Polymers selective for nitro-containing compounds and methods of using the same

Patent metadata

Field	Value
Publication number	US-9243096-B2
Application number	US-201313745713-A
Country	US
Kind code	B2
Filing date	Jan 18, 2013
Priority date	Dec 7, 2006
Publication date	Jan 26, 2016
Grant date	Jan 26, 2016

Abstract

Porous beads are provided of a polymer of a non-acidic monomer and a cross-linker having polar functionality, one of which is hydrophilic, the other of which is hydrophobic, further comprising residues of polyvinyl alcohol. The beads may be molecularly imprinted or non-molecularly imprinted. The use of such beads in the removal of nitroso-containing compounds from material containing them is also disclosed. Also disclosed is a non-molecularly imprinted polymer which is selectively adsorbent for at least one tobacco specific nitrosamine in the presence of nicotine, said polymer being a polymerization product of a non-acidic monomer and a cross-linker having polar functionality, one of which is hydrophilic, the other of which is hydrophobic.

First claim

The invention claimed is:

1. Beads for selectively removing a nitroso-containing compound from material containing the compound and nicotine, said beads comprising an adsorbent polymer of a non-acidic monomer and a cross-linker having polar functionality, one of which is hydrophilic, the other of which is hydrophobic, said beads having selectivity for said nitroso-containing compound over nicotine.

2. The beads of claim 1 , wherein the beads are of average diameter 10-1000 μm, comprise <10 vol. % fines of diameter <10 μm, have a pore volume of 0.2-1.5 ml/g, have a B.E.T. surface area of 20-500 m 2 /g and have an average pore diameter of 30-300 Å.

3. The beads of claim 1 , wherein the beads are of average diameter 10-100 μm, comprise <10 vol. % fines of diameter <10 μm, have a pore volume of 0.5-1.5 ml/g, have a B.E.T. surface area of 50-500 m 2 /g and have an average pore diameter of 50-200 Å.

4. The beads of claim 1 , wherein moieties of the cross-linker in the polymer are in molar excess of moieties of the monomer.

5. The beads of claim 4 , wherein the molar ratio of the moieties of the cross-linker and monomer is from 3:1 to 10:1.

6. The beads of claim 4 , wherein the molar ratio of the moieties of the cross-linker and monomer is from 4:1 to 6:1.

7. The beads of claim 1 , wherein the non-acidic monomer is selected from 2-hydroxyethylmethacrylate (HEMA), 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, 2-(4-vinylphenyl)-1,3-propane diol, acrylamide, methacrylamide, N-methyl acrylamide, diethylamino ethylmethacrylate (DEAEM) and mixtures thereof, and the cross-linker is hydrophobic.

8. The beads of claim 7 , wherein the cross-linker is selected from ethylene glycol dimethacrylate (EDMA), trimethylol propane trimethacrylate (“TRIM”), tetramethylene glycol dimethacrylate, N,N′-methylenebisacrylamide, N,N′-ethylenebisacrylamide, N,N′-butylenebisacrylamide, N,N′-hexamethylenebisacrylamide and mixtures thereof.

9. The beads of claim 1 , wherein the non-acidic monomer is selected from styrene, methyl styrene, ethyl styrene, vinyl toluene, 2-vinyl pyridine, 2-ethylhexyl acrylate (EHA), butyl methyl acrylate (BMA), methyl methacrylate and mixtures thereof and the cross-linker is hydrophilic.

10. The beads of claim 9 , wherein the cross-linker is selected from di(ethylene glycol)dimethacrylate (“DEDMA”), pentaerythritol tetraacrylate, tri(ethylene glycol)dimethacrylate, tetra(ethylene glycol)dimethacrylate, poly(ethylene glycol)dimethacrylate and pentaerythritol triacrylate (PETRA) and mixtures thereof.

11. The beads of claim 1 , wherein the polymer is a copolymer of 2-hydroxyethylmethacrylate (HEMA) and a hydrophobic crosslinker.

12. The beads of claim 11 , wherein the polymer is a copolymer of 2-hydroxyethylmethacrylate (HEMA) and ethylene glycol dimethacrylate (EDMA).

13. The beads of claim 1 , wherein the polymer is a copolymer of 2- or 3-hydroxypropylmethacrylate (HEMA) and a hydrophobic crosslinker.

14. The beads of claim 13 , wherein the polymer is a copolymer of 2 or 3-hydroxypropylmethacrylate (HEMA) and ethylene glycol dimethacrylate (EDMA).

15. The beads of claim 1 , wherein the beads are molecularly imprinted for removal of nitroso compounds from material containing such compounds.

16. The beads of claim 1 , wherein the beads are not molecularly imprinted but can selectively remove nitroso-containing compounds from material containing such compounds.

17. The beads of claim 1 , wherein the beads are selective for removal of at least one of the compounds listed below from material containing said at least one compound and nicotine:
4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (“NNK”);
4-(methylnitrosamino)-4-(3-pyridyl)butanal (“NNA”);
N-nitrosonornicotine (“NNN”);
N-nitrosoanabasine (“NAB”);
N-nitrosoanatabine (“NAT”);
4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (“NNAL”);
4-(methylnitrosamino)-4-(3-pyridyl)-1-butanol (“iso-NNAL”);
4-(methylnitrosamino)-4-(3-pyridyl)butanoic acid (“iso-NNAC”).

18. The beads of claim 1 , wherein the beads are porous.

19. The method of claim 18 , wherein the amount of polyvinyl alcohol is 2.5-4.5 wt % based on the weight of monomers.

20. A method of making beads for selectively removing a nitroso-containing compound from material containing the compound and nicotine, said beads being of a non-acidic monomer and a cross-linker having polar functionality, one of which is hydrophilic, the other of which is hydrophobic, the method comprising suspension polymerizing a monomer phase comprising initiator, the non-acidic monomer and the cross-linker having polar functionality in an aqueous phase, said beads having selectivity for said nitroso-containing compound over nicotine.

21. The method of claim 20 , wherein the polymerizing is conducted in the presence of toluene or other non-polar porogen.

22. The method of claim 21 , wherein the amount of amount of initiator is 1.75-10 wt % based on the weight of the monomers.

23. The method of claim 22 , wherein the polymer is the result of polymerization with 2.5-5 wt % initiator based on the weight of monomers.

24. The method of claim 20 , wherein the monomer phase further comprises a structural analogue of a TSNA, and further comprising the step of removing the structural analog from the porous beads to give molecularly imprinted beads.

25. The method of claim 20 , wherein the aqueous phase comprises polyvinyl alcohol in an amount such that polyvinyl alcohol residues become present in the beads.

26. A method for selectively removing a nitroso-containing compound from material containing the compound and nicotine, said method comprising contacting the material with an aqueous phase comprising beads of a selectively adsorbent polymer of a non-acidic monomer and a cross-linker having polar functionality, one of which is hydrophilic, the other of which is hydrophobic, said beads having selectivity for said nitroso-containing compound over nicotine.

27. The method of claim 26 , wherein any of the following apply:
(a) the aqueous phase comprises polyvinyl alcohol in an amount such that polyvinyl alcohol residues become present in the beads;
(b) the beads are molecularly imprinted for removal of nitroso-containing compounds from material containing them;
(c) the beads can remove nitroso-containing compounds from material containing them but are not molecularly imprinted;
(d) the non-acidic monomer is selected from 2-hydroxyethylmethacrylate (HEMA), 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, 2-(4-vinylphenyl)-1,3-propane diol, acrylamide, N-methyl acrylamide and mixtures thereof, and the cross-linker is hydrophobic;
(e) the cross-linker is selected from ethylene glycol dimethacrylate (EDMA), trimethylol propane trimethacrylate (“TRIM”), tetramethylene glycol dimethacrylate, N,N′-methylenebisacrylamide, N,N′-ethylenebisacrylamide, N,N′-butylenebisacrylamide, N,N′-hexamethylenebisacrylamide and mixtures thereof;
(f) the non-acidic monomer is selected from styrene, methyl styrene, ethyl styrene, 2-vinyl pyridine, vinyl toluene, ethylhexyl acrylate (EHA), butyl methyl acrylate (BMA), methyl methacrylate and mixtures thereof and the cross-linker is hydrophilic;
(g) the cross-linker is selected from N,N′-methylenebisacrylamide, di(ethylene glycol)dimethacrylate (“DEDMA”), pentaerythrit

Assignees

• Karlsson Ola John Ivar
• Billing Johan Fredrik
• Yilmaz Ecevit
• Svensson Stark Jan Robert Christian
• British American Tobacco Co

Inventors

• Karlsson Ola John Ivar
• Billing Johan Fredrik
• Yilmaz Ecevit
• Svensson Stark Jan Robert Christian

Classifications

• C08F222/20 Primary

  Esters containing oxygen in addition to the carboxy oxygen · CPC title

• C08F222/1006

  of polyhydric alcohols or polyhydric phenols · CPC title

• A24B15/245 Primary

  Nitrosamines · CPC title

• C08F220/20

  of polyhydric alcohols or phenols {, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate} · CPC title

• B01J20/28061

  being in the range 100-500 m2/g · CPC title