RU2199574C1 - Chemical marker - Google Patents

Abstract

FIELD: identification of commercial products. SUBSTANCE: invention relates to compounds used for hidden marking of substances, materials, and articles that can be applied when performing various-type expertises at commercial and industrial enterprises. For that aim, C16-C26-n- alkanes, individually or as mixtures, are introduced directly into substances to be marked (chemicals, diesel fuel, kerosene, paraffins, Vaselines, anticorrosive compositions, cosmetic and therapeutic preparations, etc.) or chemical marker-containing compositions are prepared and put on product packaging or are introduced into adhesive formulations or other constituents of products. EFFECT: increased efficiency of marking and identification. 2 dwg, 4 ex

Description

 The invention relates to petrochemistry, specifically to compounds used for hidden labeling of substances, materials, products, and can be applied when conducting various types of examinations in commercial and industrial enterprises.

 It is known the use of special compounds used for hidden labeling of substances, materials and products in order to identify them, determine the ways of their distribution on the market, establish the place of manufacture and confirm the fact of contact interaction [Mitrichev B.C. Forensic examination of materials, substances and products. Ed. Saratov University, 1980, p. 9-90.]. As a chemical marker, liquid paint is used, which has characteristic absorption bands in the visible region of the spectrum [Leistner L., Buytash P. Chemistry in Forensics. M., World, 1990, p. 181-280]. The paint contains fluorescein, feather-like dyes, Belofors of various grades, derivatives of coumarin or 1,3,5-triphenylpyrazoline [Stepanov B.I. Introduction to the chemistry and technology of organic dyes. M., Chemistry, 1984, p. 546-551]. The paint is packaged in special bags of thin synthetic material, which after tearing leave traces of paint on substances, materials and products. Examination of such labeled products makes it possible to substantiate a conclusion on issues of interest.

 The disadvantages of the known chemical marker are the ability to remove it from materials and products with a solution of hydrochloric acid or organic solvents [Stepanov B. I. Introduction to the chemistry and technology of organic dyes. M., Chemistry, 1984, p. 546-551], the impossibility of obtaining unambiguous conclusions on the results of the analysis, because many organic substances are characterized by their own luminescence, for example paraffin, paraffin oil, pine resin, mineral oils, rosin, bitumen, etc., which significantly complicates the identification of the introduced marker [Pilipenko AT, Pyatnitsky IV Analytical chemistry, t. 1. M., Chemistry, 1990, p. 352-363].

The objective of the invention is to increase the efficiency of labeling and identification of introduced compounds through the use of n-alkanes C ₁₆ -C ₂₆ or mixtures thereof as a chemical marker for hidden labeling of substances, materials and products.

The technical result is achieved by the introduction of n-alkanes C ₁₆ -C ₂₆ or mixtures thereof directly into the composition of the marked substances (chemicals or mixtures thereof, diesel fuel, kerosene, paraffins of various grades, petroleum jelly, anti-corrosion compounds, cosmetic or pharmaceutical preparations, etc. ) or by preparing compositions containing a chemical marker, which are applied to the packaging of products, are introduced into adhesive compositions and other components of the product. Detection and unambiguous identification of a chemical marker is carried out using gas-liquid chromatography (GLC) or chromatography-mass spectrometry.

As a chemical marker, n-alkanes of the “h” brand are used, containing from 16 to 26 carbon atoms in a chain, which are obtained by synthetic methods using organomagnesium compounds, according to the Würz method or alkenes reduction [A. Petrov Chemistry of alkanes. M. Science, 1974, 244 pp.]. They are colorless, solid substances with melting points of 18.1-57.0 ^o With boiling points from 287.1 to 262 ^o With (15 mm RT. Art.). Alkanes containing 15 and fewer carbon atoms are not used as a chemical marker, because they are liquid under normal conditions, easily volatilized during use and are contained in significant quantities in petroleum products with boiling points up to 300 ^o C, and alkanes containing 27 or more carbon atoms are difficult to access and expensive substances. The proposed chemical marker meets the requirements necessary for its use:
- has a strictly individual, difficult to repeat and not changing during long-term storage composition;
- is determined in relatively low concentrations in the range of 1.0-5.0 wt.% by the widespread GLC method;
- has no toxic properties;
- has a large number of options for the composition of the marker, which eliminates the possibility of its repetition or coincidence;
- It is easily made in laboratory conditions and is simply disguised as serial substances, materials and products.

A feature of the proposed chemical marker is the possibility of its use for marking complex mixtures of organic compounds, for example, petroleum products. This is because the relative content of normal saturated hydrocarbons in oil products, in the production scheme of which distillation is always present, is close to the normal Gaussian distribution. The introduction of the proposed chemical marker of a certain composition violates the Gaussian distribution of alkanes in the oil product and the ratio of the individual components of the mixture becomes atypical (abnormal), which is clearly seen when studying mixtures by capillary gas-liquid chromatography. As a chemical marker, you can use one individual alkane for labeling simple substances or a mixture of 2-3 alkanes containing C ₁₆ -C ₂₆ . The use of n-alkanes C ₁₆ -C ₂₆ as a chemical marker for substances, materials and products is not described in the literature. The introduction of a larger number of these hydrocarbons as a chemical marker increases the number of abnormal peaks in the chromatogram, which increases the reliability of the determination of labeled substances, materials and products. The number of labeling options depends on the number of individual alkanes in the chemical marker. For example, the use of these eleven n-alkanes as a chemical marker allows you to get 4096 options for labeling, which immediately differ from each other already in the form of chromatograms.

The invention is illustrated by examples of the use of n-alkanes With ₁₆ -C ₂₆ as a chemical marker of substances, materials and products.

Example 1. As a petroleum product undergoing chemical labeling, use purified technical grade paraffin grade "T" with a melting point of 52 ^o C and an oil content of 2.3%. The quality of paraffin corresponds to GOST 23683-94. A 150 ml two-necked flask equipped with a mechanical stirrer and heating is charged with 50.0 g of brand T paraffin, 2.5 g of n-docosane C ₂₂ H ₄₆ and 4.0 g of n-tetracosan C ₂₄ H ₅₀ . The mixture is heated to 80 ^{° C.} , kept at this temperature until the mixture is completely melted, then the stirrer is turned on and the melt is stirred for 15 minutes. Thus labeled paraffin is poured into a beaker and cooled to room temperature. To shoot the chromatograms, 1% solutions of the starting and labeled paraffin in hexane are prepared.

Chromatographic analysis conditions: laboratory gas chromatograph "Fisons-GC 8000", detector - PID; capillary column "HP-Ultra-1" 12.5 m long, 0.2 mm in diameter with a stationary phase thickness of 0.33 microns; carrier gas is helium; flow divider injector 1:20; carrier gas velocity 1.0 ml / min; sample volume 1.0 μl; temperature of the injector 280 ^o C; detector temperature 310 ^o C; the temperature program of the thermostat is 1 min at 100 ^o C, then the temperature rises at a speed of 10 deg / min to 300 ^o C and is held for 10 min at 300 ^o C. The chromatograms of the initial and labeled paraffins are shown in FIGS. 1 and 2. FIG. 1, the content of normal saturated hydrocarbons in the initial paraffin, starting with a hydrocarbon with the smallest carbon chain (depending on the grade of C ₁₈ -C ₂₀ paraffin), first increases and when it reaches a maximum in the middle of the fraction (C ₂₃ -C ₂₇ ) it begins to decrease uniformly to With ₃₄ -C ₃₆ grams of paraffin with a chemical marker (figure 2), it differs sharply from the original sample by its atypicality and clear individualization of the introduced hydrocarbons. Paraffins with such a hydrocarbon composition are not found in natural substances, petroleum products, materials and products. Paraffin with a chemical marker and the initial sample simply differ in appearance of the chromatograms.

 Labeled paraffin adheres well to clothing, other materials and products, as well as the skin of the hand of a person in contact with it. Any low-boiling hydrocarbon (hexane, heptane, cyclohexane, benzene, etc.) is used as a solvent for removing labeled paraffin from the surface, and then the presence of a marker is determined by chromatographic method. All materials and products labeled or made using labeled paraffin, after one year of storage in the open air, retained a chemical paraffin marker that can be easily determined by chromatography: hydrophobic paper, leather goods, furniture, fabrics, matches, candles, hydrophobic paraffin coating of explosive charges .

The use of food paraffin (P-1, P-2, P-3) or medical vaseline (GOST 3582-59) labeled with a chemical marker based on n-alkanes C ₁₆ -C ₂₆ allows us to label food products, medicines and cosmetics in a similar way .

Example 2. Labeling of a powder of a herbal preparation (tobacco leaf extract) is carried out as follows. 5.0 g of paraffin labeled in Example 1 are dissolved in 75 ml of hexane. 10 g of ASK grade silica gel is ground in a porcelain mortar, transferred to a beaker and poured with a prepared solution of paraffin in hexane. The mixture is vigorously stirred until complete absorption of the solution with silica gel. The resulting powder is scattered with a thin layer on a glass plate, dried first in air and then in an oven at 35 ^o C for 2 hours until the smell of hexane disappears completely. The prepared carrier with a chemical marker is masked by color for the preparation. The carrier is stained with 5.0 ml of cold tea extract with vigorous stirring at room temperature in a light brown color and dried in air. To the mass of the drug add 1.0 wt.% Colored silica gel with a chemical marker, the mixture is stirred. We mark the plastic packaging of the preparation with 0.5 g of silica gel powder. The proposed chemical marker allows you to uniquely identify all users of the drug by silica gel particles on clothing and hands, as well as the distribution of the drug and its initial source. The research technique includes extraction of labeled paraffin with hexane and comparison of chromatograms of the obtained extracts.

Example 3. Dissolve 1.0 wt.%, N-hexadecane C ₁₆ H ₃₄ in illuminating kerosene grade KS-25 with a boiling range of 150-280 ^o C. Chromatographic analysis of the source and labeled with a chemical marker kerosene is carried out under the conditions of example 1. Comparison of chromatograms indicates the presence of an abnormal peak of the introduced marker (hexadecane). Using the source and marked kerosene, two experimental fires are carried out, which are then extinguished by a fire extinguisher. In the residual liquids after fires, a chemical marker (hexadecane) is determined by GLC and chromatography-mass spectrometry. GLC analysis is carried out analogously to example 1. The results of the analysis show that in the residual liquid after a fire using the original kerosene in the chromatogram there is no abnormal peak in the chemical marker. An abnormal peak of a chemical marker is present in the liquid residues after a fire with marked kerosene, and its relative intensity due to evaporation of light fractions doubled. To confirm the structure of the compound of the anomalous peak in the chromatogram, we carry out a chromato-mass-spectrometric analysis.

Analysis conditions: chromatograph company "Perkin-Elmer" model "Autosystem XL". The mixture is separated on a PE-35MS quartz capillary column with an internal diameter of 0.18 mm and a length of 20 m under the following conditions: stationary phase - methyl silicone fluid; carrier gas is helium; temperature of the evaporator and interface 300 ^o C; the initial temperature of the thermostat is 50 ^o C with holding in isothermal mode for 5 min, then heating is first at a speed of 5 deg / min ^-1 up to 250 ^o C, and then at a speed of 10 deg / min ^-1 up to 300 ^o C with subsequent exposure in isothermal mode 10 minutes; the volumetric velocity of the carrier gas is 0.3 ml / min ^-1 ; sample volume - 0.5 μl; the analysis was performed with a division of the stream 1:30. Use a Perkin-Elmer mass selective quadrupole detector model TurboMass. Ionization is carried out by electron impact with an energy of ionizing electrons of 70 eV. To identify chromatographic peaks, the experimental mass spectra are compared with the mass spectra of the catalog (EPA NiH, USA), and empirical spectrostructural correlations are also used [N. Wulfson, V. G. Zaikin, A. I. Mikaya Mass spectrometry of organic compounds. M., Chemistry, 1986, 312 p .; Beynon J. Mass spectrometry and its application in organic chemistry. M., Mir, 1964, 347 pp.].

According to the results of the chromatography-mass spectrometric study of the abnormal peak, the contained substance is identified as hexadecane, an introduced chemical marker. In the mass spectrum there is a peak of a molecular ion with a mass number of 226 and intense peaks of fragmentation ions:
Mass number: 39; 41; 42; 43; 55; 56; 57; 70; 71; 85; 226.

 Intensity,%: 135; 590; 160; 1000; 261; 159; 936; 105; 508; 349; 190.

 The mass spectrum of the anomalous peak completely coincides with the mass spectrum of hexadecane from the catalog.

Example 4. In a reactor with a stirrer and electric heating, 100 g of lubricant of PVK cannon grease manufactured by the Orenburg Oil Refinery with a dropping point of 62 ^° C are loaded. The reactor is heated to 80 ^° C, held for 20 minutes until the grease completely melts, the mixer is turned on and 2.0 g of -tetracosane C ₂₄ H ₅₀ and 1.0 g of n-hexacosane C ₂₆ H ₅₄ . The dropping point of a lubricant with a chemical marker, measured in a special device according to GOST 19537-93, has not changed, which indicates a low sensitivity of this indicator to the introduced chemical marker. Chromatograms of the initial and marked PVC grease are recorded under the conditions of Example 1, but at an evaporator temperature of 360 ^° C. Two abnormal peaks of the chemical marker n-tetracosane and n-hexacosane in the marked grease are clearly visible on the chromatogram. The prepared marked grease is used for the corrosion protection of various metal products: automobile parts, household appliances and tools, weapons, ammunition, etc. Using the GLC method, the introduced chemical marker is easily detected without changes after one year of storage, and on the surface of the instruments after their operation during this period. On the surface of materials (paper, wooden table, fabric materials) that had a contact interaction with the tool, traces of lubrication with a chemical marker remain, clearly differing in two abnormal peaks in the chromatograms.

Thus, the proposed chemical marker based on n-alkanes C ₁₆ -C ₂₆ meets the requirements, is uniquely identified in complex mixtures of compounds, and can be used for marking almost any substance, material and product.

Claims (1)

The use of n-alkanes C ₁₆ -C ₂₆ or mixtures thereof as a chemical marker.

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