Polymers Selective for Tobacco Specific Nitrosamines and Methods of Using the Same

• US 20130139835A1
• Filed: 01/18/2013
• Published: 06/06/2013
• 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
• Granted Patent: US 9,265,283 B2
• Time in Patent Office: Days
• US Class Current: 131/298
• CPC Class Codes: A24B 15/245 Nitrosamines
• CPC Class Codes: A24B 15/30 by organic substances A24B15/281 takes precedence
• CPC Class Codes: A24B 15/32 by acyclic compounds
• CPC Class Codes: A24D 3/14 of organic materials as additive of ion exchange materials A24D3/12
• CPC Class Codes: B01D 15/3852 using imprinted phases or molecular recognition; using imprinted phases
• CPC Class Codes: B01J 20/268 Polymers created by use of a template, e.g. molecularly imprinted polymers
• CPC Class Codes: C08F 220/68 Esters
• CPC Class Codes: C08F 222/102 of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• CPC Class Codes: C08F 222/104 of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate

Abstract

A class of molecularly imprinted polymers that specifically recognizes and binds to TSNAs are useful, for example, in analysis and separation of TSNAs from biological fluids. Such polymers are also useful in methods of treating and manufacturing tobacco products and materials. Also disclosed are selectively adsorbent non-molecularly imprinted polymer of a non-acidic monomer and a cross-linker having polar functionality, one of which is hydrophilic, the other of which is hydrophobic, and the use of such polymers in the treatment of materials containing nicotine and nitrosamine.

Claims

1. A method for removing nitrosamine from material containing nitrosamine, said method comprising contacting the material with an adsorbent non-molecularly imprinted polymer of a non-acidic monomer and a cross-linker having polar functionality, one of which is hydrophilic, the other of which is hydrophobic.

2. The method 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, N-methyl acrylamide and mixtures thereof, and the cross-linker is hydrophobic.

3. The method of claim 2, 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.

4. The method of claim 1, wherein 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.

5. The method of claim 1, wherein 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.

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

7. The method of claim 1, wherein the polymer is a copolymer of 2-hydroxyethylmethacrylate (HEMA) and ethylene glycol dimethacrylate (EDMA).

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

9. The method of any of claim 1, wherein the polymer is a copolymer of 2 or 3-hydroxypropylmethacrylate (HEMA) and ethylene glycol dimethacrylate (EDMA).

10. The method of claim 1, wherein the polymer is porous.

11. The method of claim 10, wherein the porosity is the result of polymerization in chloroform, toluene, acetonitrile or other pore-forming solvent.

12. The method of claim 1, wherein:

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

or

(b) 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

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

1 to 6;

1.

13. The method of claim 1, wherein the material is tobacco, a tobacco material or a tobacco product.

14. The method of claim 1, 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.

15. The method of claim 14, 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.

16. The method of claim 14, having any of the following features:

(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.

17. A tobacco product, smoking article or smoke filter comprising tobacco and a selectively adsorbent non-molecularly imprinted polymer of a non-acidic monomer and a cross-linker having polar functionality, one of which is hydrophilic, the other of which is hydrophobic.

18. A tobacco product or smoking article containing tobacco material reduced in nitrosmaines relative to nicotine, the reduction having been effected by treating the tobacco material with water or other extraction fluid to form an extract, treating the extract with a selectively adsorbent non-molecularly imprinted polymer of a non-acidic monomer and a cross-linker having polar functionality, one of which is hydrophilic, the other of which is hydrophobic, and recombining material remaining in the extract with the tobacco material.