IP Library Granted Patent US 7,883,749
Granted Patent B2
US 7,883,749 · App. 11/375,487 · Granted Feb 8, 2011

Method for coating an object with a graft polymer layer

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Quick Facts
Patent No.
US 7,883,749
App. No.
11/375,487
Granted
Feb 8, 2011
Kind
B2
Abstract

A method for coating a device, such as an industrially or medically applicable device, with a polymer layer is provided. The method includes contacting the device with a grafting initiator comprising at least one photoinitiator group, exposing the device to radiation, contacting the device with a polymerizable monomer, and again exposing the device to radiation.

Claims (45)

1. A method for coating an object with a polymer layer comprising:

placing the object into a container;

filling the container with a first solution comprising a non-polymeric grafting initiator comprising at least one photoinitiator group capable of generating a free radical active species upon absorption of electromagnetic energy, wherein the photoinitiator group is selected from the group consisting of an initiator that is insoluble in polar solvent and a positively charged initiator;

irradiating the container having the first solution and the object, resulting in the grafting initiator binding to the object;

removing the first solution from the container;

filling the container with a second solution comprising a polymerizable monomer having at least one free-radical polymerizable group; and

irradiating the container having the second solution and the object, wherein the non-polymeric grafting initiator acts as a photoinitiator for a free-radical polymerization reaction, resulting in the polymerization of the polymerizable monomer and formation of a polymer layer on the object.

2. The method of claim 1 , further comprising bubbling an inert gas through the first solution to remove non-inert gas from the first solution.

3. The method of claim 1 , further comprising bubbling an inert gas through the second solution to remove non-inert gas from the second solution.

4. The method of claim 1 , further comprising rinsing the object.

5. The method of claim 1 , wherein filling the container with the first solution includes adding an amount of the first solution sufficient to surround the object.

6. The method of claim 1 , wherein filling the container with the second solution includes adding an amount of the second solution sufficient to surround the object.

7. The method of claim 1 , wherein the initiator that is insoluble in polar solvent is selected from the group consisting of tetrakis (4-benzoylbenzyl ether), the tetrakis (4-benzoylbenzoate ester) of pentaerythritol, an acylated derivative of tetraphenylmethane.

8. The method of claim 1 , wherein the positively charged initiator includes a quaternary ammonium group.

9. The method of claim 8 , wherein the initiator that includes a quaternary ammonium group is selected from the group consisting of ethylenebis(4-benzoylbenzyldimethylammonium) dibromide (Diphoto-Diquat); hexamethylenebis(4-benzoylbenzyldimethylammonium) dibromide (Diphoto-Diquat); 1,4-bis(4-benzoylbenzyl)-1,4-dimethylpiperazineadiium dibromide (Diphoto-Diquat); bis(4-benzoylbenzyl)hexamethylenetetraminediium dibromide (Diphoto-Diquat): bis[2-(4-benzoylbenzyldimethylammonio)ethyl]-4-benzoylbenzylmethylammonium tribromide (Triphoto-Triquat): 4,4-bis(4-benzoylbenzyl)morpholinium bromide (Diphoto-Monoquat); ethylenebis[(2-(4-benzoylbenzyldimethylammonio)ethyl)-4-benzoylbenzylmethylammonium]tetrabromide (Tetraphoto-Tetraquat); 1,1,4,4-tetrakis(4-benzoylbenzyl)piperazinediium Dibromide (Tetraphoto-Diquat); and N,N-bis[2-(4-benzoylbenzyloxy)ethyl]-2-aminoethanesulfonic acid, sodium salt (Diphoto-Monosulfonate), and analogues thereof.

10. A method for coating an object with a polymer layer comprising the steps of:

establishing fluid communication between a container and a fluid maintenance station, the container having the object disposed therein;

dispensing a first solution into the container from the fluid maintenance station, the first solution comprising a non-polymeric grafting initiator comprising at least one photoinitiator group capable of generating a free radical active species upon absorption of electromagnetic energy, wherein the photoinitiator group is selected from the group consisting of an initiator that is insoluble in polar solvent and a positively charged initiator;

interrupting fluid communication between the container and the fluid maintenance station;

irradiating the container resulting in the grafting initiator binding to the object;

re-establishing fluid communication between the container and the fluid maintenance station;

removing the first solution from the container and dispensing a second solution into the container from the fluid maintenance station, the second solution comprising a polymerizable monomer having at least one free-radical polymerizable group; and

interrupting fluid communication between the container and the fluid maintenance station; and

irradiating the container, wherein the non-polymeric grafting initiator acts as a photoinitiator for a free-radical polymerization reaction resulting in the polymerization of the polymerizable monomer and formation of a polymer layer on the object.

11. The method of claim 10 , further comprising conveying the container to an irradiation station.

12. The method of claim 10 , further comprising bubbling inert gas through the first solution in the container to remove non-inert gas.

13. The method of claim 10 , further comprising bubbling inert gas through the second solution in the container to remove non-inert gas.

14. The method of claim 10 , further comprising conveying the container from the fluid maintenance station to an irradiation station.

15. The method of claim 10 , further comprising conveying the container from an irradiation station to a fluid maintenance station.

16. The method of claim 10 , wherein the initiator that is insoluble in polar solvent is selected from the group consisting of tetrakis (4-benzoylbenzyl ether), the tetrakis (4-benzoylbenzoate ester) of pentaerythritol, an acylated derivative of tetraphenylmethane.

17. The method of claim 10 , wherein the positively charged initiator includes a quaternary ammonium group.

18. The method of claim 17 , wherein the initiator that includes a quaternary ammonium group is selected from the group consisting of ethylenebis(4-benzoylbenzyldimethylammonium) dibromide (Diphoto-Diquat); hexamethylenebis(4-benzoylbenzyldimethylammonium) dibromide (Diphoto-Diquat); 1,4-bis(4-benzoylbenzyl)-1,4-dimethylpiperazineadiium dibromide (Diphoto-Diquat); bis(4-benzoylbenzyl)hexamethylenetetraminediium dibromide (Diphoto-Diquat): bis[2-(4-benzoylbenzyldimethylammonio)ethyl]-4-benzoylbenzylmethylammonium tribromide (Triphoto-Triquat): 4,4-bis(4-benzoylbenzyl)morpholinium bromide (Diphoto-Monoquat); ethylenebis[(2-(4-benzoylbenzyldimethylammonio)ethyl)-4-benzoylbenzylmethylammonium]tetrabromide (Tetraphoto-Tetraquat); 1,1,4,4-tetrakis(4-benzoylbenzyl)piperazinediium Dibromide (Tetraphoto-Diquat); and N,N-bis[2-(4-benzoylbenzyloxy)ethyl]-2-aminoethanesulfonic acid, sodium salt (Diphoto-Monosulfonate), and analogues thereof.

19. A method for coating an object comprising the steps of:

placing the object into a translucent container attached to a conveyor mechanism;

conveying the translucent container to a fluid maintenance station and filling the translucent container with a first solution comprising a non-polymeric grafting initiator comprising at least one photoinitiator group capable of generating a free radical active species upon absorption of electromagnetic energy, wherein the photoinitiator group is selected from the group consisting of an initiator that is insoluble in polar solvent and a positively charged initiator;

conveying the translucent container to an irradiation station and irradiating the container, resulting in the grafting initiator binding to the object;

conveying the translucent container to the fluid maintenance station and removing the first solution from the container and filling the container with a second solution comprising a polymerizable monomer having at least one free-radical polymerizable group, said filling sufficient to surround said object with second solution; and

conveying the translucent container to the irradiation station and irradiating the translucent container wherein the non-polymeric grafting initiator acts as a photoinitiator for a free-radical polymerization reaction, resulting in the polymerization of the polymerizable monomer and formation of a polymer layer on the object.

20. The method of claim 19 , the conveyor mechanism comprising a conveyor track.

21. The method of claim 19 , further comprising bubbling inert gas through the first solution in the container to remove non-inert gas.

22. The method of claim 19 , further comprising bubbling inert gas through the second solution in the container to remove non-inert gas.

23. The method of claim 19 , further comprising rinsing the object.

24. The method of claim 19 , wherein the initiator that is insoluble in polar solvent is selected from the group consisting of tetrakis (4-benzoylbenzyl ether), the tetrakis (4-benzoylbenzoate ester) of pentaerythritol, an acylated derivative of tetraphenylmethane.

25. The method of claim 19 , wherein the positively charged initiator includes a quaternary ammonium group.

26. The method of claim 25 , wherein the initiator that includes a quaternary ammonium group is selected from the group consisting of ethylenebis(4-benzoylbenzyldimethylammonium) dibromide (Diphoto-Diquat); hexamethylenebis(4-benzoylbenzyldimethylammonium) dibromide (Diphoto-Diquat); 1,4-bis(4-benzoylbenzyl)-1,4-dimethylpiperazineadiium dibromide (Diphoto-Diquat); bis(4-benzoylbenzyl)hexamethylenetetraminediium dibromide (Diphoto-Diquat): bis[2-(4-benzoylbenzyldimethylammonio)ethyl]-4-benzoylbenzylmethylammonium tribromide (Triphoto-Triquat): 4,4-bis(4-benzoylbenzyl)morpholinium bromide (Diphoto-Monoquat); ethylenebis[(2-(4-benzoylbenzyldimethylammonio)ethyl)-4-benzoylbenzylmethylammonium]tetrabromide (Tetraphoto-Tetraquat); 1,1,4,4-tetrakis(4-benzoylbenzyl)piperazinediium Dibromide (Tetraphoto-Diquat); and N,N-bis[2-(4-benzoylbenzyloxy)ethyl]-2-aminoethanesulfonic acid, sodium salt (Diphoto-Monosulfonate), and analogues thereof.

Assignments (3)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 8, 2025
From: SURMODICS, INC.
To: SURMODICS COATINGS, LLC
Reel/Frame 073928/0178 →
RELEASE OF SECURITY INTEREST Recorded Nov 24, 2025
From: MIDCAP FUNDING IV TRUST
To: SURMODICS, INC.; SURMODICS SHARED SERVICES, LLC; SURMODICS HOLDINGS, LLC; SURMODICS COATINGS, LLC; SURMODICS MD, LLC; SURMODICS COATINGS MFG, LLC; SURMODICS IVD, INC.; SURMODICS MD OPERATIONS, LLC; NORMEDIX, INC.
Reel/Frame 073690/0186 →
SECURITY INTEREST Recorded Aug 23, 2024
From: SURMODICS, INC.; SURMODICS SHARED SERVICES, LLC; SURMODICS HOLDINGS, LLC; SURMODICS COATINGS, LLC; SURMODICS MD, LLC; SURMODICS COATINGS MFG, LLC; SURMODICS IVD, INC.; SURMODICS MD OPERATIONS, LLC; NORMEDIX, INC.
To: MIDCAP FUNDING IV TRUST
Reel/Frame 068762/0423 →