Porous supports having azlactone-functional surfaces

• US 5,344,701 A
• Filed: 06/09/1992
• Issued: 09/06/1994
• Est. Priority Date: 06/09/1992
• Status: Expired due to Term

• Current Assignee: 3M Company
• Original Assignee: 3M Company
• Inventors: Milbrath, Dean S., Ortina, Gary J., Lyons, Christopher S., Rasmussen, Jerald K., Coleman, Patrick L., Gagnon, David R., Stahl, Julie B.
• Primary Examiner(s): BERMAN, SUSAN W
• Application Number:
  US07/896,107
• Time in Patent Office: 819 Days
• Field of Search: 428/308.4, 428/304.4, 428/308.8, 428/315.5, 428/319.3, 428/308.4, 522/116, 522/136, 522/173
• US Class Current: 428/304.4
• 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: B01J 20/28023 Fibres or filaments fibres or filaments in the form of membranes B01J20/28038; B01J20/28007 takes precedence
• CPC Class Codes: B01J 20/28033 Membrane, sheet, cloth, pad, lamellar or mat
• CPC Class Codes: B01J 20/286 Phases chemically bonded to a substrate, e.g. to silica or to polymers
• CPC Class Codes: B01J 20/3204 Inorganic carriers, supports or substrates
• CPC Class Codes: B01J 20/321 consisting of a polymer obtained by reactions involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 20/3212 consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
• CPC Class Codes: B01J 20/3219 involving a particular spacer or linking group, e.g. for attaching an active group
• CPC Class Codes: B01J 20/3255 comprising a cyclic structure containing at least one of the heteroatoms nitrogen, oxygen or sulfur, e.g. heterocyclic or heteroaromatic structures
• CPC Class Codes: B01J 20/3274 Proteins, nucleic acids, polysaccharides, antibodies or antigens
• CPC Class Codes: B01J 20/3276 Copolymers
• CPC Class Codes: B01J 20/3278 Polymers being grafted on the carrier
• CPC Class Codes: B01J 20/328 Polymers on the carrier being further modified
• CPC Class Codes: B01J 2220/54 Sorbents specially adapted for analytical or investigative chromatography
• CPC Class Codes: C07K 17/08 the carrier being a synthetic polymer
• CPC Class Codes: C08F 226/06 by a heterocyclic ring containing nitrogen
• CPC Class Codes: C08F 8/30 Introducing nitrogen atoms or nitrogen-containing groups
• CPC Class Codes: C12N 11/082 obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C12N 11/084 Polymers containing vinyl alcohol units
• CPC Class Codes: C12N 11/087 Acrylic polymers
• CPC Class Codes: G01N 33/54353 : with ligand attached to the carrier via a chemical coupling agent coatings G01N33/54393
• CPC Class Codes: Y10T 428/249953 : Composite having voids in a component [e.g., porous, cellular, etc.]
• CPC Class Codes: Y10T 428/249954 : With chemically effective material or specified gas other than air, N, or carbon dioxide in void-containing component
• CPC Class Codes: Y10T 428/249958 : Void-containing component is synthetic resin or natural rubbers
• CPC Class Codes: Y10T 428/249959 : Void-containing component is wood or paper
• CPC Class Codes: Y10T 428/249978 : Voids specified as micro
• CPC Class Codes: Y10T 428/249991 : Synthetic resin or natural rubbers

Abstract

Supports having azlactone-functional surfaces, adduct supports prepared from such azlactone-functional supports, and methods of preparing both are disclosed. Azlactone functionality is introduced to surfaces of a pre-existing support in a manner which retains useful physical and chemical characteristics of the pre-existing support. One method involves exposing surfaces with high energy radiation to generate free radical reaction sites on the surfaces and causing azlactone-functional moieties to react with the free radical reaction sites. Another method involves coating surfaces with azlactone monomers, crosslinking monomers, and optionally co-monomers and polymerizing the monomers to form a polymerized coating of azlactone-functionality on the surfaces. Another method involves dispersion polymerization of azlactone-functional moieties to produce azlactone-functional particles within pores and interstices of a pre-existing support. Adduct supports are formed by coupling nucleophilic reagents, such as biologically active materials, to azlactone-functional moieties of the support.

Claims

1. A chemically reactive support, comprising:

a porous pre-existing support having surfaces and azlactone-functional moieties contacting only the surfaces and modifying reactivity of only such surfaces while retaining useful porosity of the pre-existing support;

wherein said contacting is selected from the group consisting of chemically grafting the azlactone-functional moieties to the surfaces, crosslinking the azlactone-functional moieties in a coating over the surfaces, and forming crosslinked particles of the azlactone-functional moieties in contact with the surfaces.

2. The chemically reactive support according to claim 1, wherein the azlactone-functional moieties comprise monomers, prepolymers, oligomers, or polymers comprising oxazolinone moieties of the formula:

##STR4## wherein R¹ and R² independently can be an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 5 to 12 ring atoms, an arenyl group having 6 to 26 carbon atoms and 0 to 3 S, N, and nonperoxidic O heteroatoms, or R¹ and R² taken together with the carbon to which they are joined can form a carbocyclic ring containing 4 to 12 ring atoms, and

n is an integer 0 to 1.

3. The chemically reactive support according to claim 2, wherein the azlactone-functional moieties are derived from 2-alkenyl azlactones comprising:

2-ethenyl-1,3-oxazolin-5-one,

2-ethenyl-4-methyl-1,3-oxazolin-5-one,

2-isopropenyl-1,3-oxazolin-5-one,

2-isopropenyl-4-methyl-1,3-oxazolin-5-one,

2-ethenyl-4,4-dimethyl-1,3-oxazolin-5-one,

2-isopropenyl-4,4-dimethyl-1,3-oxazolin-5-one,

2-ethenyl-4-methyl-4-ethyl-1,3-oxazolin-5-one,

2-isopropenyl-4-methyl-4-butyl-1,3-oxazolin-5-one,

2-ethenyl-4,4-dibutyl-1,3-oxazolin-5-one,

2-isopropenyl-4-methyl-4-dodecyl-1,3-oxazolin-5-one,

2-isopropenyl-4,4-diphenyl-1,3-oxazolin-5-one,

2-isopropenyl-4,4-pentamethylene-1,3-oxazolin-5-one,

2-isopropenyl-4,4-tetramethylene-1,3-oxazolin-5-one,

2-ethenyl-4,4-diethyl-1,3-oxazolin-5-one,

2-ethenyl-4-methyl-4-nonyl-1,3-oxazolin-5-one,

2-isopropenyl-4-methyl-4-phenyl-1,3-oxazolin-5-one,

2-isopropenyl-4-methyl-4-benzyl-1,3-oxazolin-5-one,

2-ethenyl-4,4-pentamethylene-1,3-oxazolin-5-one,

2-ethenyl-4,4-dimethyl-1,3-oxazolin-5-one, 2-isopropenyl-4,4-dimethyl-1,3-oxazolin-5-one, or combinations thereof.

4. The chemically reactive support according to claim 1, wherein the pre-existing support is a ceramic, glassy, metallic, or polymeric material.

5. The chemically reactive support according to claim 4, wherein the pre-existing support is a polymeric material.

6. The chemically reactive support according to claim 5, wherein the porous, polymeric material is a woven web, a nonwoven web, a microporous fiber, or a microporous membrane.

7. The chemically reactive support according to claim 6, wherein the porous, polymeric material is a polyolefin and wherein the azlactone-functional moieties are derived from 2-ethenyl-4,4-dimethyl-1,3-oxazolin-5-one.

8. The chemically reactive support according to claim 5, wherein the azlactone-functional moieties are grafted to surfaces of the porous, polymeric material.

9. The chemically reactive support according to claim 5, wherein the azlactone-functional moieties are crosslinked in a coating over surfaces of the porous, polymeric material.

10. The chemically reactive support according to claim 5, wherein the azlactone-functional moieties are crosslinked particles contacting the surfaces of the porous, polymeric material.

11. A chemically reactive support, comprising:

a porous pre-existing support having surfaces and azlactone-functional moieties chemically grafted only to the surfaces and modifying reactivity of only such surfaces while retaining useful porosity of the pre-existing support.

12. The chemically reactive support according to claim 11, wherein the azlactone-functional moieties comprise monomers, prepolymers, oligomers, or polymers comprising oxazolinone moieties of the formula:

##STR5## wherein R¹ and R² independently can be an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 5 to 12 ring atoms, an arenyl group having 6 to 26 carbon atoms and 0 to 3S, N, and nonperoxidic O heteroatoms, or R¹ and R² taken together with the carbon to which they are joined can form a carbocyclic ring containing 4 to 12 ring atoms, and

n is an integer 0 or 1.

13. The chemically reactive support according to claim 12, wherein the azlactone-functional moieties are derived from 2-alkenyl azlactones comprising:

2-ethenyl-1,3-oxazolin-5-one,

2-ethenyl-4-methyl-1,3-oxazolin-5-one,

2-isopropenyl-1,3-oxazolin-5-one,

2-isopropenyl-4-methyl-1,3-oxazolin-5-one,

2-ethenyl-4,4-dimethyl-1,3-oxazolin-5-one,

2-isopropenyl-4,4-dimethyl-1,3-oxazolin-5-one,

2-ethenyl-4-methyl-4-ethyl-1,3-oxazolin-5-one,

2-isopropenyl-4-methyl-4-butyl-1,3-oxazolin-5-one,

2-ethenyl-4,4-dibutyl-1,3-oxazolin-5-one,

2-isopropenyl-4-methyl-4-dodecyl-1,3-oxazolin-5one,

2-isopropenyl-4,4-diphenyl-1,3-oxazolin-5-one,

2-isopropenyl-4,4-pentamethylene-1,3-oxazolin-5-one,

2-isopropenyl-4,4-tetramethylene-1,3-oxazolin-5one,

2-ethenyl-4,4-diethyl-1,3-oxazolin-5-one,

2-ethenyl-4-methyl-4-nonyl-1,3-oxazolin-5-one,

2-isopropenyl-4-methyl-4-phenyl-1,3-oxazolin-5-one,

2-isopropenyl-4-methyl-4-benzyl-1,3-oxazolin-5-one,

2-ethenyl-4,4-pentamethylene-1,3-oxazolin-5-one,

2-ethenyl-4,4-dimethyl-1,3-oxazolin-5-one,

2-isopropenyl-4,4-dimethyl-1,3-oxazolin-5-one, or combinations thereof.

14. The chemically reactive support according to claim 11, wherein the pre-existing support is a ceramic, glassy, metallic, or polymeric material.

15. The chemically reactive support according to claim 14, wherein the pre-existing support is a polymeric material.

16. The chemically reactive support according to claim 15, wherein the porous, polymeric material is a woven web, a nonwoven web, a microporous fiber, or a microporous membrane.

17. The chemically reactive support according to claim 16, wherein the porous, polymeric material is a polyolefin and wherein the azlactone-functional moieties are derived from 2-ethenyl-4,4-dimethyl-1,3-oxazolin-5-one.

18. A chemically reactive support, comprising:

a porous pre-existing support having surfaces and azlactone-functional moieties crosslinked in a coating over only the surfaces and modifying reactivity of only such surfaces while retaining useful porosity of the pre-existing support.

19. The chemically reactive support according to claim 18, wherein the azlactone-functional moieties comprise monomers, prepolymers, oligomers, or polymers comprising oxazolinone moieties of the formula:

##STR6## wherein R¹ and R² independently can be an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 5 to 12 ring atoms, an arenyl group having 6 to 26 carbon atoms, and 0 to 3S, N, and nonperoxidic O heteroatoms, or R¹ and R² taken together with the carbon to which they are joined can form a carbocyclic ring containing 4 to 12 ring atoms, and

n is an integer 0 or 1.

20. The chemically reactive support according to claim 19, wherein the azlactone-functional moieties are derived from 2-alkenyl azlactones comprising:

2-ethenyl-1,3-oxazolin-5-one,

2-ethenyl-4-methyl-1,3-oxazolin-5-one,

2-isopropenyl-1,3-oxazolin-5-one,

2-isopropenyl-4-methyl-1,3-oxazolin-5-one, 2-ethenyl-4,4-dimethyl-1,3-oxazolin-5-one,

2-isopropenyl-4,4-dimethyl-1,3-oxazolin-5-one,

2-ethenyl-4-methyl-4-ethyl-1,3-oxazolin-5-one,

2-isopropenyl-4-methyl-4-butyl-1,3-oxazolin-5-one,

2-ethenyl-4,4-dibutyl-1,3-oxazolin-5-one,

2isopropenyl-4-methyl-4-dodecyl-1,3-oxazolin-5-one,

2isopropenyl-4,4-diphenyl-1,3-oxazolin-5-one,

2isopropenyl-4,4-pentamethylene-1,3-oxazolin-5-one,

2isopropenyl-4,4-tetramethylene-1,3-oxazolin-5-one,

2-ethenyl-4,4-diethyl-1,3-oxazolin-5-one,

2-ethenyl-4-methyl-4-nonyl-1,3-oxazolin-5-one,

2-isopropenyl-4-methyl-4-phenyl-1,3-oxazolin-5-one,

2-isopropenyl-4-methyl-4-benzyl-1,3-oxazolin-5-one,

2-ethenyl-4,4-pentamethylene-1,3-oxazolin-5-one,

2-ethenyl-4,4-dimethyl-1,3-oxazolin-5-one, 2-isopropenyl-4,4-dimethyl-1,3-oxazolin-5-one, or combinations thereof.

21. The chemically reactive support according to claim 18, wherein the pre-existing support is a ceramic, glassy, metallic, or polymeric material.

22. The chemically reactive support according to claim 21, wherein the pre-existing support is a polymeric material.

23. The chemically reactive support according to claim 22, wherein the porous, polymeric material is a woven web, a nonwoven web, a microporous fiber, or a microporous membrane.

24. The chemically reactive support according to claim 23, wherein the porous, polymeric material is a polyolefin and wherein the azlactone-functional moieties are derived from 2-ethenyl-4,4-dimethyl-1,3-oxazolin-5-one.

25. A chemically reactive support, comprising:

a porous pre-existing support having surfaces and azlactone-functional moieties in crosslinked particles contacting only the surfaces and modifying reactivity of only such surfaces while retaining useful porosity of the pre-existing support.

26. The chemically reactive support according to claim 25, wherein the azlactone-functional moieties comprise monomers, prepolymers, oligomers, or polymers comprising oxazolinone moieties of the formula:

##STR7## wherein R¹ and R² independently can be an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, an aryl group having 5 to 12 ring atoms, an arenyl group having 6 to 26 carbon atoms and 0 to 3S, N, and nonperoxidic O heteroatoms, or R¹ and R² taken together with the carbon to which they are joined can form a carbocyclic ring containing 4 to 12 ring atoms, and

n is an integer 0 to 1.

27. The chemically reactive support according to claim 26, wherein the azlactone-functional moieties are derived from 2-alkenyl azlactones comprising:

2-ethenyl-1,3-oxazolin-5-one,

2-ethenyl-4-methyl-1,3-oxazolin-5-one,

2-isopropenyl-1,3-oxazolin-5-one,

2-isopropenyl-4-methyl-1,3-oxazolin-5-one,

2-ethenyl-4,4-dimethyl-1,3-oxazolin-5-one

2-isopropenyl-4,4-dimethyl-1,3-oxazolin-5-one,

2-ethenyl-4-methyl-4-ethyl-1,3-oxazolin-5-one,

2-isopropenyl-4-methyl-4-butyl-1,3-oxazolin-5-one,

2-ethenyl-4,4-dibutyl-1,3-oxazolin-5-one,

2-isopropenyl-4-methyl-4-dodecyl-1,3-oxazolin-5-one,

2-isopropenyl-4,4-diphenyl-1,3-oxazolin-5-one,

2-isopropenyl-4,4-pentamethylene-1,3-oxazolin-5-one,

2-isopropenyl-4,4-tetramethylene-1,3-oxazolin-5-one,

2-ethenyl-4,4-diethyl-1,3-oxazolin-5-one,

2-ethenyl-4-methyl-4-nonyl-1,3-oxazolin-5-one,

2-isopropenyl-4-methyl-4-phenyl-1,3-oxazolin-5-one,

2-isopropenyl-4-methyl-4benzyl-1,3-oxazolin-5-one,

2-ethenyl-4,4-pentamethylene-1,3-oxazolin-5-one,

2-ethenyl-4,4-dimethyl-1,3-oxazolin-5-one, 2-isopropenyl-4,4-dimethyl-1,3-oxazolin-5-one, or combinations thereof.

28. The chemically reactive support according to claim 27, wherein the pre-existing support is a ceramic, glassy, metallic, or polymeric material.

29. The chemically reactive support according to claim 28, wherein the pre-existing support is a polymeric material.

30. The chemically reactive support according to claim 29, wherein the porous, polymeric material is a woven web, a nonwoven web, a microporous fiber, or a microporous membrane.

31. The chemically reactive support according to claim 30, wherein the porous, polymeric material is a polyolefin and wherein the azlactone-functional moieties are derived from 2-ethenyl-4,4-dimethyl-1,3-oxazolin-5-one.