CN101664228A - Calixarene additive capable of simultaneously and optionally reducing benzo (alpha) pyrene and phenol contents in cigarette smoke and application method thereof - Google Patents
Calixarene additive capable of simultaneously and optionally reducing benzo (alpha) pyrene and phenol contents in cigarette smoke and application method thereof Download PDFInfo
- Publication number
- CN101664228A CN101664228A CN200910307638A CN200910307638A CN101664228A CN 101664228 A CN101664228 A CN 101664228A CN 200910307638 A CN200910307638 A CN 200910307638A CN 200910307638 A CN200910307638 A CN 200910307638A CN 101664228 A CN101664228 A CN 101664228A
- Authority
- CN
- China
- Prior art keywords
- cigarette
- additive
- pyrene
- benzo
- cigarette smoke
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a calixarene additive capable of simultaneously and optionally reducing benzo (a) pyrene and phenol contents in cigarette smoke and an application method thereof. In the invention, deep-cavity P-(1-(4-hydroxyphenyl)-1-methylethyl) calyx (8) aromatic compound is selected as the additive material, and the compound is added in a common and conventional filter tip which bettercan be suitable for a compound filter, with the additive amount being arbitrarily adjusted according to the needs. By using the molecular recognition function and the cavity size select effect of thecalyx (8) aromatic compound, the additive can be optionally combined with the benzo (a) pyrene and phenol molecules in the cigarette smoke. When the additive is added into the filler with the amount of 10mg/per cigarette, 33.2 percent of benzo (a) pyrene content and 41.4 percent of phenol content in the cigarette smoke can be simultaneously reduced, and other chemical compositions in the smoke arebasically not influenced, thus achieving the goal of selective harm reduction.
Description
Technical field
The present invention relates to utilize the method and technology of [a] pyrene of benzo in the calixarene compound selectivity reducing cigarette fume and phenol content, particularly the method and technology of benzo [a] pyrene and phenol content in utilization cup [8] aromatic compound while selectivity reducing cigarette fume.
Background technology
The reducing tar and reducing harm of cigarette product is to be related to smoker and the healthy major issue of involuntary smoker, has caused the great attention of tobacco business.For many years, tobacco research institution and tobacco productive corporation are devoted to the research of reducing cigarette tar and reducing harm reduction aspect always both at home and abroad, have obtained lot of research, and the harmful components in the cigarette smoke have had reduction by a relatively large margin relatively.But the harm reduction method and technology selectivity of Cai Yonging was not high in the past, had partly influenced the original style taste of cigarette.Therefore, the new selective harm reduction method and technology of research and development has become the emphasis and the focus of cigarette industry harm reduction research.
Polycyclic aromatic hydrocarbon in the tobacco and Volatile Phenols compounds are all few, and content is all very low.Polycyclic aromatic hydrocarbon in the cigarette smoke and Volatile Phenols compounds mainly produce in the cigarette burning process.Polycyclic aromatic hydrocarbon is a topmost class carcinogenic substance in the cigarette smoke, and aldehydes matter not only produces harmful effect to the cigarette sensory evaluating smoking, also skin and respiratory mucosa is had strong impulse effect and short cancer effect.Recently, thank to sword equality and carried out cigarette smoke harmfulness index research (tobacco science and technology, 2009, (2): 5-15), research relates to 3 kinds of polycyclic aromatic hydrocarbons such as benzo [a] pyrene, benzo [a] anthracene and Chrysene, and 7 kinds of phenolic compounds such as phenol, hydroquinones, resorcinol, catechol, paracresol, metacresol, orthoresol, result of study shows that benzo [a] pyrene and phenol belong to 2 kinds in the most representative 7 kinds of cigarette smoke harmful components, other 5 kinds is CO, HCN, NNK, NH
3And crotonaldehyde.Therefore, the method and technology of benzo [a] pyrene and phenol content has crucial meaning in the research reduction cigarette smoke.
People had once explored many methods and had been used for reducing polycyclic aromatic hydrocarbon in the cigarette smoke, wherein mostly be in pipe tobacco and add tobacco additive agent, polycyclic aromatic hydrocarbon reduces to some extent in the flue gas though make, but owing to intervened pipe tobacco normal combustion process, so the mouthfeel of flue gas often is affected, and also can increase other harmful components sometimes.The technology of utilizing composite filter tip to reduce polycyclic aromatic hydrocarbon in the flue gas also has many reports.Nineteen ninety-five, Tang Pingtao etc. discover composite filter tip can effectively reduce benzo in the main flume [a] pyrene, tar etc. (the Chinese public health journal, 1995,4:231-233); 1998, Li Shaomin etc. utilized the selective absorption principle of molecular sieve, improved the absorption property of NaY molecular sieve by modification, Copper Ion Exchange etc., the composite filter tip of making can be removed (Chinese patents such as tar in the flue gas and polycyclic aromatic hydrocarbon, CN1172617A, CN1198905A, 1998); Calendar year 2001, Meng thousand is auspicious invented a kind of selectivity remove smoke in carcinogenic cigarette filter tip additive (Chinese patent, CN1285171A, 2001).These composite filter tip technology mainly reduce polycyclic aromatic hydrocarbon by filtering tar, and selectivity is not strong.
At present, in the majority to the report of aldehydes matter in the cigarette smoke with analyzing detecting method research, considerably less to the research of its removal.1975, Morie etc. once studied the filtering selectivity of filter tip to half volatile matter in the flue gas, mention o-cresol and phenol selectivity (Beitr.Tabakforsch.Int., 1975,8 (3): 145-149,150-152); 2009, Yu Tao etc. studied filtration (Chinese tobacco journal, 2009,15 (3): 25-28) of acetate fiber filter tip to aldehydes matter in the cigarette smoke.Still there is not report about the additives of filter tip of phenol in the selectivity filtering cigarette smoke and the additives of filter tip of while selectivity filtering benzo [a] pyrene and phenol.
Summary of the invention
Calixarenes is that a class is by contraposition fortified phenol and the formaldehyde oligomerization macrocyclic compound with unique cavity structure that condensation forms under alkali condition.Calixarenes can form inclusion compound, thereby be widely used in host-guest complexation and bionics in conjunction with neutral organic molecule, polymer molecule, metal ion and anion.In order to make calixarenes just need the size of expansion calixarenes cavity in conjunction with big organic guest molecule, this respect has been done a lot of effort, has several deep cavity shape calixarenes to synthesize out by the derivatization at the calixarenes upper limb.We once studied and had synthesized a kind of deep cavity shape cup [8] aromatic compound (Chinese patent, CN101367713A, 2009).We think, suitable calixarene compound is added in the cigarette filter, utilize the molecular recognition effect and the cavity size selection effect thereof of calixarenes, might in the cigarette smoking process, optionally filter out some harmful components in the flue gas, reach the purpose of harm reduction.At present, do not see the research report and the patent documentation of this respect as yet.
The purpose of this invention is to provide a kind of interpolation is convenient, can optionally reduce [a] pyrene of benzo in the cigarette smoke and phenol content simultaneously cigarette filter-tip additive agent and application process thereof.
The objective of the invention is to be achieved through the following technical solutions:
Described cigarette additive is a calixarene compound, is deep cavity shape cup [8] aromatic compound.
Described cup [8] aromatic compound is right-[1-(4-hydroxy phenyl)-1-Methylethyl] cup [8] aromatic hydrocarbons (relative molecular mass 1920).
The application process of described cigarette additive is for being applied in the cigarette filter, as the additive of composite tip stick.
Cigarette additive of the present invention can effectively reduce benzo in the cigarette smoke [a] pyrene content, phenol content as the composite tip stick additive.
The addition of described cigarette filter-tip additive agent is that 3-20mg/ props up cigarette, and addition can reduce the amount of benzo [a] pyrene as required and the amount of phenol is regulated, and preferred addition is that 8-12mg/ props up cigarette.
Additive deep cavity shape cup of the present invention [8] aromatic compound has excellent selectivity filtering effect to the benzo in the cigarette smoke [a] pyrene molecule and phenol molecule.
The skeleton of described cup [8] aromatic compound is a big ring-type hydrophobic cavity that is made of 8 phenyl ring unit, and this cavity structure can form super molecular compound by the non-covalent bond effect with the suitable guest molecule of size.
Described non-covalent bond effect is meant hydrogen bond, electrostatic interaction, Van der Waals force, hydrophobic effect and ∏-stacking effect etc.
The present invention by the dark cavity configuration of described cup [8] aromatic compound realize with cigarette smoke in the combining of suitable ingredients molecule, having only size, suitable can enter cavity and can produce the material of described non-covalent bond effect with cavity structure could be combined, thereby have the selectivity of height.Novelty of the present invention is not appeared in the newspapers in association area yet.
Additive of the present invention is a solid powdery, is suitable for preparing composite tip stick; Addition is little, and can regulate arbitrarily as required; Can be significantly benzo [a] pyrene and phenol content in the selectivity reducing cigarette fume simultaneously; This technology is workable, has very big application value.
The present invention compared with the prior art, remarkable advantage is:
This technology can reduce [a] pyrene of benzo in the cigarette smoke and phenol content significantly simultaneously.
This technology material addition is few, does not change cigarette odor-absorbing substantially, and the production application feasibility is big.
This technology addition manner is simple, easy to operate.
The specific embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further, and the present invention can implement by the described arbitrary mode of summary of the invention.
Embodiment 1
Take by weighing a certain amount of right-[1-(4-hydroxy phenyl)-1-Methylethyl] cup [8] aromatic hydrocarbons, prop up cigarette with 10mg/ and make an addition in the mouth rod, make the test cigarette that filter tip contains additive of the present invention, with the contrast cigarette do contrast test.The contrast cigarette is not except that containing the additive, and other is all identical with the test cigarette as material auxiliary material, dimensions, mouth rod etc.
To test cigarette and contrast cigarette and under the standard suction condition, aspirate with SM400 type automatic smoking machine, according to standard and the general flue gas detection method of tobacco business, require to collect the flue gas sample according to different test items, carry out the analyzing and testing of the relevant harmful components of flue gas then.Tar content detects and is undertaken by standard GB/T 19609-2004; Polycyclic aromatic hydrocarbon detects with GC-MS; Phenolic compound detects with high performance liquid chromatography-fluorescence detection; Carbonyls detects with high performance liquid chromatography-uv detection method; Tobacco-specific nitrosamine detects with the liquid chromatography-tandem mass spectrometry method; HCN detects with Continuous Flow Analysis instrument method; CO content detects in the smoking machine aspiration procedure automatically.Cigarette smoke correlation analysis testing result demonstrates the effect that additive of the present invention has preferably benzo [a] pyrene and phenol content in the selectivity reducing cigarette fume simultaneously.Concrete data result sees Table 1.
Table 1 additive harm reduction effect assessment
Table 1 additive harm reduction effect assessment (continuing)
| ?NNK *(ng/ props up) | The range of decrease (%) | HCN (g/ props up) | The range of decrease (%) | Crotonaldehyde (g/ props up) | The range of decrease (%) | |
| The contrast cigarette | ?8.25 | ?126.48 | ?25.80 | |||
| The test cigarette | ?7.99 | 3.2 | ?114.91 | ?9.1 | ?23.38 | 9.4 |
* NNK, promptly 4-(methyl nitrosamino group)-1-(3-pyridine radicals)-1-butanone is a kind of tobacco-specific nitrosamine.
Embodiment 2
Take by weighing a certain amount of right-[1-(4-hydroxy phenyl)-1-Methylethyl] cup [8] aromatic hydrocarbons, prop up cigarette with 8mg/ and make an addition in the mouth rod, make the test cigarette that filter tip contains additive of the present invention, with the contrast cigarette do contrast test.The contrast cigarette is not except that containing the additive, and other is all identical with the test cigarette as material auxiliary material, dimensions, mouth rod etc.
To test cigarette and contrast cigarette and under the standard suction condition, aspirate with SM400 type automatic smoking machine, according to standard and the general flue gas detection method of tobacco business, require to collect the flue gas sample according to different test items, carry out the analyzing and testing of the relevant harmful components of flue gas then.The analytical method technology of each analyzing and testing project is with embodiment 1.The correlation analysis of cigarette smoke detects data result and sees Table 2, demonstrates the effect that additive of the present invention has preferably benzo [a] pyrene and phenol content in the selectivity reducing cigarette fume simultaneously equally.
Table 2 additive harm reduction effect assessment
| Tar (mg/ props up) | The range of decrease (%) | CO (mg/ props up) | The range of decrease (%) | Benzo [a] pyrene (ng/ props up) | The range of decrease (%) | Phenol (g/ props up) | The range of decrease (%) | |
| The contrast cigarette | ?12.25 | ?15.30 | ?8.76 | ?46.41 | ||||
| The test cigarette | ?11.35 | 7.3 | ?15.05 | 1.6 | ?6.02 | 31.3 | ?26.86 | 42.1 |
Table 2 additive harm reduction effect assessment (continuing)
| ?NNK *(ng/ props up) | The range of decrease (%) | HCN (g/ props up) | The range of decrease (%) | Crotonaldehyde (g/ props up) | The range of decrease (%) | |
| The contrast cigarette | ?8.31 | ?123.92 | ?26.34 | |||
| The test cigarette | ?8.02 | 3.5 | ?115.15 | 7.1 | ?23.80 | 9.6 |
Embodiment 3
Take by weighing a certain amount of right-[1-(4-hydroxy phenyl)-1-Methylethyl] cup [8] aromatic hydrocarbons, prop up cigarette with 12mg/ and make an addition in the mouth rod, make the test cigarette that filter tip contains additive of the present invention, with the contrast cigarette do contrast test.The contrast cigarette is not except that containing the additive, and other is all identical with the test cigarette as material auxiliary material, dimensions, mouth rod etc.With embodiment 1, harm reduction effect data and embodiment 1 are approaching to cigarette smoke harm reduction Evaluation on effect method and technology for additive.
Claims (5)
1. the cigarette additive of benzo [a] pyrene and phenol content in the selectivity reducing cigarette fume simultaneously is characterized in that described additive is right-[1-(4-hydroxy phenyl)-1-Methylethyl] cup [8] aromatic compound.
2. the application process of calixarene compound is characterized in that, with calixarene compound right-[1-(4-hydroxy phenyl)-1-Methylethyl] cup [8] aromatic hydrocarbons be applied in the cigarette filter as cigarette additive.
3. application process according to claim 2 is characterized in that, right-[1-(4-hydroxy phenyl)-1-Methylethyl] cup [8] aromatic hydrocarbons is used the additive as the cigarette composite tip stick.
4. according to claim 2 or 3 described application processes,, it is characterized in that the addition of calixarene compound is that 3-20mg/ props up cigarette in cigarette filter.
5. application process according to claim 4 is characterized in that, addition is that 8-12mg/ props up cigarette.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103076389A CN101664228B (en) | 2009-09-24 | 2009-09-24 | Calixarene additive capable of simultaneously and optionally reducing benzo (alpha) pyrene and phenol contents in cigarette smoke and application method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103076389A CN101664228B (en) | 2009-09-24 | 2009-09-24 | Calixarene additive capable of simultaneously and optionally reducing benzo (alpha) pyrene and phenol contents in cigarette smoke and application method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101664228A true CN101664228A (en) | 2010-03-10 |
| CN101664228B CN101664228B (en) | 2011-09-07 |
Family
ID=41801132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009103076389A Active CN101664228B (en) | 2009-09-24 | 2009-09-24 | Calixarene additive capable of simultaneously and optionally reducing benzo (alpha) pyrene and phenol contents in cigarette smoke and application method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101664228B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921364A (en) * | 2010-09-10 | 2010-12-22 | 浙江中烟工业有限责任公司 | Polycationic additive capable of reducing benzo[a]pyrene in cigarette smoke and preparation method thereof |
| CN101948553A (en) * | 2010-09-10 | 2011-01-19 | 浙江中烟工业有限责任公司 | Polyanion composite material for reducing benzo (a) pyrene contained in cigarette smoke and preparation method |
| CN102002888A (en) * | 2010-09-16 | 2011-04-06 | 湖南中烟工业有限责任公司 | Cellulose paper capable of reducing benzo(a)pyrene content of smoke of cigarettes, preparation method thereof and use thereof |
| CN102132951A (en) * | 2010-12-29 | 2011-07-27 | 华宝食用香精香料（上海）有限公司 | Method for preparing additive capable of reducing release amount of crotonic aldehyde in smoke of cigarette |
| JP2016531582A (en) * | 2013-09-06 | 2016-10-13 | マサチューセッツ インスティテュート オブ テクノロジー | Filter material containing functionalized cellulose |
| CN107129510A (en) * | 2017-03-03 | 2017-09-05 | 福建中烟工业有限责任公司 | Thia cup [4] arene derivatives modifying titanium dioxide and preparation method thereof |
-
2009
- 2009-09-24 CN CN2009103076389A patent/CN101664228B/en active Active
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921364A (en) * | 2010-09-10 | 2010-12-22 | 浙江中烟工业有限责任公司 | Polycationic additive capable of reducing benzo[a]pyrene in cigarette smoke and preparation method thereof |
| CN101948553A (en) * | 2010-09-10 | 2011-01-19 | 浙江中烟工业有限责任公司 | Polyanion composite material for reducing benzo (a) pyrene contained in cigarette smoke and preparation method |
| CN101921364B (en) * | 2010-09-10 | 2012-03-21 | 浙江中烟工业有限责任公司 | Polycationic additive capable of reducing benzo [a] pyrene in cigarette smoke and preparation method thereof |
| CN101948553B (en) * | 2010-09-10 | 2012-07-11 | 浙江中烟工业有限责任公司 | Polyanion composite material for reducing benzo (a) pyrene contained in cigarette smoke and preparation method |
| CN102002888A (en) * | 2010-09-16 | 2011-04-06 | 湖南中烟工业有限责任公司 | Cellulose paper capable of reducing benzo(a)pyrene content of smoke of cigarettes, preparation method thereof and use thereof |
| CN102002888B (en) * | 2010-09-16 | 2012-05-30 | 湖南中烟工业有限责任公司 | Cellulose paper capable of reducing benzo(a)pyrene content of smoke of cigarettes, preparation method thereof and use thereof |
| CN102132951A (en) * | 2010-12-29 | 2011-07-27 | 华宝食用香精香料（上海）有限公司 | Method for preparing additive capable of reducing release amount of crotonic aldehyde in smoke of cigarette |
| JP2016531582A (en) * | 2013-09-06 | 2016-10-13 | マサチューセッツ インスティテュート オブ テクノロジー | Filter material containing functionalized cellulose |
| US11109619B2 (en) | 2013-09-06 | 2021-09-07 | Massachusetts Institute Of Technology | Filter materials including functionalized cellulose |
| CN107129510A (en) * | 2017-03-03 | 2017-09-05 | 福建中烟工业有限责任公司 | Thia cup [4] arene derivatives modifying titanium dioxide and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101664228B (en) | 2011-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101664228B (en) | Calixarene additive capable of simultaneously and optionally reducing benzo (alpha) pyrene and phenol contents in cigarette smoke and application method thereof | |
| CN101150964B (en) | Filter cigarette | |
| Sepetdjian et al. | Phenolic compounds in particles of mainstream waterpipe smoke | |
| TWI304327B (en) | Method of treating tobacco extract to remove magnesium ions, method of preparing regenerated taobacco material, and regenerated tobacco material | |
| CN101947435B (en) | Chitosan polycation additive for reducing phenols in cigarette smoke | |
| CN102809621B (en) | Method for detecting content of eugenol in cigarette mainstream smoke | |
| CN101433372A (en) | Filter material of cigarette filter stick and cigarette filter stick | |
| CN104351946A (en) | Cigarette filter rod for selectively reducing phenol content in smoke gas of cigarettes as well as preparation method and application of cigarette filter rod | |
| CN101261254B (en) | Determination method for transfer behaviors index of alkaline spices in cigarette | |
| CN101169397B (en) | Method for determining propane diols and glyceryl alcohol in cigarette main flue | |
| CN103743768A (en) | Evaluation method for substance migration in smoking of cigarette filter stick | |
| CN103604677A (en) | Separation method of acid flavor components in cigarette mainstream smoke gas | |
| EP2517584A1 (en) | Composite filter comprising biological composition | |
| CN103341347A (en) | Adsorbent for selectively reducing release amount of volatile carbonyl and phenol compounds in cigarette smoke and preparation method and application of adsorbent | |
| CN101103841A (en) | Tobacco product | |
| US11839232B2 (en) | Method for preparing tar extract having aromatic characteristics by using discarded cigarette butt, and use thereof in cigarette | |
| CN106908541B (en) | The chiral analysis of nicotine closes phase chromatographic tandem mass spectrography in a kind of cigarette mainstream flue gas | |
| CN103141940A (en) | Entrapment agent for selectively lowering crotonaldehyde content in cigarette smoke and filter stick | |
| CN104777256B (en) | Analysis method for simultaneously determining six polyphenol contents in flue-cured tobacco | |
| CN102221591B (en) | Method for evaluating adsorption effect of filter tip additive on phenolic compound in smoke | |
| CN101822426B (en) | Application method of para-[1-(4-methoxyphenyl)-1-methylethyl] calix [8] arene | |
| Dagnon et al. | The effect of cigarette design on the content of phenols in mainstream tobacco smoke | |
| CN103616310B (en) | The method of Fast Evaluation porous filter tip additives for absorbing effect | |
| CN101266232A (en) | Determination method for transfer behaviors index of aldehyde ketone spices monomer in cigarette | |
| CN104473324A (en) | Application of cyclodextrin polymer for selectively reducing phenol content in cigarette smoke |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |