluoropolymers, polyesters, polyethers, polyamides and blends and copolymers thereof.

3. A method according to claim 1 wherein the irradiating step is accomplished by an irradiation method selected from the group consisting of plasma discharge, corona discharge, electron beam, and gamma radiation.

9. A method according to claim 1 or 4 wherein the acrylamide monomer is at a concentration in the aqueous solution in the range of about 20 to 40 percent by weight.

10. A method according to claim 9 wherein the ceric ion in the solution is at a concentration in the range of about 0.0002 to 0.0005 mole of ceric ion per mole of monomer.

11. A method according to claim 1 or 4 further comprising the step of attaching a biomolecule to the grafted surface.

12. A method according to claim 11 wherein the biomolecule is selected from the group consisting of albumin, fibrinogen fibronectin, heparin, glycoproteins, immunoglobulins, and growth factors.

13. A method according to claim 11 further comprising the step of applying between the grafted surface and biomolecule a coupling agent which is at least bifunctional.

14. A method according to claim 13 wherein the coupling agent is selected from the group consisting of ethylenediamine and polyethyleneimine.

4. A method for modifying the surface characteristics of a solid polymeric material comprising the steps of;

(a) irradiating a surface of the polymeric material in the presence of an oxygen source by an irradiation method selected from the group consisting of plasma discharge, corona discharge, electron beam, and gamma radiation;

(b) applying to the irradiated surface an aqueous solution including acrylamide monomer and ceric ion, whereby the monomer is grafted to the irradiated surface.

5. A method according to claim 4 wherein the polymeric material is selected from the group consisting of polyurethanes, silicones, polyolefins, fluoropolymers, polyesters, polyethers, and polyamides.

6. A method according to claim 4 wherein the irradiation applied is corona discharge radiation applied to the polymeric material at an intensity in the range of about 0.2 to 1.0 kilowatts.

7. A method according to claim 4 wherein the irradiation applied is a radio frequency plasma applied to the polymeric material at an intensity in the range of about 15 to 25 watts.

8. A method according to claim 4 wherein the irradiation applied is an electron beam applied to the polymeric material at an intensity in the range of about 1 to 3 Kgray.