Functionalized polymeric media for separation of analytes
View Patent ↗Separation of a variety of analytes that are polar, nonpolar and ionic using functionalized polymeric media is disclosed. Preformed rigid particles of highly crosslinked homopolymer of polyvinylidene compounds are functionalize using the residual vinyl groups onto which monovinyl compounds are covalently bonded through polymerization. The functionalization imparts desirable surface properties for separation applications such as liquid chromatography and solid phase extraction.
1. Functionalized polymer beads prepared by
a) polymerizing a polyvinylidene monomer to form a self-crosslinked homopolymer; and then
b) polymerizing a functional monomer to covalently bond to said homopolymer.
2. The functionalized polymer beads of claim 1 wherein said polyvinylidene monomer is selected from the group consisting of divinylbenzene, trivinylbenzene, divinylpyridine, divinyltoluene, divinylnaphthalene, ethyleneglycol dimethylacrylate and N,N-methylenediacrylamide.
3. The functionalized polymer beads of claim 2 wherein said polyvinylidene monomer is divinylbenzene.
4. The functionalized polymer beads of claim 1 wherein said homopolymer is poly(divinylbenzene).
5. The functioned polymer beads of claim 1 wherein said functional monomer is a monovinyl compound.
6. The functionalized polymer beads of claim 5 wherein said monovinyl compound bears a polar moiety or an ionic moiety.
7. The functionalized polymer beads of claim 1 wherein said functional monomer is selected from the group consisting of N-methyl-N-vinylacetamide, aminostyrene, methylacrylate, ethylacrylate, hydroxymethylacrylate, hydroxyethylacrylate and N-vinylcaprolactam.
8. The functionalized polymer beads of claim 7 wherein said functional monomer is N-methyl-N-vinylacetamide.
9. The functionalized polymer beads of claim 8 wherein said beads comprise 0.5-3.0 millimoles of N-methyl-N-vinylacetamide per gram of functionalized polymer beads.
10. The functionalized polymer beads of claim 1 wherein said functional monomer is selected from the group consisting of N-(4-vinylbenzyl)-N,N-dimethylamine, vinylbenzyltrimethylammonium chloride, 4-vinylbenzoic acid, styrene sulfonic acid and methacrylic acid.
11. The functionalized polymer beads of claim 1 wherein said functional monomer is glycidylmethacrylate.
12. The functionalized polymer beads of claim 11 which are further reacted with ethylenediamine, diethylamine, polyethyleneimine, hydroxypropyl sulfonic acid, hydroxylbenzene sulfonic acid or hydroxybenzoic acid.
13. The functionalized polymer beads of claim 11 which are further reacted with ethylenediamine.
14. A method for preparing a functionalized polymer bead, said method comprising the steps of:
a) polymerizing a polyvinylidene monomer to form a homopolymer; and then
b) polymerizing a functional monomer which covalently binds to said homopolymer.
15. The method of claim 14 wherein following step (a) residual vinyl groups remain on said homopolymer.
16. The method of claim 14 wherein said functional monomers form a functional polymer which is covalently bonded to said homopolymer via a residual vinyl group.
17. The method of claim 14 wherein said polyvinylidene monomer is selected from the group consisting of divinylbenzene, trivinylbenzene, divinylpyridine, divinyltoluene, divinylnaphthalene, ethyleneglycol dimethylacrylate and N,N-methylenediacrylamide.
18. The method of claim 14 wherein said polyvinylidene monomer is divinylbenzene.
19. The method of claim 14 wherein said functional monomer is a monovinyl compound.
20. The method of claim 19 wherein said monovinyl compound bears a polar moiety or an ionic moiety.
21. The method of claim 14 wherein said functional monomer is selected from the group consisting of N-methyl-N-vinylacetamide, aminostyrene, methylacrylate, ethylacrylate, hydroxyethylacrylate, hydroxyethylacrylate, and N-vinylcaprolactam.
22. The method of claim 14 wherein said functional monomer is N-methyl-N-vinylacetamide.
23. The method of claim 22 wherein said functionalized polymer bead comprises 0.5-3.0 millimoles of N-methyl-N-vinylacetamide per gram of functionalized polymer bead.
24. The method of claim 14 wherein said functional monomer is selected from the group consisting of N-(4-vinylbenzyl)-N,N-dimethylamine, vinylbenzyltrimethylammonium chloride, 4-vinylbenzoic acid, styrene sulfonic acid and methacrylic acid.
25. The method of claim 14 wherein said functional monomer is glycidylmethacrylate.
26. The method of claim 25 further comprising:
c) reacting the functionalized polymer bead produced by step (b) with ethylenediamine, diethylamine, polyethyleneimine, hydroxypropyl sulfonic acid, hydroxylbenzene sulfonic acid or hydroxybenzoic acid.
27. The method of claim 25 further comprising:
c) reacting the functionalized polymer bead produced by step (b) with ethylenediamine.
28. The method of claim 14 wherein step (b) is catalyzed by a free radical under anaerobic conditions.
29. The method of claim 28 wherein a free radical catalyst is utilized, said free radical catalyst being selected from the group consisting of benzoyl peroxide, tert-butylbenzoate, caproyl peroxide, azodiisobutyronitrile and azodiisobutyramide.
30. The method of claim 29 wherein said free radical catalyst is azodiisobutyronitrile.
31. A method of separating an analyte from a solution comprising said analyte and a first solvent, said method comprising contacting said solution with functionalized polymer beads of claim 1 whereby said analyte is adsorbed onto said functioned polymer bead.
32. The method of claim 31 wherein, after contacting said fictionalized polymer beads with said solution, said functionalized polymer beads are washed with said first solvent.
33. The method of claim 31 wherein said analyte is released from said functionalized polymer beads by washing said functionalized polymer beads with a second solvent.
34. The method of claim 32 wherein said first solvent is aqueous.
35. The method of claim 33 wherein said second solvent is methanol.
36. The method of claim 31 wherein said analyte is selected from the group consisting of acetaminophen, resorcinal, pindolol, procainamide, primidone, phenobarbital, niacinamide and bupivacaine.
37. The method of claim 31 wherein said functionalized polymer beads comprise N-methyl-N-vinylacetamide functional groups.
38. A method of separating analytes in a mixture by passing said mixture through a column of functionalized polymer beads of claim 1 .
39. The method of claim 38 wherein an aqueous buffer is used as a mobile phase.
40. The method of claim 38 wherein said method comprises high performance liquid chromatography.
41. The method of claim 38 wherein said analytes are organic acids.
42. The method of claim 38 wherein said analytes are isomers of each other.
43. The method of claim 38 wherein said functionalized polymer beads comprise N-methyl-N-vinylacetamide.
44. The method of claim 38 wherein said functionalized polymer beads comprise an anion exchanger.
45. The method of claim 44 wherein said functionalized polymer beads comprise vinylbenzyltrimethylammonium chloride.
46. The method of claim 38 wherein said analytes are separated by washing said functionalized polymer beads with a series of solvents.
47. The method of claim 46 wherein said series of solvents comprises methanol an acid, and acidified methanol.