Antimicrobial polymer

• US 6,797,743 B2
• Filed: 05/07/2001
• Issued: 09/28/2004
• Est. Priority Date: 09/27/2000
• Status: Expired due to Fees

• Current Assignee: The Michigan Biotechnology Institute
• Original Assignee: The Michigan Biotechnology Institute
• Inventors: Taylor, Andrew C., McDonald, William F., Wright, Stacy C.
• Primary Examiner(s): Woodward, Ana
• Application Number:
  US09/850,324
• Publication Number:
  US 20030032765A1
• Time in Patent Office: 1,240 Days
• Field of Search: 523/122, 524/403, 524/413, 524/434
• US Class Current: 523/122
• CPC Class Codes: A01N 2300/00 Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48
• CPC Class Codes: A01N 25/10 Macromolecular compounds
• CPC Class Codes: A01N 25/24 containing ingredients to enhance the sticking of the active ingredients
• CPC Class Codes: A01N 25/34 Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
• CPC Class Codes: A01N 59/16 Heavy metals; Compounds thereof
• CPC Class Codes: A01N 59/20 Copper
• CPC Class Codes: A61K 2800/54 Polymers characterized by specific structures/properties
• CPC Class Codes: A61K 2800/58 Metal complex; Coordination compounds
• CPC Class Codes: A61K 8/88 Polyamides
• CPC Class Codes: A61Q 17/005 Antimicrobial preparations
• CPC Class Codes: A61Q 19/00 Preparations for care of the skin
• CPC Class Codes: C08K 3/015 Biocides macromolecular substances as carriers for biocide material A01N25/10
• CPC Class Codes: C08K 3/08 Metals
• CPC Class Codes: C08K 3/24 Acids; Salts thereof C08K3/16 takes precedence

Abstract

A polymeric composition having antimicrobial properties and a process for rendering the surface of a substrate antimicrobial are disclosed. The polymeric composition comprises a crosslinked chemical combination of (i) a polymer having amino group-containing side chains along a backbone forming the polymer, (ii) an antimicrobial agent selected from metals, metal alloys, metal salts, metal complexes and mixtures thereof, and (iii) a crosslinking agent containing functional groups capable of reacting with the amino groups. In one example embodiment, the polymer is a polyamide formed from a maleic anhydride or maleic acid ester monomer and alkylamines thereby producing a polyamide having amino substituted alkyl chains on one side of the polyamide backbone; the crosslinking agent is a phosphine having the general formula (A)₃P wherein A is hydroxyalkyl; and the metallic antimicrobial agent is selected from chelated silver ions, silver metal, chelated copper ions, copper metal, chelated zinc ions, zinc metal and mixtures thereof.

Claims

1. A polymeric composition having antimicrobial properties, the polymeric composition comprising:

a crosslinked chemical combination of (i) a polymer having side chains along a backbone forming the polymer, at least two of the side chains containing an amino group, (ii) an antimicrobial agent selected from the group consisting of metals, metal alloys, metal salts, metal complexes and mixtures thereof, and (iii) a crosslinking agent containing at least two functional groups capable of reacting with the amino groups;

wherein the polymer is a polyamide, and the polyamide is synthesized by (i) reacting a monomer selected from the group consisting of unsaturated carboxylic acids, esters of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, and mixtures thereof, and a first amine to form an intermediate reaction product, wherein the first amine is selected from the group consisting of RR₁NH, RNH₂, polyalkylene polyamines and mixtures thereof, and (iii) reacting the intermediate reaction product and a second amine to form the polyamide, wherein the second amine is selected from the group consisting of R₂R₃NH, R₂NH, polyalkylene polyamines and mixtures thereof, wherein R, R₁, R₂, and R₃ are the same or different and each R, R₁, R₂ and R₃ contains between 1 and 50 carbon atoms and is optionally substituted with heteroatoms oxygen, nitrogen, sulfur, phosphorus, or combinations thereof; and

at least one of the selected amines includes at least two amino groups.

2. The polymeric composition of claim 1 wherein R and R₁ are alkyl.

3. The polymeric composition of claim 2 wherein the amine comprises tetradecylamine.

4. The polymeric composition of claim 1 wherein the second amine comprises a polyalkylene polyamine.

5. The polymeric composition of claim 4 wherein the polyalkylene polyamine comprises pentaethylenehexamine.

6. The polymeric composition of claim 1 wherein the monomer is selected from the group consisting of unsaturated dicarboxylic acids, esters of unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, and mixtures thereof.

7. The polymeric composition of claim 6 wherein the monomer is selected from the group consisting of maleic anhydride, maleic acid esters, and mixtures thereof.

8. The polymeric composition of claim 7 wherein the first amine comprises tetradecylamine.

9. The polymeric composition of claim 7 wherein the second amine comprises a polyalkylene polyamine.

10. The polymeric composition of claim 9 wherein the polyalkylene polyamine comprises pentaethylenehexamine.

11. The polymeric composition of claim 6, wherein the antimicrobial agent is selected from the group consisting of chelated silver ions, silver metal, chelated copper ions, copper metal, chelated zinc ions, zinc metal and mixtures thereof.

12. The polymeric composition of claim 7 wherein the antimicrobial agent is selected from the group consisting of chelated silver ions, silver metal, chelated copper ions, copper metal, chelated zinc ions, zinc metal and mixtures thereof.

13. The polymeric composition of claim 1 wherein the antimicrobial agent is selected from the group consisting of chelated silver ions, silver metal, chelated copper ions, copper metal, chelated zinc ions, zinc metal and mixtures thereof.

14. The polymeric composition of claim 1 wherein the monomer comprises a maleic acid ester.

15. The polymeric composition of claim 1 wherein the monomer comprises maleic anhydride.

16. The polymeric composition of claim 1 wherein the crosslinking agent is selected from the group consisting of phosphines having the formula (A)₃P, wherein A is hydroxyalkyl, and mixtures thereof.

17. The polymeric composition of claim 16 wherein the crosslinking agent is tris(hydroxymethyl)phosphine.

18. The polymeric composition of claim 1, further comprising a second crosslinked chemical combination of (i) a second polymer having side chains along a backbone forming the second polymer, at least two of the side chains containing an amino group, (ii) a second antimicrobial agent selected from the group consisting of metals, metal alloys, metal salts, metal complexes and mixtures thereof, and (iii) a second crosslinking agent containing at least two functional groups capable of reacting with the amino groups, wherein the antimicrobial agent and the second antimicrobial agent are different.

19. The polymeric composition of claim 18 wherein the second polymer is a polyamide, and the polyaxmde is synthesized by reacting a monomer selected from the group consisting of unsaturated carboxylic acids, esters of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, and mixtures thereof, and an amine, wherein the amine is selected from the group consisting of RR₁NH, RNH₂, polyalkylene polyamines and mixtures thereof, wherein the R and R₁ groups are the same or different and each contain between about 1 and 50 carbon atoms and are optionally substituted with heteroatoms oxygen, nitrogen, sulfur, and phosphorus and combinations thereof, wherein at least one of the selected amines includes at least two amino groups.

20. The polymeric composition of claim 18 wherein:

the crosslinking agent and the second crosslinking agent are selected from the group consisting of phosphines having the formula (A)₃P, wherein A is hydroxyalkyl, and mixtures thereof.

21. The polymeric composition of claim 18 wherein:

the antimicrobial agent is selected from the group consisting of chelated copper ions, copper metal, and mixtures thereof, and the second antimicrobial is selected from the group consisting of chelated silver ions, silver metal, and mixtures thereof.

22. The polymeric composition of claim 18 wherein:

the antimicrobial agent is selected from the group consisting of chelated copper ions, copper metal, and mixtures thereof, and the second antimicrobial is selected from the group consisting of chelated zinc ions, zinc metal, and mixtures thereof.

23. A polyamide material comprising:

(A) a crosslinked polymeric material formed by a process comprising;

(i) reacting a reaction mixture comprising a monomer selected from the group consisting of maleic anhydride, maleic acid esters, and mixtures thereof, and one or more amines selected from polyalkylene polyamines and amines having the formula R-NH₂ to form an intermediate reaction product, wherein the R group contains between 1 and 50 carbon atoms and is optionally substituted with heteroatoms oxygen, nitrogen, sulfur, phosphorus, and combinations thereof;

wherein at least one of the selected amines includes at least two amino groups; and

(ii) reacting the intermediate reaction product and the one or more amines to form a polyamide; and

(iii) reacting the polyamide with a crosslinking agent to from a crosslinked polymer, wherein the crosslinking agent includes at least two functional groups capable of reacting with amino groups; and

(B) copper ions, copper metal, or a mixture thereof.

24. The polyamide material of claim 23, wherein the selected amines comprise tetradecylamine and pentaethylenehexamine.

25. A polyamide material comprising:

(A) a polymer formed by a process comprising;

(i) reacting a reaction mixture comprising a monomer selected from the group consisting of unsaturated carboxylic acids, esters of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, and mixtures thereof, and one or more amines selected from polyalkylene polyamines and amines having the formula R-NH₂ to form an intermediate reaction product, wherein the R group contains between 1 and 50 carbon atoms and is optionally substituted with heteroatoms oxygen, nitrogen, sulfur, phosphorus, and combinations thereof, wherein at least one of the selected amines includes at least two amino groups; and

(ii) reacting the intermediate reaction product and the one or more amines to form a polyamide; and

(B) an antimicrobial agent selected from the group consisting of a metal, a metal alloy, a metal salt, a metal complex, and mixtures thereof.

26. A polyamide material comprising:

(A) a crosslinked polymeric material formed by a process comprising;

(i) reacting a reaction mixture comprising a monomer selected from the group consisting of unsaturated carboxylic acids, esters of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, and mixtures thereof, and one or more amines selected from polyalkylene polyamines and amines having the formula R-NH₂ to form an intermediate reaction product, wherein the R group contains between 1 and 50 carbon atoms and is optionally substituted with heteroatoms oxygen, nitrogen, sulfur, phosphorus, and combinations thereof, wherein at least one of the selected amines includes at least two amino groups; and

(ii) reacting the intermediate reaction product and the one or more amines to form a polyamide; and

(iii) reacting the polyamide with a crosslinking agent to from a crosslinked polymer, wherein the crosslinking agent includes at least two functional groups capable of reacting with amino groups; and

(B) an antimicrobial agent selected from the group consisting of a metal, a metal alloy, a metal salt, a metal complex, of and mixtures thereof.

27. The polyamide material of claim 26 wherein the monomer comprises at least one unsaturated carboxylic monomer selected from the group consisting of maleic anhydride, maleic acid esters, and mixtures thereof.

28. The polyamide material of claim 26 wherein the antimicrobial agent includes chelated silver ions, silver metal, chelated copper ions, copper metal, chelated zinc ions, zinc metal, or mixtures thereof.

29. A crosslinked polymeric material formed from:

(A) a polyamide formed from a mixture which comprises;

(i) one or more monomers selected from the group consisting of maleic anhydride, maleic acid esters, and mixtures thereof; and

(ii) one or more amines selected from the group consisting of R-NH₂, a polyalkylene polyamine, and mixtures thereof, wherein the R group R-contains between 1 and 50 carbon atoms and is optionally substituted with heteroatoms oxygen, nitrogen, sulfur, phosphorus, or combinations thereof;

wherein one or more of the selected amines includes at least two amino groups;

(B) one or more antimicrobial agents selected from the group consisting of metals, metal alloys, metal salts, metal complexes and mixtures thereof; and

(C) one or more crosslinking agents selected from the group consisting of aliphatic isocyanate compounds having 2 or more —

N═

C═

O groups;

aromatic isocyanate compounds having 2 or more —

N═

C═

O groups;

aliphatic aldehyde compounds having 2 or more —

CHO groups;

aromatic aldehyde compounds having 2 or more —

CHO groups;

phosphines having the general formula (A)₂P(B) wherein A is hydroxyalkyl, and B is hydroxyalkyl, alkyl, or amyl;

epoxy resins having end groups of the formula;

and mixtures thereof.

30. The crosslinked polymeric material of claim 29, wherein the monomer comprises maleic anhydride mono-ethyl ester.

31. The crosslinked polymeric material of claim 29, wherein the one or more amines comprise tetradecylamine.

32. The crosslinked polymeric material of claim 29, wherein the one or more amines comprise pentaethylenehexamine.

33. The crosslinked polymeric material of claim 29, wherein the one or more antimicrobial agents comprise chelated silver ions, silver metal, or a mixture thereof.

34. The crosslinked polymeric material of claim 29, wherein the one or more antimicrobial agents comprise chelated copper ions, copper metal, or a mixture thereof.

35. The crosslinked polyamide material of claim 29, wherein the one or more crosslinking agents comprise glutaraldehyde.

36. The crosslinked polymeric material of claim 29, wherein the one or more crosslinking agents comprise a phosphine formed from the reaction of tetrakis(hydroxymethyl)phosphonium chloride and triethylamine.

37. The crosslinked polymeric material of claim 29, wherein the one or more crosslinking agents comprise tris(hydroxymethyl)phosphine.