RU2010546C1 - Cigarette filter - Google Patents

Abstract

FIELD: tobacco industry. SUBSTANCE: filter has separate parts made from filaments of an organic polymer. An adsorbing substance made from lignin impregnated with a silicone monomer is positioned between these parts. EFFECT: improved structure. 2 cl, 3 tbl

Description

 The invention relates to the tobacco industry and may find application in the manufacture of filter cigarettes.

 Known filters are a fibrous structure using charcoal.

 The disadvantage of these filters is that they do not completely exclude the harmful effects of a number of components of tobacco smoke.

 Various filters are known for smoking articles, in particular for cigarettes, which reduce the toxic effects of tobacco smoke.

 For this, filtering devices are used, the basis of which, as a rule, is acetate, cellulose or cellulose acetate-fiber with substances deposited on it, having adsorption properties or impregnated with these substances.

As such, activated carbon, inorganic and organic salts of mercaptoalkanesulfonic acids of the general formula HSXSO ₃ H (X = (CH ₂ ) _n , n = 2-6, cysteine and acetylcysteine, phthalocyanines are used.

 The disadvantage of these filters is that the spectrum of substances absorbed by these filters is limited in all cases, and the filters themselves can degrade with the formation of toxic compounds when heated.

 So, for example, when using phthalocyanine as a sorbent, the following decomposition products can form - organic cyanides, ammonia, benzene derivatives, etc.

 A known filter for cigarettes made of porous hydroxyapatite (natural origin or obtained by precipitation).

Hydroxyapatite is a material with a particle size of 5 to 20 microns, used in an amount of 0.1 to 20% by weight of tobacco and can be represented by the formula
3 [Ca ₃ (PO ₄ ) ₂ ] M (OH) ₂ , where M is the cation of calcium, strontium or tin.

 Hydroxyapatites are mainly used, in which the M - cation is represented by calcium, since this material is non-toxic and highly effective.

 The hydroxyapatite filter is produced in combination with fibrous material or activated carbon and can be made in the form of a tablet, sleeve, mouthpiece, etc.

 The advantages of this filter for cigarettes are some increase in the efficiency of absorption of harmful substances.

 The disadvantage of this filter is that it does not absorb a wide range of carcinogenic and toxic substances from tobacco smoke.

A known filter containing a base of acetate, cellulose or cellulose acetate fiber, comprising an adsorbing agent, which is a complex of an iron salt with organic low molecular weight ligands, while the adsorbing agent contains ferrous salts as iron salts, and sodium dithiocarbamate alkyl derivatives as ligands while the content of the adsorbing agent is 3.6 to 13 wt. % of the filter fiber, the ferrous salt is selected from the series FeSO ₄ , FeCl ₂ , Fe (NO ₃ ) ₂ , the filter contains dimethyldithiocarbamate or diethyldithiocarbamate as alkyl derivatives of sodium dithiocarbamate.

 The disadvantage of this filter is the limited range of absorbed substances, in particular, absorbing nitric oxide from tobacco smoke, it does not reduce the content of carcinogens such as multi-core aromatic hydrocarbons (pyrene, benz, perylene, dibenz) and nitrosoamines, as well as trace elements such as magnesium, strontium, copper, lead, arsenic, cadmium, chromium, manganese, iron, cobalt, nickel, which also have toxic and carcinogenic effects.

 Known acetate-cellulose filter containing 10% triacetin as an adsorbent.

 This filter selectively absorbs carcinogenic N-nitroso compounds; N-nitrosodimethylamine up to 75%, N-nitrosodiethylamine up to 50%, N-nitrosopyrrolidine up to 74%, resin up to 35%, nicotine up to 28%.

 The disadvantage of this filter is that it practically does not absorb benz [a] pyrene and carcinogenic metals.

Closest to the proposed invention is a filter for cigarettes made of fibers of an organic polymer impregnated with an organic agent, which is an organosilicon monomer N, N'-bis (3-triethoxysilylpropyl) - thiocarbamide (C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NH-C (S) -NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , the amount of which is 6 - 15.3 wt. % by weight of fibers.

 The positive quality of this filter is that it allows you to capture carcinogenic and toxic substances, namely carcinogenic metals, N-nitroso compounds and benz [a] pyrene better than known cigarette filters.

 The prototype is a filter for cigarettes, consisting of individual parts made of fibers of an organic polymer, and placed between these parts of an absorbent agent.

 The disadvantage of the filter is that it does not differ from the known cigarette filters in absorbing carbon monoxide, nicotine and tar.

 In addition, it does not fully capture N-nitroso compounds.

 All of the above cigarette filters as a whole do not reduce the content of carcinogenic compounds in the main stream of tobacco smoke by more than 50%, while each of the known filters is able to reduce the content of only a certain class of chemical compounds with carcinogenic and toxic properties.

 Therefore, the urgent task of developing a filter for cigarettes, which would reduce the level of carcinogenic benzo [a] pyrene, carcinogenic metals and volatile nitroso compounds, as well as carbon monoxide, tar and nicotine in the main stream of tobacco smoke, which would reduce the risk of cancer due to with smoking.

 The aim of the invention is to increase the degree of purification of the main stream of tobacco smoke from carbon monoxide, tar, nicotine, carcinogenic benz [a] pyrene, carcinogenic metals and volatile N-nitroso compounds.

The goal is achieved due to the fact that in the filter for cigarettes, consisting of separate parts with an adsorbing agent, between them made of organic polymer fibers, for example, cellulose, cellulose acetate or acetate fiber, as an adsorbent agent containing lignin impregnated with organosilicon monomer N, N'-bis (3-triethoxysilylpropyl) -thiocarbamide (C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NH-C (S) - NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , the amount of lignin is determined by the formula:
G = 0.31 ˙ D ² ˙ L, where G is the weight of lignin, mg;
D is the diameter of the cigarette filter, mm;
L - the length of the filter filled with lignin is 2.5 mm ± 0.5 mm, lignin and organosilicon monomer in the adsorbing agent are in a ratio of 100: 6.38.

 Lignin, one of the main structural components of plants, especially wood, is now understood to mean natural polymer products resulting from the dehydrogenation of three main precursors: coniferyl, sinal and p-coumarols. Ferulic and caffeic acids are structural elements of lignin. The structure of lignin obtained by mechanical grinding practically does not contain altered elements and most corresponds to lignin in its natural state.

L·g, где π = 3,14;
D - диаметр сигаретного фильтра, в данном случае равный 9 мм;
g - удельный вес лигнина, равный 0,39 мг/мм³;
L - длина фильтра, заполняемая лигнином, равна в данном случае 2 мм.The lignin weight (G) is calculated from the relation
G =

L g, where π = 3.14;
D is the diameter of the cigarette filter, in this case equal to 9 mm;
g is the specific gravity of lignin, equal to 0.39 mg / mm ³ ;
L is the length of the filter filled with lignin, equal in this case 2 mm

постоянная величина, равная 0,31, а L D переменные, то приходим к формуле для определения G, представленной выше. Практически вес лигнина в одном сигаретном фильтре может колебаться от 44 до 66 мг. Например, при весе (G) лигнина равном 50 мг вес пропитывающего мономера составляет около 3,13 мг. Для приготовления раствора мономера используют органический растворитель Н-ГЕКСАН (C₆ ^чH₁₄- чистый), ТУ6-09-3375-78.Given that

constant value equal to 0.31, and LD variables, then we come to the formula for determining G presented above. Practically, the weight of lignin in one cigarette filter can range from 44 to 66 mg. For example, with a weight (G) of lignin equal to 50 mg, the weight of the impregnating monomer is about 3.13 mg. To prepare the monomer solution, an organic solvent N-HEXAN (C ₆ ^h H ₁₄ - pure), TU6-09-3375-78, is used.

 Lignin is impregnated with this monomer in a ratio of 100: 6.38.

 The proposed filter for cigarettes constructively can be performed by known technological methods that are used in the manufacture of combined cigarette filters.

For example, consider a combined cigarette filter 18 mm long, consisting of two parts made of cellulose and acetate fibers, between which an adsorbent agent (lignin soaked in monomer) is placed. The preparation of filter cigarettes for analysis for nicotine, tar and carbon monoxide was carried out according to the methods described by the International Organization for Standards (ISO, Geneva). Cigarettes prokurivali according to ISO standard under the following conditions: all the cigarettes prior to analysis were conditioned for 48 hours at 22 ^{° C} and 60% relative humidity and prokurivali 20 station-rotary smoker machine firm "BORGWALDT" RM20 / SC (FRG) at a volume of puff equal to 35 ml, puff duration - 2 s, frequency - one puff in 1 min per one Cambridge filter used for chemical analysis of tobacco products.

In the determination of benzo [a] pyrene, condensate was used from five cigarettes smoked through the Cambridge filter, which were extracted with benzene in an ultrasonic bath for 30 min twice. The resulting extract was evaporated on a rotary evaporator to 5 ml at 35 ^{° C,} then 1 ml was used for thin layer chromatography, a layer of loose alumina Brockmann grade 2 in hexane-benzene system. After the development of the chromatogram, the luminescence zone of benz [a] pyrene was isolated under an ultraviolet lamp, and benz [a] pyrene was determined in the obtained fraction on a Hitacni-850 spectrofluorimeter (Japan) at liquid nitrogen temperature.

When determining the carcinogenic volatile N-nitro compounds, smoke from 50 cigarettes was passed through two series-connected liquid traps with citrate-phosphate buffer (pH 4.5) containing 20 millimoles (mmol) of ascorbic acid. The absorption solution was extracted with methylene chloride (CH ₂ Cl ₂ ), water and the extract were separated 1 time, then it was extracted with 50 ml of a bipolar alkali solution (2 M NaOH) and brought to a volume of 5 ml in a water bath under a stream of nitrogen. The resulting solution was analyzed on a Tsvet gas chromatograph with a thermal energy detector TEA 502A (USA) specific for volatile N-nitroso compounds.

Analysis was performed under the following conditions: column temperature - 150 ^{° C,} 225 ^{° C} evaporator, pyrolyzer 470 ° ^C Column - glass respectively with 2.5 m in length and 4 mm in diameter, filled with "Carbowax" 20M + 2% alkaline solution (KOH ), the carrier gas is argon, the flow rate is 40 ml / min.

 When detecting metals, smoke from five cigarettes was smoked through a Cambridge filter and extracted in an ultrasonic bath. The resulting extract was filtered through a porous ceramic filter funnel, then washed 2 times with 5 ml of 5-normal (5N) nitric acid. The pure and whole extract, including the washing volume, was poured into a Kjeldahl flask and evaporated by heating to wet salts. The residue was diluted to 15 ml with deionized water and the resulting solution was analyzed on a JV-48 plasma emission spectrometer (Jobin-Ivon, France).

 Cigarettes for experiments were selected from one batch by weight 933 ± 20 mg.

 In the table. 1 shows the test results of a combined cigarette filter containing 50 mg of lignin treated (impregnated) with a monomer. In this case, filter A was treated with a one percent solution of monomer, filter B was 3.0%, and filter C was 5% (solvent N-HEXAN was pure).

100% , где А - абсолютная разница между контрольным и опытным (Б) значением.The absorption capacity of the filter (%) is calculated by the formula

100%, where A is the absolute difference between the control and experimental (B) value.

 From the analysis results it is seen (Table 1) that filter C turned out to be more acceptable, both in its ability to absorb tar, nicotine and carbon monoxide, and in its ability to absorb benz [a] pyrene.

 The absorption efficiency of nicotine is 50%, resin 42%, benz [a] pyrene 68.7%.

 The test results of filter C for the absorption capacity of metals are given in table. 2.

From the table. 2 shows that the filter C effectively absorbs carcinogenic metals:
nickel (64.7%), chromium (80%),
cadmium (68.6%), lead (57.4%).

 The test results of filter C for absorption capacity for carcinogenic volatile N-nitroso compounds are given in table. 3.

 From the table. Figure 3 shows that filter C effectively absorbs the carcinogenic volatile N-nitroso compounds with respect to the control filter (N-nitrosodimethylamine 92.9%, N-nitrosopyrrolidine 76.9%).

 The high absorption and selective ability of lignin to the studied chemical compounds is explained by its features of the chemical and physical structure, as well as by the mechanism of filtering tobacco smoke.

 It is generally believed that two main mechanisms are involved in smoke filtration: diffusion and direct capture of smoke particles, the size of which is in the range of 0.1 - 1.0 microns.

 Carbon monoxide, carcinogenic volatile N-nitroso compounds are in smoke in the gas phase state and therefore interact with the structural elements of ferulic lignin and caffeic acids, which have a high ability to inhibit the formation and reaction of nitrosation, as can be seen from the table. 3.

 On the other hand, having a large absorption surface, lignin effectively absorbs metal ions, which are deposited on smoke particles absorbed by direct capture of particles. Since lignin is a solid sorbent, it creates a pressure drop, which, in turn, increases the removal of resins from the main stream of tobacco smoke. The proposed filter for cigarettes, in comparison with all known filters, effectively absorbs carbon monoxide (6.25%), tar (42%), nicotine 50%, benz [a] pyrene (68.7%), carcinogenic metals (nickel - 64.7%, chromium - 80%, cadmium - 68.6%, lead - 57.4%) and volatile N-nitroso compounds (N-nitrosodimethylamine - 92.9%, N-nitrosopyrrolidine - 76.9%).

 Thus, this filter can reduce the risk of cancer due to cigarette smoking. The advantage of the proposed filter is that its manufacturing technology is quite simple (filter fiber impregnation is not required), well-known technological methods are used, which reduces the cost of cigarettes.

 In addition, the palatability of cigarettes is improved.

 Since lignin and organosilicon monomer in the adsorbing agent are in a ratio of 100: 6.38 (only about 6.3 wt.% Of the mass of lignin is taken on a cigarette), the consumption of monomer (compared with the prototype) is reduced by an average of two which also significantly reduces the cost of cigarettes. (56) Swiss Patent No. 526928, cl. A 24 C 5/48, 1972.

Claims (4)

CIGARETTE FILTER, consisting of individual parts made of fibers of an organic polymer and placed between these parts of an adsorbent agent, characterized in that the adsorbent agent is a lignin impregnated with an organosilicon monomer N, N'-bis (3-triethoxysilylpropylthiocarbamide) (C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NH-C (S) - -NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ .  2. The filter according to claim 1, characterized in that the ratio of lignin and the organosilicon monomer contained therein is 100: 6.38.  3. The filter according to paragraphs. 1 and 2, characterized in that the length of the filter filled with lignin is 1.5 - 2.5 mm.  4. The filter according to claim 1, characterized in that it is made of cellulosic, cellulose acetate or acetate fiber.

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