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

• US 9,243,096 B2
• Filed: 01/18/2013
• Issued: 01/26/2016
• Est. Priority Date: 12/07/2006
• Status: Active Grant

• Current Assignee: British American Tobacco Limited (British American Tobacco PLC)
• Original Assignee: British American Tobacco Limited (British American Tobacco PLC)
• Inventors: Karlsson, Ola John Ivar, Billing, Johan Fredrik, Yilmaz, Ecevit, Svensson Stark, Jan Robert Christian
• Primary Examiner(s): Cordray, Dennis
• Application Number:
  US13/745,713
• Publication Number:
  US 20130139834A1
• Time in Patent Office: 1,103 Days
• Field of Search: 131/297, 131/331, 131/332, 131/290, 131/298, 131/347, 131/360
• US Class Current: 1/1
• CPC Class Codes: A24B 15/245 Nitrosamines
• CPC Class Codes: B01D 15/265 Adsorption chromatography
• CPC Class Codes: B01J 20/26 Synthetic macromolecular compounds
• CPC Class Codes: B01J 20/261 obtained by reactions only involving carbon to carbon unsaturated bonds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds per se C08F
• CPC Class Codes: B01J 20/265 modified or post-treated polymers polymer carriers or substrates subjected to further impregnating or coating B01J20/3208
• CPC Class Codes: B01J 20/267 Cross-linked polymers
• CPC Class Codes: B01J 20/268 Polymers created by use of a template, e.g. molecularly imprinted polymers
• CPC Class Codes: B01J 20/28004 Sorbent size or size distribution, e.g. particle size
• CPC Class Codes: B01J 20/28059 being less than 100 m2/g
• CPC Class Codes: B01J 20/28061 being in the range 100-500 m2/g
• CPC Class Codes: B01J 20/28069 Pore volume, e.g. total pore volume, mesopore volume, micropore volume
• CPC Class Codes: B01J 20/28083 being in the range 2-50 nm, i.e. mesopores
• CPC Class Codes: B01J 20/3057 Use of a templating or imprinting material molecularly imprinted polymers B01J20/268; filling pores of a substrate or matrix followed by the removal of the substrate or matrix
• CPC Class Codes: B01J 20/3064 Addition of pore forming agents, e.g. pore inducing or porogenic agents
• CPC Class Codes: C08F 220/20 of polyhydric alcohols or phenols , e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• CPC Class Codes: C08F 222/102 of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate

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.

Claims

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 μ

m, comprise <

10 vol. % fines of diameter <

10 μ

m, have a pore volume of 0.2-1.5 ml/g, have a B.E.T. surface area of 20-500 m²/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 μ

m, comprise <

10 vol. % fines of diameter <

10 μ

m, have a pore volume of 0.5-1.5 ml/g, have a B.E.T. surface area of 50-500 m²/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”

), pentaerythritol tetraacrylate, tri(ethylene glycol)dimethacrylate, tetra(ethylene glycol)dimethacrylate, poly(ethylene glycol)dimethacrylate and pentaerythritol triacrylate (PETRA) and mixtures thereof;

(h) the polymer is a copolymer of 2-hydroxyethylmethacrylate (HEMA) and a hydrophobic crosslinker;

(i) the polymer is a copolymer of 2-hydroxyethylmethacrylate (HEMA) and ethylene glycol dimethacrylate (EDMA);

(j) the polymer is a copolymer of 2- or 3-hydroxypropylmethacrylate (HEMA) and a hydrophobic crosslinker;

(k) the polymer is a copolymer of 2 or 3-hydroxypropylmethacrylate (HEMA) and ethylene glycol dimethacrylate (EDMA);

(l) the moieties of the cross-linker in the polymer are in molar excess of the moieties of the monomer;

(m) the moieties of the cross-linker and monomer are present in the polymer in a molar ration of from 3;

1 to 10;

1;

or

(n) the molar ratio of moieties of the cross-linker and non-acidic monomer in the polymer is from 4;

1 to 6;

1.

28. The method of claim 26, wherein the material is tobacco a tobacco material or a tobacco product.

29. The method of claim 28, wherein:

the tobacco material is treated with an extraction fluid to form an extract;

the extract is treated with the polymer; and

material remaining in the extract is recombined with the tobacco material; and

the polymer is washed after treatment of the extract, and nicotine is recovered from the washings and nicotine in the washings is recombined with the treated fluid.

30. The method of claim 29, wherein the polymer is washed after treatment of the extract, and nicotine is recovered from the washings and nicotine in the washings is recombined with the treated fluid.

31. The method of claim 26, wherein any of the following apply:

(a) producing tobacco leaf, treating the leaf with the polymer in order to reduce the TSNA content of the leaf, producing a consumable tobacco product therefrom and supplying the tobacco product to a consumer so as to deliver the nicotine;

(b) an analysis, detection, quantification, separation, extraction, chromatography, sample preparation, chemical sensors, or solid phase extraction;

(c) any of an analysis, detection, quantification, separation, extraction, chromatography, sample preparation, chemical sensors, or solid phase extraction when performed on biological fluid;

(d) wherein the tobacco product is produced by the thermal decomposition of a material containing tobacco, a tobacco substitute or a mixture thereof;

(e) the material is produced by the thermal decomposition of a material containing tobacco, a tobacco substitute or a mixture thereof by heating the material to a temperature below its combustion temperature;

(f) the material is produced by the thermal decomposition of a material containing tobacco, a tobacco substitute or a mixture thereof by combustion of the material.

32. A tobacco product, smoking article or smoke filter comprising tobacco and porous beads for selectively removing a nitroso-containing compound from material containing the compound and nicotine, said beads being 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.

33. A kit comprising beads for selectively removing a nitroso-containing compound from material containing the compound and nicotine, said beads comprising a polymer of a non-acidic monomer and cross-linker having polar functionality, one of which is hydrophilic, the other of which is hydrophobic, and being selective relative to nicotine for at least one nitroso-containing compound, and further comprising one or more of the following items:

(a) instructions for using the beads to perform at least one of analysing, detecting, quantifying, separating, extracting, reducing or removing nitroso-containing compounds in or from a sample;

(b) a column for solid phase extraction (“

SPE”

), chromatography or other filtration techniques;

(c) a quantity of any of the foregoing beads divided into discrete quantities suitable for loading into the filtration column;

(d) an SPE, chromatography or other filtration column packed with a quantity of any of the foregoing beads;

(e) reagents for conditioning the column;

(f) reagents for eluting the column and re-generating the beads; and

(g) one or more of a spatula, measuring cylinder, beaker or other tool for handling the ingredients.

34. The kit of claim 33, wherein any of the following apply:

(a) the beads contain residues of polyvinyl alcohol;

(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”

), pentaerythritol tetraacrylate, tri(ethylene glycol)dimethacrylate, tetra(ethylene glycol)dimethacrylate, poly(ethylene glycol)dimethacrylate and pentaerythritol triacrylate (PETRA) and mixtures thereof;

(h) the polymer is a copolymer of 2-hydroxyethylmethacrylate (HEMA) and a hydrophobic crosslinker;

(i) the polymer is a copolymer of 2-hydroxyethylmethacrylate (HEMA) and ethylene glycol dimethacrylate (EDMA);

(j) the polymer is a copolymer of 2- or 3-hydroxypropylmethacrylate (HEMA) and a hydrophobic crosslinker;

(k) the polymer is a copolymer of 2 or 3-hydroxypropylmethacrylate (HEMA) and ethylene glycol dimethacrylate (EDMA);

(l) the moieties of the cross-linker in the polymer are in molar excess of the moieties of the monomer;

(m) the moieties of the cross-linker and monomer are present in the polymer in a molar ration of from 3;

1 to 10;

1;

or

(n) the molar ratio of moieties of the cross-linker and non-acidic monomer in the polymer is from 4;

1 to 6;

1.