CN1149941C - Prepn. of stuffing for filter tip of cigarette - Google Patents
Prepn. of stuffing for filter tip of cigarette Download PDFInfo
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- CN1149941C CN1149941C CNB02107089XA CN02107089A CN1149941C CN 1149941 C CN1149941 C CN 1149941C CN B02107089X A CNB02107089X A CN B02107089XA CN 02107089 A CN02107089 A CN 02107089A CN 1149941 C CN1149941 C CN 1149941C
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Abstract
The present invention relates to a preparation method of filling materials for a filter tip of a cigarette. One proportion of brand molecular nicotine, one to eight proportions of function monomers and one to forty proportions of cross-linking agents are dissolved in proper amount of polymerized solvent (such as chloroform, carrene, etc.) according to molar ratios, initiator is added and treated by ultrasound dissolution, and the mixture is sealed after nitrogen inflation and deoxidization; a rigid solid product is obtained by the reaction with ultraviolet irradiation for more than 12 hours under low temperature (from-5 to-4 DEG C). The product is hot treated by more than 5 hours under the temperature of 60 to 120 DEG C, the product is pulverized, sieved and deposited repeatedly to remove fine powderthen, and the product is extracted by taking methyl alcohol / methyl acid as solvent to obtain granular brand polymers of nicotine molecules (the grain diameter is smaller than 150 microns). Nicotine in smoke generated by tobacco combustion is effectively removed by the specific effect on the nicotine from the brand polymers of nicotine molecules, and simultaneously, the brand polymers of nicotine molecules have certain capacity for removing other toxic materials such as tar, etc.
Description
Technical field
The present invention relates to a kind of preparation method of stuffing for filter tip of cigarette, specifically, relate to a kind of stuffing for filter tip of cigarette that utilizes the molecular imprinting technique preparation to remove nicotine.
Background technology
Molecular imprinting technique a kind of new technique [L.Pauling.J.Am.Chem.Soc..1940 that " key " action principle grows up when biological internal antibody of simulation and AI, 62:2643], utilize this technology can prepare the macromolecular material that specific compound (promptly branding molecule or template molecule) is had the predetermined molecules recognition capability.Molecular imprinting technique is risen in 20th century the seventies, the G.Wulff[G.Wulff.Angew.Chem.Int.Ed.Engl.1995 of Germany, 34:1812] and the K.Mosbach[M.Kempe of Sweden, K.Mosbach.J.Chromatogr.A.1995,694:3] basis of having established covalent type molecular brand and non-covalent type molecular brand respectively.The preparation process of molecular brand polymer is: at first, branding molecule (or claiming template molecule) and function monomer form reversible compound or compound by intermolecular interaction (as covalent effect power, noncovalent interaction power or metal ligand exchange etc.) in polymer solvent; Then, add crosslinking agent, initator under UV-irradiation or heating condition, cross-linked polymeric becomes the highly cross-linked high molecular polymer with three-dimensional net structure, thereby this compound or compound are fixed among the high molecular polymer; With suitable method the branding molecule is discharged from high molecular polymer, in molecular brand polymer, just formed spatial form and position of functional group all with branding molecule corresponding " memory " hole, specific effect by between such hole and the branding molecule can reach the purpose that the branding molecular specificity is separated, analyzes.Utilize the molecular brand polymer of molecular imprinting technique preparation because the preparation method is simple, physics and chemical stability is good and have the selectivity of " being scheduled to " to branding molecule, make this technology obtain development rapidly, the application at aspects such as chiral separation, analog antibody, simulation biology sensor, catalysis and organic syntheses comes into one's own more and more widely.
(nicotine nicotine) is the highest toxicant of content in the tobacco to nicotine, and the nicotine content in the general dried tobacco is about 1%～4%.In the smog that result of combustion of tobacco produces, nicotine is main harmful substance in the particulate part.China is world cigarette consumption big country, and how effectively to reduce the harm that smoking causes health is the hot issue that society is concerned about always.Present employed cigarette filter generally is to add filter materials such as activated carbon, perlite in diacetate fiber tow or polypropylene fiber tow.But these materials do not have selectivity to nicotine, can only remove nicotine in the smog by non-specific adsorption, and removal amount is minimum.And document [A.Zander, P.Findlay, T.Renner, B.Sellergren.Anal.Chem.1998,70:3304] and [H.S.Andersson, J.G.Karlsson, S.A.Piletsky, K.Schnidt, K.Mosbach, I.A.Nicholls.J.Chromatogr.A.1999,848:39] in, the molecular brand polymer of nicotine only limits to use in solution, does not see the nicotine that is used for adsorbing smog.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of stuffing for filter tip of cigarette, this material preparation method is simple, and nicotine is had selectivity, can reduce the content of nicotine in the tobacco smoke greatly.
For achieving the above object, the present invention primary raw material and preparation method of preparing molecular brand polymer is respectively:
(1) function monomer:
The F1 methacrylic acid (methacrylic acid, MAA)
The F2 trifluoromethyl acrylate (trifluoromethylacrylic acid, TFMAA)
F3 acrylic acid (acrylic acid)
F4 itaconic acid (itaconic acid)
F5 4-vinyl benzoic acid (4-vinylbenzoic acid)
F6 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid (2-acrylamido-2-methyl-1-propanesulphonic acid)
F7 N acrylamide base propionic acid (N-acrylamidopropinic)
Function monomer of the present invention can be one or more the mixture in the above-mentioned functions monomer.
(2) crosslinking agent:
The C1 ethylene glycol dimethacrylate (ethylene glycol dimethacrylate, EDMA)
C2 trimethoxy propane trimethyl acrylic ester (trimethylolpropanetrimethacrylate, TRIM)
C3 pentaerythritol triacrylate (pentaerythritol triacrylate)
C4 tetramethylol methane tetraacrylate (pentaerythritol tetraacrylate)
C5 divinylbenzene (divinylbenzene)
C6 N, and N '-methylene diacrylamine (N, N '-methylenediacrylamide)
C7 p-N, N '-1,4-phenylene diacrylamine (N, N '-1,4-phenylenediacrylamide)
C8 3,5-(N, N '-diacrylamine base) benzoic acid (3,5-bis (acryloylamido) benzoicacid)
C9 N, and the two acryloyl groups of O--L-phenylalanine (N, O-bisacryloyl-L-phenylalanine)
Crosslinking agent of the present invention can be one or more the mixture in the above-mentioned crosslinking agent.
(3) initator:
A. azodiisobutyronitrile (azobis (isobutyronitrile), AIBN)
B.1,1 ' azo two cyclohexanenitriles (1,1 ' azobis (cyclohexanecarbonitrile), ABCHC)
(4) preparation method
To brand molecule nicotine, function monomer, crosslinking agent is dissolved in an amount of polymer solvent (as chloroform, carrene etc.) with certain molar ratio example (1: 1: 1-1: 8: 40), add initator, through ultrasonic dissolution, seal behind the deaeration by nitrogen stripping, more than 12 hours, obtain hard solid product in the ultraviolet down irradiation reaction of low temperature (5-4 ℃).This product is in 60-120 ℃ of heat treatment more than 5 hours, then crushing screening and repeatedly sedimentation and be solvent extraction removing smalls with methyl alcohol/acid, obtain granular nicotine molecular brand polymer (particle diameter is less than 150 μ m).
The present invention to the specific effect of nicotine, has removed the nicotine in the smog that result of combustion of tobacco produces by the nicotine molecular brand polymer efficiently, simultaneously other noxious material such as tar etc. is also had certain removal ability.
The specific embodiment
Generally, for a polymerisation, monomer and crosslinking agent all only use a kind of, use mix monomer once in a while.The following examples and application examples are example with a kind of monomer and crosslinking agent when the present invention is carried out concrete elaboration substantially.But technology contents of the present invention is not limited in this.
The preparation of embodiment 1, MAA-EDMA system nicotine molecular brand polymer
To brand molecule nicotine, function monomer MAA, crosslinking agent EDMA is dissolved in right amount in the polymer solvent of (every mM (mmol) reactant adds the 6mL solvent) with certain molar ratio example (1: 4: 20), present embodiment is polymer solvent with the chloroform, can be polymer solvent also with carrene, its effect is the same, add a small amount of azodiisobutyronitrile (reactant gross mass 5/1000000ths) and be initator, through ultrasonic dissolution, seal behind the deaeration by nitrogen stripping, more than 12 hours, obtain hard solid product in the ultraviolet down irradiation reaction of low temperature (5-4 ℃).This product is in 100 ℃ of heat treatments more than 5 hours, crushing screening and sedimentation is removing smalls repeatedly then, and (v/v) be solvent extraction at 90: 10, obtains granular nicotine molecular brand polymer (particle diameter is less than 150 μ m) with methyl alcohol/acid.
The preparation of embodiment 2, other nicotine molecular brand polymer
(1) adopt the method described in the embodiment 1 to prepare other nicotine molecular brand polymer, adopt 1,1-azo two cyclohexanenitriles are initator.Adopting the mol ratio of nicotine and function monomer during concrete operations is 1: 1-1: 8; The mol ratio of nicotine and crosslinking agent is 1: 1-1: 40 (seeing Table 1).
Embodiment 3, do not adding under the situation that brands molecule, with adopting embodiment 1 described method to prepare non-brand polymer.
Application examples 1, the nicotine molecular brand polymer of embodiment 1 preparation is joined in the nicotine solution, vibration is more than 12 hours, the nicotine molecular brand polymer is 15.0-20.0mg/g to the adsorbance of nicotine; And under same operation blank polymer is 4.0-6.0mg/g to the adsorbance of nicotine.
Application examples 2, heating make the acetonitrile solution gasification of nicotine, make the polymer of this gas by embodiment 1 preparation under air-flow drives.With methyl alcohol/acid flushing nicotine molecular brand polymer, there is the nicotine of 70%-90% to be adsorbed by molecular brand polymer.
Application examples 3, heating make the mixed solution gasification that contains nicotine, pyridine, benzene, toluene, anthracene, make gaseous mixture pass through the polymer of embodiment 1 preparation under air-flow drives.After the wash-out, there is the nicotine of 70%-90% to be adsorbed, simultaneously also can removes noxious materials such as pyridine in the gaseous mixture, benzene, toluene, anthracene by non-specific adsorption by molecular brand polymer.
Application examples 4, adopt the prepared nicotine molecular brand polymer selective absorption nicotine of embodiment 2.Concrete result of use sees Table 1.
The when corresponding nicotine molecular brand polymer of mole of function monomer and crosslinking agent is to the selective removal effect of nicotine during table 1. preparation nicotine molecular brand polymer
Function
aCrosslinking agent
bSelection to nicotine
Monomer C
1C
2C
3C
4C
5C
6C
7C
8C
9The property removal effect
F
1 4∶20
c?4∶4 4∶4 4∶4 8∶40 2∶20 2∶10 1∶1 6∶10 70％-90％
F
2 4∶20 4∶4 4∶4 4∶4 8∶40 1∶10 1∶10 1∶1 1∶1 80％-90％
F
3 8∶20 8∶8 8∶8 8∶8 6∶30 4∶20 4∶20 1∶2 1∶4 70％-78％
F
4 1∶5 2∶2 2∶2 2∶2 3∶15 1∶3 1∶3 2∶4 2∶8 80％-90％
F
5 5∶10 5∶5 5∶5 5∶5 4∶40 3∶6 3∶6 4∶20 4∶20 75％-83％
F
6 1∶4 1∶1 1∶1 1∶1 1∶5 2∶4 2∶6 3∶12 3∶9 75％-85％
F
7 6∶18 5∶5 5∶5 5∶5 8∶16 4∶20 4∶20 3∶6 3∶6 70％-75％
Annotate: a) function monomer in the table is corresponding to the listed function monomer F of summary of the invention
1, F
2, F
3, F
4, F
5, F
6, F
7
B) crosslinking agent in the table is corresponding to crosslinking agent C listed in the summary of the invention
1, C
2, C
3, C
4, C
5, C
6, C
7, C
8, C
9
C) mol ratio that the proportionate relationship that provides refers to brand molecule nicotine in the table is 1 o'clock, the mol ratio between the function monomer of being expert at and the crosslinking agent of column.
Claims (5)
1, a kind of preparation method of stuffing for filter tip of cigarette, its preparation method is as follows:
To brand molecule nicotine, function monomer, friendship and get agent example=1: 1 in molar ratio: 1-1: be dissolved in chloroform or carrene polymer solvent at 8: 40, addition is that every mM (mmol) reactant adds the 5-7ml polymer solvent, 1,000,000/slender acanthopanax by the reactant gross mass goes into initator, through ultrasonic dissolution, seal behind the deaeration by nitrogen stripping,-5-4 ℃ down ultraviolet ray irradiation reaction obtain solid product more than 12 hours;
More than 5 hours, also sedimentation is to remove smalls repeatedly for crushing screening in 60-120 ℃ of heat treatment for this product, and using methyl alcohol/acid (90: 10) is solvent extraction, obtains granular nicotine molecular brand polymer.
2, preparation method as claimed in claim 1, it is characterized in that described function monomer is: methacrylic acid, trifluoromethyl acrylate, acrylic acid, itaconic acid, 4-vinyl benzoic acid, 2-acrylamido-2-methyl isophthalic acid-propane sulfonic acid are or/and N acrylamide base propylene.
3, preparation method as claimed in claim 1, it is characterized in that, described crosslinking agent is: ethylene glycol dimethacrylate, trimethoxy propane trimethyl acrylic ester, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, divinylbenzene, N, N '-methylene diacrylamine, p-N, N '-1,4-phenylene diacrylamine, 3,5-(N, N '-diacrylamine base) benzoic acid is or/and N, O-bisacrylamide base-L-phenylalanine.
4, preparation method as claimed in claim 1 is characterized in that, described initator is: azodiisobutyronitrile or 1,1 '-azo two cyclohexanenitriles.
5, preparation method as claimed in claim 1 is characterized in that, described granular nicotine molecular brand polymer particle diameter is less than 150 μ m.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02107089XA CN1149941C (en) | 2002-03-13 | 2002-03-13 | Prepn. of stuffing for filter tip of cigarette |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02107089XA CN1149941C (en) | 2002-03-13 | 2002-03-13 | Prepn. of stuffing for filter tip of cigarette |
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| CN1375246A CN1375246A (en) | 2002-10-23 |
| CN1149941C true CN1149941C (en) | 2004-05-19 |
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| CNB02107089XA Expired - Fee Related CN1149941C (en) | 2002-03-13 | 2002-03-13 | Prepn. of stuffing for filter tip of cigarette |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1864567B (en) * | 2006-06-19 | 2011-03-16 | 云南烟草科学研究院 | Compound filter product containing natural plant absorptive material, preparation method and application thereof |
| CN112515237B (en) * | 2020-12-04 | 2021-11-23 | 新火智造(深圳)有限公司 | Manufacturing method of environment-friendly wrapping-free heating non-combustion naked cigarette bomb |
| CN112471590B (en) * | 2020-12-04 | 2021-11-02 | 新火智造(深圳)有限公司 | Environment-friendly wrapping-free heating non-combustion naked cigarette bomb |
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