Method of evaluating effect of nanocomponents on sanitary-chemical properties of polymer materials

FIELD: chemistry.

SUBSTANCE: before testing in a heat chamber, samples of polymer materials are activated with UV radiation in the 248-365 nm wavelength range for 3-30 minutes with radiation power density of 1-15 mW/cm2. Analysis of volatile organic compounds is carried out while comparing the obtained chromatograms of gas samples collected from the heat chamber when testing samples of polymer materials with selected additives based on nanostructured bentonite powder and nanostructured bentonite powder intercalated with metal ions - magnesium (Mg2+ ), scandium (Sc3+), chromium (Cr3+), manganese (Mn2+), iron (Fe2+), cobalt (Co2+), nickel (Ni2+), copper (Cu2+), zinc (Zn2+), tin (Sn2+), cerium (Ce3+) or a mixture of bentonite powders intercalated with ions of said metals. The results of comparing chromatograms of gas samples are used to evaluate the effect of nanocomponents on the predicted sanitary-chemical properties of the designed polymer materials.

EFFECT: realisation of the present invention widens technological capabilities and increases reliability of results of evaluating the effect of modifying mineral nanocomponents on predicted sanitary-chemical properties based on release of volatile organic compounds from the designed polymer materials.

8 cl, 7 ex, 2 tbl, 4 dwg

 

The technical field

The invention relates to hygiene, sanitation and medicine, in particular to methods of assessing the impact of nanocomponents on sanitary-chemical properties of polymeric materials to predict their safety on the toxicity of volatile organic compounds.

Polymeric materials belong to the class of complex multicomponent structures, preferably on the basis of thermoplastic and thermosetting materials, various fillers, plasticizers, coloring agents, curing accelerators, stabilizers and other additives. The unique physico-chemical, mechanical and performance of polymeric materials causes their wide application in various spheres of human life: in industry and construction, transportation, medicine, life and other

Industrial manufactured of polymeric materials undergo a comprehensive research and monitoring on:

- sanitary-chemical properties to determine the migration of hazardous (toxic) organic volatile compounds in the environment, in contact with the polymer material;

- physico-mechanical properties to determine their mechanical, thermal characteristics, the electrified etc.;

hygienic and microbiological properties to determine the effect of these materials on the development of microflora;

other researchers who reported depending on the technological requirements for these materials for their use in the system environment or in a living organism.

The disadvantage of polymeric materials, which limits the possibility of their widespread use (especially in confined spaces), is the process of toxic volatile organic compounds migrating into the air, intensifying when exposed to thermal, oxidative, light, ozone, radiation and other environmental factors.

Given these circumstances polymeric materials are diagnosed on sanitary-chemical properties to evaluate the toxicity of volatile organic compounds, classification of which is set by the world health organization (who) and which include phenol-, methanol-, toluene-, amino compounds and other harmful organic compounds subject to sanitary-chemical control.

Prior art

To assess the sanitary-chemical properties of polymeric materials, preferably using methods of gas and liquid chromatography, allowing to effectively identify and analyze volatile organic compounds (VOCS)released from polymeric materials.

Currently, for analysis of VOCS emitted from materials, including polymeric materials, use the following guidance documents.

National standard of the Russian Federation. GOST R ISO 16000-6-2007 Air confined space. Part 6. The definition of yuchih organic compounds in the air of the confined space and the test cell by active sampling onto sorbent Tenax TA with subsequent thermal desorption and gas chromatography analysis using FFM/PID" (28.03.2007,).

MUK 4.1.618-96 "guidelines for gas chromatography-mass spectrometric determination of volatile organic compounds in ambient air" (31.10.1996,).

HOWTO MUK 4.1.994-00 Sanitary-chemical evaluation of polymeric materials intended for use in videodisplay terminals, personal electronic computing machines and systems on their basis" (29.10.2000 year).

State standard "Materials and products construction polymer finishing on the basis of polyvinyl chloride. Method of sanitary-chemical assessment" (No. 332, 01.01.1985 year).

HOWTO MU 2.1.2.1829-04 "Sanitary-hygienic evaluation of polymeric and polymer-containing building materials and structures intended for use in the construction of residential, public and industrial buildings" (06.01.2004,).

ISO 14624-3A, Space systems - Safety and compatibility of materials - Part 3: Determination of offgassed products from materials and assembled articles. This international technique is used for the safety assessment of release of materials and equipment in confined spaces, areas for spacecraft and space systems.

According to methodological documents the purpose of the sanitary-chemical research - qualitative identification and quantitative determination of the gas in the environment of chemicals that are released from the mater is Alov, including polymeric materials.

Samples of polymeric materials in model laboratory conditions are in heat chambers (climate chambers). The heat chamber is sealed, has the technical means to maintain and control temperature and humidity. Sampling from the heat chambers is performed using a suction device. Procedures for sample preparation and analysis methods are selected depending on the type of test materials.

Measurement tools, accessories, chemical reagents, laboratory glassware shall be determined in accordance with the methods of analysis of harmful volatile chemicals.

For conducting gas and liquid chromatography LOS used: the heat chamber; a suction unit, a pump for sampling, flow meter (calibration gas flow), sorption tubes (for VOC concentrations on the solid polymeric sorbent), gas chromatography capillary column for separation of the analyzed substances), a device for thermal desorption of VOCS from the sorption tubes, gas-liquid chromatograph with a flame ionization detector (PID) and/or mass spectrometer detector (MSD).

Measurement of VOC concentrations based on their concentration of the gas sample on a solid polymer sorbent, followed by thermal desorption, cryogenic is ocherovanie (capture) in the capillary, gas chromatographic separation on a glass capillary column with the identification of VOCs using a PID and/or FFM.

The FFM can be used to identify and quantify VOCS, while the signals of the PID are only used for the quantitative determination of VOCS.

For reliable identification and quantification of chemical substances migrating from a polymeric material, samples of the materials in the model laboratory conditions is carried out after their process of aging in natural conditions over a long period of 2-6 months, which is necessary for stabilization (normalization) process of gas release from polymeric materials. However, technological extract reduces efficiency and limits the use of the known methods of analysis (including gas-liquid chromatography) in the design of new polymeric materials, including those containing nanocomponent (nanoparticles), which requires an assessment of the safety of their use and impact on the projected sanitary-chemical properties of the tested materials.

It is known that the improvement of properties of polymeric materials, including the ability to inhibit the secretion of volatile organic compounds (VOCS), provided what ispolzovaniem modifying mineral additives on the basis of micro - and nanocomponents (see, for example, the article "the System of quality control of polymeric materials in modern construction technologies" (authors Tpeskova and other Bulletin of science, No. 1, 2007, s-196), which is the closest analog of the present invention.

Assessment of sanitary-chemical properties of polymeric materials in this technical solution is in the gas chromatographic analysis of volatile organic compounds from the gas samples taken from the heat chamber when testing samples of polymeric materials, modified mineral additives.

To test the use of polymeric materials with mineral additives in the form of talc, related to environmentally sound mineral, used especially in medicine and sanitation.

From this technical solution, it follows that the inhibition of volatile organic compounds from testing of polymeric materials due to sorption efficiency of this mineral Supplement.

These studies, however, indicate that during long-term operation of the sorption activity of these supplements is reduced, which affects the sanitary-chemical properties of the polymeric material.

For identification and determination of the emission of volatile organic compounds from the test samples it can withstand for a long time (with the according standard methods for stabilization (normalization) process gas. In the limited technological capabilities and the efficiency of forecasting sanitary-chemical properties of the emission from the design of polymeric materials, including nanocomponents, reducing the reliability of the estimates.

The invention

The technical result of the present invention is to enhance the technological capabilities of the evaluation of the sanitary-chemical properties of the emission, in improving the reliability of estimates of projected sanitary-chemical properties of the emission from the design of polymeric materials with nanocomponents.

To achieve the technical result of the proposed method of assessing the impact of nanocomponents on sanitary-chemical properties of polymeric materials consisting in the gas chromatographic analysis of volatile organic compounds from the gas samples taken from the heat chamber when testing samples of polymeric materials, modified mineral additives, the polymer samples of materials before they are checked in the chambers activate the UV radiation in the wavelength range 248-365 nm for 3-30 min at a power density of radiation 1-15 mW/cm2analysis of volatile organic compounds is carried out at the comparison of gas chromatograms of samples taken from the heat chamber when testrow the research Institute of polymeric materials with modifying additives on the basis of nanostructured powder of bentonite and nanostructured powder of bentonite, intercalated by ions of metals such as magnesium (Mg2+), scandium (Sc3+), chromium (Cr3+), manganese (Mn2+), iron (Fe2+), cobalt (Co2+), Nickel (Ni2+), copper (Cu2+), zinc (Zn2+), tin (Sn2+), cerium (CE3+or a mixture powder of bentonite intercalated by ions of these metals, and the results of the comparison of gas chromatograms of samples and assess the impact of nanocomponents projected on sanitary-chemical properties of the designed polymer materials.

In the present invention for testing the use of polymeric materials based on polyvinyl chloride, polyurethanes and silicones in the amount of 0.3 to 5 wt % of nanostructured additives.

In the present invention, the sampling of the gas medium from the heat chamber when testing samples of polymeric materials is carried out at temperatures of 25-28°C and 40-50°C and the process is conducted within 2-15 days with the subsequent processing of the obtained chromatograms for the respective temperatures.

In the present invention for obtaining nanostructured bentonite (montmorillonite), intercalated by ions of metals such as magnesium (Mg2+), scandium (Sc3+), chromium (Cr3+), manganese (Mn2+), iron (Fe2+), cobalt (Co2+), Nickel (Ni2+), copper (Cu2+), zinc (Zn2+), tin (Sn2+), cerium (CE3+) using the semi - bentonite, pre-enriched sodium ions in the processing of 3-10% aqueous solution of sodium chloride, followed by purification from the anions of chlorine, which is then intercalary 0.3 to 20% aqueous solutions of inorganic salts of these metals, cleaned from salts of sodium, crushed and dried.

In the present invention as modifying nanocomponents use a mixture of powders of bentonite intercalated by ions of cerium and copper ions, Nickel, iron at their weight ratio, as (5-10):1.

In the present invention for the intercalation of prefabricated bentonite enriched with cations of sodium, preferably, using a 0.3 to 2.0% aqueous solution of nitric acid salt of cerium CE(NO3)3·6H2O.

In the present invention, the enriched bentonite cations sodium and intercalation of the obtained semi-finished product is used the weight ratio of bentonite:water solution of 1-(10-40).

In the present invention for testing the use of polymeric materials with nanostructured mineral filler with a particle size of not more than 150-200 nm.

When implementing the present invention are expanding technological capabilities and reliability of obtaining results on the effect of modifying mineral nanocomponents projected on sanitary-chemical properties for selection leukemogenicity compounds of the design of polymeric materials, what explains:

- use to assess the sanitary-chemical properties of polymeric materials mode, simulating technological exposure of polymeric materials to stabilize (normalization) in these processes outgassing;

- use to simulate the process of aging of polymeric materials of activated their UV-radiation, energy impact, which promotes the dissociation of the weak links in the polymer emitting part of the volatile organic compounds that stabilizes (normalizes) the process of gassing and ensures the accuracy of identification and quantitative determination of chemical compounds that are released from polymeric materials when tested in a heat chamber;

- comparative analysis of gas chromatograms of samples obtained by heat treatment of test specimens polymeric materials used nanocomponents confirming their impact on the evolution and providing reliability prediction sanitary-chemical properties outgassing polymer materials;

- use for analysis of samples of polymeric materials with the selected nanocomponents based bentonite (montmorillonite), intercalated by ions of these metals, providing inhibition of oxidative processes in polymers is caused by the action of metal ions on peroxide or alkyl radicals, which improves the reliability of the forecasting sanitary-chemical properties of the designed polymer materials;

- use to assess the sanitary-chemical properties of polymeric materials based on polyvinyl chloride, polyurethanes and silicones, are widely used in various industries, including medicine, and to which high demands are placed on the prediction of their sanitary-chemical properties.

In the analysis of the prior art are not identified technical solutions with a set of features of the present invention described above and provides the result.

The analysis of the prior art demonstrates compliance with the proposed technical solution criteria invention of "novelty", "inventive step".

The present invention can be industrially realized by using known manufacturing processes, equipment and materials, including those designed to assess the impact of nanocomponents on sanitary-chemical properties of polymeric materials.

The implementation of the invention

The invention is illustrated by figures and tables.

Figure 1 and Table 1 presents the results of gas chromatographic analysis of the emission of volatile organic compounds from testing the samples of polymeric materials based on silicone.

2, 3 and Table 2 presents the results of gas chromatographic analysis of the emission of volatile organic compounds from the test samples of polymeric materials based on polyvinyl chloride.

Figure 4 shows the results of gas chromatographic analysis of the emission of volatile organic compounds from the test samples of polymeric materials based on polyurethane.

For the process you used the following materials.

Polymeric materials based on:

- silicones RTV 4408"A" and RTV 4408"," manufacturer Bluestar Silicones. France, this product is intended for medical products, in particular, Exo - and orthoprothuses and items for household purposes;

- plastisol (polyvinyl chloride + plasticizers) brand D-23M, Russia;

- polyurethane foam, for which manufacturing (molding method using a reaction injection molding) was used polyol as one component of the drug Voralux™ NC 490 (Dow Chemical Company) and isocyanate component - drug Specflex™ NE 371 (Dow Chemical Company).

These materials are widely used in various industries and areas of life, including medicine. Intensifying when exposed to various environmental factors the aging process, degradation of polymeric materials is accompanied by the allocation of the of these toxic compounds.

At the present stage of designing materials to improve their operational characteristics are achieved, including through the use in the compositions of modifying nanocomponents (nanostructured additives), whose influence on the projected material must be evaluated.

In the present invention assesses the impact on the design of polymeric materials nanocomponents on the basis of nanostructured bentonite Na-form (montmorillonite), which for the modification of polymeric materials is the most optimal.

Natural layered mineral bentonite (montmorillonite) belongs to the class of alkaline bentonite (bentonite, Na-form), in which the content of montmorillonite 75-85 wt.%. This mineral component is most effective for the modification of polymeric materials due to its environmental, safety, sorption activity and cation exchange capacity (up to 150 mg·EQ/100 g).

To modify the selected polymeric materials (on the basis of the above materials - silicone, polyvinyl chloride, polyurethane foam) use the following compounds and products of the examples.

Example 1.

Nanostructured powder of bentonite (montmorillonite), which is dried and crushed (for example, in jet mills) to the size of powder particles of not more than 150-200 nm. Formed in MEA is icenii this mineral nanoparticles have a large surface energy and adsorption activity. Specific mineral properties determined the feasibility of its use in the modification of the design of polymeric materials to predict their sanitary-chemical properties according to the release.

Example 2.

Obtaining prefabricated bentonite enriched with sodium ions.

Bentonite Na-form enriched with Na+ cations in the processing of 3-10% aqueous solution of sodium chloride, followed by purification of chlorine anions. Preferably, use a 5% aqueous solution of sodium chloride, maintain the bentonite in this solution, then repeatedly decanted when the rinsing deionized water to pH=7 (removal of anions of chlorine), pulverized using an ultrasonic disperser Sonopuls HD 2070, Bandelin) and dried. The size of powder particles of not more than 150-200 nm.

To obtain prefabricated bentonite enriched with sodium ions, used 500 g of bentonite of example 1.

Example 3.

Development of nanostructured powder of bentonite intercalated by ions of metals such as magnesium (Mg2+), scandium (Sc3+), chromium (Cr3+), manganese (Mn2+), iron (Fe2+), cobalt (Co2+), Nickel (Ni2+), copper (Cu2+), zinc (Zn2+), tin (Sn2+).

For production of powders of bentonite use the semi-finished product according to example 2, which modify (intercalary) 0.3 to 20% water, R is the cross-sections of inorganic salts of magnesium, scandium, chromium, manganese, iron, cobalt, Nickel, copper, zinc, tin.

As inorganic salts for intercalation, preferably, use, 15% aqueous solutions of sulfates or nitrates of metals such as copper sulfate (CuSO4), ferrous sulfate (FeSO4), zinc sulfate (ZnSO4or ZnCl2.

Example 4.

Development of nanostructured powder of bentonite intercalated by ions of cerium (CE3+) (bentonite in cerium form).

This product is obtained by modification of 0.3-2.0% aqueous solution of nitric acid salt of cerium CE(NO3)3·6H2O semi-finished product according to example 2.

Bentonite in cerium form the most optimal for the purposes of the present invention.

When this product came from the fact that the cerium (metal of variable valence) is the most effective on the electrochemical activity of the metal. Cerium reacts with oxygen with the formation of cerium dioxide (CeO2).

Ions, nanoparticles of cerium dioxide and cerium exhibit antioxidant properties, have inactivating and inhibitory effects on oxygen-containing compounds, peroxide and hydroperoxide radicals generated during oxidative processes in technical materials (including polymer), as well as biological materials and tissues.

In particular, to obtain bentonite, interc the isolation ions of cerium used a 0.5% aqueous solution of cerium nitrate CE(NO 3)3·6N2O. Received after intercalation, cleaning and grinding powder of bentonite contains cerium in an amount of not more than 0.5 wt %. The particle size distribution of the bentonite in cerium form - not more than 200 nm.

Specifically for the implementation of this example used 50 g of CE(NO3)3·6N2O.

For the realization of examples 2-4 were used the weight ratio of bentonite:water solution as 1:(10-40) and preferably 1:20.

Method for plasma analysis (ICP) to determine the metal content in nanostructured powders of bentonite (examples 3, 4), intercalated by ions of these metals.

The amount of cerium in the product according to example 4 was 1.5 wt%.

In nanostructured powder of bentonite intercalated, in particular copper ions, the amount of copper - 2 wt.%.

For evaluation of particle size of powders of bentonite according to examples 1, 2, 3, 4 used method of electronic microscopy. The particle size of the analyzed nanostrukturirovannyh powders - no more than 150-200 nm.

The use of cerium assumes its synergistic compatibility with other metals, including copper, Nickel, iron.

For the purposes of the present invention may use a mixture of nanostructured powder of bentonite intercalated by ions of cerium and other metals (e.g. copper, Nickel, iron)that, before occhialino, cost.

For the purposes of the invention it is possible to use mixtures of nanostructured powder of bentonite intercalated by ions of cerium and other metals (e.g. copper, Nickel, iron) when weighing their value as (5-10):1 that the optimal forecasting sanitary-chemical properties of the designed polymer materials.

Used in nanostructured powders of bentonite according to the present invention, the metals have a biological compatibility and electrochemical activity (see number electrochemical activity of metals).

To implement the present invention when creating a projected compositions of polymeric materials using modifier nanostructured powders of bentonite in the amount of 0.3-5.0 wt.%.

The specified flow powders of bentonite for the modification of polymeric materials is optimal. Reducing the amount of bentonite in the projected compositions of polymeric materials does not improve their sanitary-chemical properties of the emission. The increase in the concentration of bentonite in polymeric materials increases costs and affects the process of dispersion of bentonite powders in the polymer matrix of the projected materials.

To assess the impact of nanocomponents on sanitary-chemical is waista were used polymeric materials in the following examples.

Example 5.

Liquid thermosets based on silicones, for example, the brand RTV 4408 "A" and RTV 4408 "In" at a ratio of 1:1, in the amount 100,0±0,1 g

In the resulting composition was dispersively using an ultrasonic disperser nanostructured powder of bentonite according to example 4 in the amount of 1.5 wt.%.

Example 5.1.

The same liquid thermosets that in example 5, but as a dispersed component in them used a nanostructured powder of bentonite of example 1 in the amount of 3 wt.%.

Capacity-prepared mixtures according to the examples 5 and 5.1 was evacuated to a complete removal of gaseous products. The resulting polymer mass was vulcanizable (overidealize). After cooling, the polymer materials were cut into samples of size 4×3 cm, received 6 samples (weighing 15 g) for each instance.

Example 6.

In the tank was mixed components: polyvinyl chloride plastisol D-17I in the number 100,0±0.1 g powder of bentonite intercalated by ions of cerium (example 4), in the amount of 1.5% by weight of plastisol. The resulting composition was mixed and subjected to dispersion using an ultrasonic disperser. The container with the prepared composition was akoumianakis to remove gaseous products. After degassing the polymer mass vulcanizates (overides), cooled.

Of the scientists polymeric material based on polyvinyl chloride manufactured samples of size 4×3 cm, received 6 samples (weighing 15 g).

Example 6.1

The same process of polymeric material of polyvinyl chloride, as in example 6, but as a component dispersed in the plastisol of polyvinyl chloride used nanostructured powder of bentonite of example 1 in the amount of 3 wt.%.

Example 7.

For the manufacture of polyurethane foam (molded using reaction injection molding) was used polyol as one component of the drug VoraluxTM NC 490 (Dow Chemical Company) and isocyanate component - drug SpecflexTM NE 371 (Dow Chemical Company). In the liquid polyol as one component was introduced a mixture of nanostructured powder of bentonite intercalated by ions of copper (Cu2+) ions and cerium (CE3+) in an amount of 3 wt.%, the weight ratio, respectively, 1:8. The weight ratio of polyol as one component:isocyanate component: 2,6:1,01. Consumption 1,085 kg - polyol as one component and 0,421 kg - isocyanate component.

In a specialized form under pressure filed polyol as one and isocyanate components, after foaming, the form was closed. The formed product was dried. Was obtained elastic product, weight - 1.4 kg, width - 34 cm, length 50 cm, profile thickness (min) - 7,0 see Made samples of the test materials in the amount of 6 units with a size of 3×4 see

Example 7.1.

The same process is ECC of polymeric material based on polyurethane, as in example 7, but as an additive dispersed in the polyol as one component used nanostructured powder of bentonite of example 1 in the amount of 3 wt.%.

Samples of polymer materials based on silicone, polyvinyl chloride and polyurethane foam (examples 5-7 .1) were tested to determine the effect of used mineral nanocomponents projected on sanitary-chemical properties according to the release.

The process of testing samples of polymeric materials was carried out as follows.

Stage I - mode simulation of technological exposure of polymeric materials to stabilize (normalization) in these processes outgassing.

For the purposes of the present invention to simulate technological exposure of samples according to examples 5-7 .1 activate their in vivo UV radiation in the wavelength range 248-365 nm at exposure 3-30 min at a power density of radiation 1-15 mW/cm2.

Specified by the present invention, the activated polymer materials optimal for stabilization (normalization) of the processes of emission of volatile organic compounds from polymeric materials, which is necessary for subsequent gas chromatographic analysis. UV radiation in the wavelength range 248-365 nm correspond to the absorption spectra selected for the study of polymeric mater what Alov. When the selected exposure mode, the power density of the radiation is irradiated surface layers of the investigated polymer materials, which are initiated processes of isolation of low molecular weight volatile organic compounds. Specified for the purposes of the present invention the mode of UV radiation allows to simulate the aging process of polymeric materials for further evaluation of their hygiene properties outgassing. Changing mode of UV radiation will lead to the strengthening of the processes of degradation of polymeric materials to change their physical-mechanical properties.

To simulate exposure of polymeric materials to stabilize (normalization) in these processes gassing specifically for samples of polymeric materials according to examples 5-7 .1 was carried out by UV radiation with wavelengths of 253 nm, exposure time of 10 min, the power density of 10 mW/cm2.

As the radiation source used, for example, He-barrier-discharge excilamps with emitter and power supply in one housing.

Phase II - analysis of volatile organic compounds emitted from the tested samples of polymeric materials during aging in the heat chamber.

Samples of polymeric materials according to examples 5-7 .1 was investigated on the influence of selected nanostructured powders of bentonite in the division of volatile organic compounds. The results were analyzed to predict the sanitary-chemical properties of the designed polymer materials with the name of the modifying additives.

We used the method thermodesorption chromatography-mass-spectrometry-based accommodation in the heat chambers for the respective examples samples tested polymeric materials, the selection of the gas sample on the sorbent with subsequent thermal desorption and gas-liquid chromatographic analysis of volatile organic compounds.

Analysis of gas samples was performed by the method of gas chromatography / mass spectrometry according to the method of GOST R ISO 16000-6-2007 Air confined space. Part 6. Determination of volatile organic compounds in the air of the confined space and the test cell by active sampling onto sorbent the Heat THAT with subsequent thermal desorption and gas chromatography analysis using the FFM/PID".

According to the method of sampling gas medium from the heat chamber was carried out with the testing of samples at temperatures of 28°C and 50°C and the exposure of the samples in the heat chamber 10 days. The adopted temperature and the exposure time are optimal to simulate aging of polymeric materials in the natural climatic conditions for the formation of the gas environment in confined spaces is the second.

Sample gases from the heat chamber with the tested samples were collected on adsorption tubes "Gerstel" manufactured by Gerstel GmbH & Co KG (Germany) with a layer of sorbent Tenax TA. The sorbent has a particle size of from 0.18 to 0.25 mm and is a porous polymer based on 2,6 diference.

The sample gas was subjected to thermal desorption on thermodesorber Gerstel TDS at a temperature of 280°C With simultaneous cryogenic trapping of volatile components at 30°C and subsequent chromatographic separation on a capillary column HP-5MS with detection quadrupole mass analyzer ion electron impact (ionization energy 70 eV) in the range m/z 2-500.

The calibration of the mass spectrometer Agilent 5973 GC MSD company Agilent Technologies (USA) with integrated desorption and overlap Gerstel TDS3 and CIS4 conducted using solutions of the target reference compounds production "Sigma-Aldrich (USA, Switzerland). In the selection of 0.5 liters of sample gas from the chamber to the detection limit of the identifiable compounds is 5×10-12g/m3.

The results of gas chromatographic analysis of the emission of volatile organic compounds (VOCS) of the tested samples on the basis of silicone are shown in Fig.1 and Table 1.

Figure 1 shows the chromatogram (a) and (b) total ion current of volatile organic compounds released the meet the but of the tested samples on the basis of silicone in example 5.1 (a) and example 5 (b) at a temperature of 28°C.

The x-axis (time) hold time LOS.

Table 1 shows a quantitative comparison of the chromatographic peaks of volatile organic compounds - products of VOC emissions from the tested samples on the basis of silicone, respectively in examples 5.1 and 5.

The results of gas chromatographic analysis of the emission of volatile organic compounds (VOCS) of the tested samples on the basis of polyvinyl chloride shown in Fig.2, 3 and in Table 2.

Figure 2 shows a chromatogram (a) and (b) total ion current of volatile organic compounds emitted respectively from the test samples on the basis of polyvinyl chloride according to example 6.1 (a) and example 6 (b) at a temperature of 28°C. the x-Axis (time) hold time LOS.

Figure 3 shows a chromatogram (a) and (b) total ion current of volatile organic compounds emitted respectively from the test samples on the basis of polyvinyl chloride according to example 6.1 (a) and example 6 (b) at a temperature of 50°C. the x-Axis (time) hold time LOS.

Table 2 shows the quantitative comparison of the chromatographic peaks of volatile organic compounds - products of VOC emissions from the tested samples on the basis of polyvinyl chloride, respectively, in examples 6.1 and 6.

The results of gas chromatographic analysis of the emission of volatile organic connected to the th (LOS) of the tested samples on the basis of polyurethane presented on Fig.4.

Figure 4 shows the chromatogram (a) and (b) total ion current of volatile organic compounds emitted respectively from the test samples based on polyurethane from example 7.1 (a) and example 7 (b) at a temperature of 28°C. the x-Axis (time) hold time LOS.

When comparing the obtained gas chromatograms of samples taken from the heat chamber with the test samples with selected additives on the basis of nanostructured powder of bentonite (example 1), nanostructured powder of bentonite intercalated by ions of cerium (CE3+) (example 4), and the mixture powder of bentonite intercalated by ions of copper (Cu2+) ions and cerium (CE3+), assess the impact of nanocomponents projected on sanitary-chemical properties of the designed polymer materials.

Comparative gas chromatographic analysis (when the temperature in the heat chamber 28°C and 50°C) VOC emissions from the tested samples on the basis of silicone (silicone polymer), polyvinyl chloride, polyurethane, modified additives selected on the basis of nanostructured powder of bentonite and Na-form (example 1), based on a nanostructured powder of bentonite CE-shape (intercalated by ions of cerium CE3+) (example 4) and a mixture of powders of bentonite CE-shape and Cu-forms (examples 3, 4) showed that the use is the use of additives in example 4 and examples 3, 4 leads to a decrease (by 1-2 orders of magnitude) the amount allocated to LOS, mainly Monomeric residues.

Modification of polyurethane foam additive (example 7, Fig.4) has led to reduced excretion of nitrogen-containing aromatic compounds, including Acrylonitrile, propylene oxide 6-8 times, except aromatic hydrocarbons (toluene, trimethylbenzene).

With increasing temperature the temperature of the polymer samples to 50°With the qualitative composition of volatile organic compounds has not changed.

Additionally carried out the analysis of samples of polyurethane foam (examples 7 and 7.1) on formaldehyde emissions using high-performance liquid chromatography chromatograph Agilent 1200 with a UV detector operating at a wavelength of 360 nm. Air samples from smoke houses were selected on the cartridges for sampling LpDNHP S10, Supelco, Inc. USA. Then the samples were loirevalley acetonitrile for chromatography and was administered the injection syringe in the separation column with BOND Eclipse XDB-C18 with subsequent determination by UV detector. Calibration of the chromatograph for subsequent quantification of formaldehyde was carried out using freshly prepared solutions DPG-derived formaldehyde (2,4-dinitrophenylhydrazine).

Modification of polyurethane foam additive on the basis of a mixture of nanostructured powders of bentonite With the forms and Cu-forms (example 7) resulted in reduction of formaldehyde emissions almost in 2 times and amounted to: sample from example 7.1 was 0.026 mg/m 3the sample from example 7-0,014 mg/m3.

Thus, the studies confirm the impact modifier selected mineral nanocomponents on sanitary-chemical properties volatile organic compounds from the tested polymeric materials and reliably assess the prediction of these properties for the design of polymeric materials.

Table 1
Sample silicone (example 5.1)Sample silicone (example 5)
At 28°CAt 50°CAt 28°CAt 50°C
Volatile organic compounds (VOCS)mg/m2mg/m2mg/m2mg/m2
Trimethylsilyloxy acid23,857,61,42,1
Trimethylsilanol16,9 48,92,2a 3.9
Trimethyloxonium8,119,60,41,7
Trichloroanisole6,835,50,33,4
Oxybisethanol10,432,61,72,9

Table 2
A sample of polyvinyl chloride (example 6.1)A sample of polyvinyl chloride (example 6)
At 28°CAt 50°CAt 28°CAt 50°C
Volatile organic compounds (VOCS)mg/m2mg/m2mg/m2mg/m2
Proportionalitybased1,914,20,30,4
Chlornitrofen-sulfones1,315,50,30,4
Isovalerianic acid1,17,80,20,9
Palmitic acid0,8a 4.90,20,8

1. The method of evaluating the effect of nanocomponents on sanitary-chemical properties of polymeric materials consisting in the gas chromatographic analysis of volatile organic compounds from the gas samples taken from the heat chamber when testing samples of polymeric materials, modified mineral additives, the polymer samples of materials before they are checked in the chambers activate the UV radiation in the wavelength range 248-365 nm for 3-30 min at a power density of radiation 1-15 mW/cm2analysis of volatile organic compounds is carried out at the comparison of gas chromatograms of samples of Ottobrunn the x of the heat chamber for testing of polymeric materials with modifying additives on the basis of nanostructured powder of bentonite and nanostructured powder of bentonite, intercalated by ions of metals such as magnesium (Mg2+), scandium (Sc3+), chromium (Cr3+), manganese (Mn2+), iron (Fe2+), cobalt (Co2+), Nickel (Ni2+), copper (Cu2+), zinc (Zn2+), tin (Sn2+), cerium (Ce3+or a mixture powder of bentonite intercalated by ions of these metals, and the results of the comparison of gas chromatograms of samples and assess the impact of nanocomponents projected on sanitary-chemical properties of the designed polymer materials.

2. The method according to claim 1, characterized in that to test the use of polymeric materials based on polyvinyl chloride, polyurethanes and silicones in the amount of 0.3 to 5 wt.% nanostructured additives.

3. The method according to claim 1, characterized in that the sampling of the gas medium from the heat chamber when testing samples of polymeric materials is carried out at temperatures of 25-28°C and 40-50°C and the process is conducted within 2-15 days with the subsequent processing of the obtained chromatograms for the respective temperatures.

4. The method according to claim 1, characterized in that as modifying nanocomponents use a mixture of powders of bentonite intercalated by ions of cerium and copper ions, Nickel, iron at their weight ratio, as (5-10):1.

5. The method according to claim 1, characterized in that for obtaining nanostructured bentonite (mo is morillonite), intercalated by ions of metals such as magnesium (Mg2+), scandium (Sc3+), chromium (Cr3+), manganese (Mn2+), iron (Fe2+), cobalt (Co2+), Nickel (Ni2+), copper (Cu2+), zinc (Zn2+), tin (Sn2+), cerium (Ce3+)use semi - bentonite, pre-enriched sodium ions in the processing of 3-10%aqueous solution of sodium chloride, followed by purification from the anions of chlorine, which is then intercalary 0.3 to 20%th aqueous solutions of inorganic salts of these metals, cleaned from salts of sodium, crushed and dried.

6. The method according to claim 5, characterized in that the intercalation of prefabricated bentonite enriched with cations of sodium, preferably using a 0.3 to 2.0%aqueous solution of nitric acid salt of cerium Ce(NO3)3·6H2O.

7. The method according to claim 5, characterized in that the enriched bentonite cations sodium and intercalation of the obtained semi-finished product is used the weight ratio of bentonite:water solution of 1-(10-40).

8. The method according to claim 1, characterized in that to test the use of polymeric materials with nanostructured mineral filler with a particle size of not more than 150-200 nm.



 

Same patents:

FIELD: textile, paper.

SUBSTANCE: at the first stage the organoleptic analysis of tested samples is carried out. At the second stage the microscopic analysis of the material structure is carried out. At the third stage the chemical analysis of the tested samples is carried out by means of their treatment with an organic dissolvent selected from the group: butyl ether of acetic acid, dimethylketone, dimethylformamide, tetrahydrofuran, furfural, cyclohexanol at the ratio of sample-dissolvent equal to 1:(10-15) at the boiling temperature of the selected dissolvent for 20-30 minutes. If a sample has dissolved fully, the conclusion is made that is pertains to leather-like materials, and if a sample has not dissolved, it is identified as leather.

EFFECT: accurate and reliable recognition of leather from leather-like materials.

2 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: method involves pre-activation of surfaces of an article and a film. The article then pressed to the surface of the film made from non-light-stabilised polyethylene and then exposed to UV radiation until a brittle layer forms.

EFFECT: formation of a coating on an article, which is adhesively bonded to the surface of the article.

FIELD: physics.

SUBSTANCE: method involves providing a specimen, irradiating the specimen with a predetermined spectrum of electromagnetic radiation, recording the interaction between the specimen and the electromagnetic radiation in a data packet and determining at least one characteristic parameter in the recorded data packet. Radiation intensity values assigned to different areas of the surface of the specimen, where said radiation interacts with said surface areas, are recorded in the data packet. The determined characteristic parameter describes air content in the specimen and/or resin content in the specimen. The assigned intensity values coinciding with a predetermined intensity range are added together to determine the air content and/or the resin content in the specimen. Analysis can also be performed to determine resin distribution and/or air distribution in the sample and homogeneity of distribution of assigned intensity values coinciding with the predetermined intensity range with respect to different areas of the surface.

EFFECT: possibility of analysing specific characteristic parameters.

6 cl, 8 dwg

FIELD: textile, paper.

SUBSTANCE: when boiling collagen, linear dimensions of leather tissue are measured before and after collagen boiling. The structure-to-structure distance is determined using difference of the sample thickness after boiling and the rated thickness of the sample before boiling, which is produced as a product of the sample thickness before boiling and a coefficient of layers number defined as a quotient from division of a lengthy sample length into the length of the sample after boiling. Invention makes it possible to realise the specified method objective.

EFFECT: method improvement.

4 ex, 3 tbl

FIELD: medicine.

SUBSTANCE: sorption of pharmacy drug derinate, representing sodium deoxyribonucleate in micropanel holes is carried out. After that analysed sample, which contains component C1q with unknown activity, is introduced into holes. Incubation is carried out and after washing and drying of panel into holes introduced are conjugate of enzyme with antibodies against component C1q and substrate of said enzyme. Activity of component C1q is calculated by amount of formed product of enzymatic reaction. Set contains flat-bottom micropanel with sorbed derinate, conjugate of enzyme with antibodies to human complement component C1q, substrate buffer and standard with known C1q activity.

EFFECT: method application makes it possible to increase reliability of determination C1q component with application as activator of available and stable preparation derinate.

2 cl, 1 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: method involves filling the surface of soot with a polymer and determining the polymer adsorption value of the soot, where the polymer used is rubber. Soot dispersion is mixed with a rubber solution. Sieve diametres of the soot aggregates are determined. The specific surface of the soot is determined and relative wear resistance of the rubber is calculated from the given relationship.

EFFECT: faster and high information content of analysis.

2 cl, 5 tbl, 1 dwg

FIELD: medicine, rescue facilities.

SUBSTANCE: method relates to evaluation of protective properties of materials of facial parts of gas masks with respect to β,β'-dichlorethylsulfide by application of its simulator - butyl-β-chlorethylsulfide. Method includes application on one side of material of gas mask facial part of simulator - butyl-β-chlorethylsulfide drops with further analytic determination of the moment of accumulation in sample of limiting amount of simulator. Butyl-β-chlorethylsulfide in tested sample is caught by sorption substrate Quantitative determination of simulator is carried out with application of photocolorimetric method of analysis Limit of sensitivity of detecting butyl-β-chlorethylsulfide constitutes 1·10-3 mg/ml with inaccuracy not exceeding 15%.

EFFECT: technical result lies in possibility to carry out evaluation of protective properties of not only rubberised fabric, but also materials of facial parts of gas masks (rubbers) of various thickness, with increase of evaluation method safety

2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of measuring a set of technological parametres of a chemical process taking place in a chemical reactor. The method of determining at least one technological parametre of a chemical process taking place in a reactor 2, involves passing a sample of the process medium of the chemical process into a lateral circuit (20, 22, 24, 26, 34, 40, 42, 36) and isolation of the said sample from the remaining process medium in the said reactor; circulation of the said sample in the said lateral circuit and its thermal processing therein to the required temperature; taking measurements of at least one technological parametre of the said sample, chosen from viscosity, pH, conductivity, turbidity, and/or taking spectrometre measurements with provision for spectrometric data at the required temperature; controlling the chemical process based on the determined at least one technological parametre. The method is realised in a system which has an output 18 and an input 28; lateral circuit (20, 22, 24, 26, 34, 40, 42, 36), connected to the reactor 2 through output 18 and input 28, which enable passage of the sample of process medium from the said reactor 2 to the said lateral circuit and back to the said reactor; a device 30 for circulating the said sample; valves V1, V2, V4, V5 for isolating the said sample in the said lateral circuit from the remaining process medium in the said reactor 2; a device for thermal processing 46, 50, 52, V7 the said sample in the said lateral circuit to the required temperature; and a device for measuring 38 at least one technological parametre, chosen from viscosity, pH, conductivity, turbidity; and/or apparatus for measuring spectrometric data at the required temperature in the said lateral circuit and apparatus for controlling the chemical process based on the measured technological parametres.

EFFECT: invention allows for taking a large number of measurements of different technological parametres, accurate measurement at temperatures different from temperature of the reactor, fast switching between measurements taken in inline and online modes, as well as prevention of clogging of equipment of the system.

18 cl, 4 dwg

FIELD: process engineering.

SUBSTANCE: proposed method relates to production of rubber-containing products, namely, to methods designed to control vulcanisation. Proposed method consists in correcting vulcanisation time depending upon that required for producing maximum modulus of rubber mix shear in vulcanising the specimens at flow metre and departure of rubber extension modulus in finished products from preset magnitudes. This allows processing disturbing effects on vulcanisation in compliance with tuber mix production and vulcanisation.

EFFECT: higher stability of mechanical characteristics of rubber-containing products.

5 dwg

FIELD: chemistry.

SUBSTANCE: invention can be used in qualitative and quantitative evaluation of degree of both structural and deformational heterogeneity of such elastomers as oriented polyethylene terephtalate (PETP) or high-pressure polyethylene (HPP), using device for sample heating. As researched polymer sample, preliminary oriented PETP or HPP plate or film is used. Sample is placed on polished substrate, and a sheet of foil made of heat-conducting material is placed on the top of sample surface. Sample is heated through the foil with flat heating element at temperature 1.5-2.5 times higher than upper limit of operating temperature Top., during 2-15 seconds and under pressure of 3-4 g/cm2. Then pressure is reduced to 0.3-0.4 g/cm2, keeping heating element on sample during 1-15 seconds. After that, heating element is removed and sample is air-cooled. Degree of heterogeneity is determined visually both on sample surface and in the volume. After shrinkage change of form of investigated material sample is studied, followed by investigation of tension of compression and stretching in detected sections of higher and delayed deformations respectively in the form of deflection of positive and negative signs, in samples of investigated PETP. Also structure-formation at over-molecular level of different sample sections is studied.

EFFECT: detecting structural heterogeneity at the level of over-molecular organisation, visualisation of heterogeneities, simplification and acceleration of detection and investigation method.

16 dwg

FIELD: chemistry.

SUBSTANCE: polymer composition contains a polycarbonate polymer (component A), coated hexaboride particles (component B) as well as metal nitride particles (component C). The hexaboride particles consist of particles of a hexaboride of at least one element selected from a group consisting of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr and Ca and a coating layer containing a metal oxide. The composition contains particles of a nitride of a metal selected from a group consisting of Ti, Zr, Hf, V, Nb and Ta. The composition is obtained by mixing in molten state coated particles of hexaboride, metal nitride and a polymer dispersant with a polycarbonate polymer.

EFFECT: invention provides the article with efficient heat-reflecting properties, excellent transparency and water-resistance.

13 cl, 1 dwg, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: polymer composition contains a polycarbonate polymer (component A), coated hexaboride particles (component B) as well as metal nitride particles (component C). The hexaboride particles consist of particles of a hexaboride of at least one element selected from a group consisting of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr and Ca and a coating layer containing a metal oxide. The composition contains particles of a nitride of a metal selected from a group consisting of Ti, Zr, Hf, V, Nb and Ta. The composition is obtained by mixing in molten state coated particles of hexaboride, metal nitride and a polymer dispersant with a polycarbonate polymer.

EFFECT: invention provides the article with efficient heat-reflecting properties, excellent transparency and water-resistance.

13 cl, 1 dwg, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention pertains to a particle comprising a composition containing a matrix and a peroxide or azo radical initiator, as well as rubber-coated products, tyres, tyre treads and belts containing particle-elastomer systems. The particle is selected from aramid, polyester, polyamide, cellulose fibre and glass fibre. The matrix is selected from an extruded polymer, wax or mixture thereof.

EFFECT: invention improved mechanical properties - modulus of elasticity, hardness and wear-resistance.

20 cl, 37 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: method of producing nanocomposites involves coating nanoparticles with mean particle size from 1 nm to 100 nm with dicarboxylic acid; mixing nanoparticles coated with dicarboxylic acid with a cross-linking agent to obtain a starting mixture; mixing the starting mixture with polyester to form a polyester-based nanocomposite.

EFFECT: low crystallisation temperature and high glass-transition temperature of the nanocomposite compared to polyester.

14 cl, 7 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the chemistry of foamed polyurethanes, particularly a polyurethane system for making elastic articles, preferably for medical purposes, for example, orthopaedic articles, technical parameters of which have improved sanitary properties which meet their operating requirements. The present invention can also be used to make polyurethane bandages. The polyurethane system for making articles with improved sanitary properties contains compositions based on a polyol compound A, an isocyanate compound B and a mineral agent C, which is dispersed in polyol compound A. The isocyanate compound B used is prepolymers of methylene diphenyl diisocyanates MDI. The mineral agent C used is a mixture of bentonite nanopowders which are intercalated with silver ions Ag+ and cerium ions Ce3+.

EFFECT: improved sanitary properties of the obtained elastic articles, with regard to both inhibiting growth of microorganisms and reducing gas release of volatile toxic organic compounds.

9 cl, 2 dwg, 5 ex

FIELD: physics.

SUBSTANCE: described is a polymeric UV absorbing composition, having E308/E524 ratio greater than 10 and attenuation coefficient E524 at 524 nm less than 2.0 l/g/cm. Said composition contains an organic resin, titanium dioxide particles and a dispersion medium. The titanium dioxide particles in the dispersion medium have average volumetric diameter less than 85 nm. The dispersion medium is preferably selected from a group consisting of glycerine ethers, glycerine esters, alkylamides, alkanolamines and mixtures thereof. The invention also discloses a method of obtaining said UV absorbing composition, involving preparation of (i) a mother composition with titanium dioxide particle concentration of 1-50% of the total weight of the mother batch, and mixing the mother composition with a substrate organic resin, or obtaining (ii) a dispersion of titanium dioxide particles in an organic dispersion medium containing at least 35% titanium dioxide particles per total weight of the dispersion, and directly adding the dispersion into the substrate organic resin. Concentration of the organic medium in the composition ranges from 20 to 95% of the total weight of the composition.

EFFECT: composition endows polymer materials with effective UV absorption and transparency, as well as nontoxicity and biodegradability.

16 cl, 6 ex

FIELD: chemistry.

SUBSTANCE: Suggested are the new polycarbonate compositions which contain sheet silicates which are modified with organic polymers through melting in the absence of solvents, and the method for their production.

EFFECT: increased thermal stability and reduced maximum decay rate in fire.

14 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention is related to the method of producing nanocomposite material and it can be used in packaging, wire (non-flammable insulation of electrical wires) and other industries. The method includes melt mixing of low density polyethylene and layered silicate. As layered silicate, natural montmorillonite is used being modified with quaternary ammonium salt. Before melt mixing, low density polyethylene is preliminarily shearly degraded at high temperature in a single screw dispergator with three temperature zones.

EFFECT: pre-treatment of the polymer helps to overcome incompatibility of the filler and material polymer base and, consequently, to significantly enhance the mechanical properties of the nanomaterial being produced.

1 dwg, 4 tbl

FIELD: chemistry.

SUBSTANCE: invention is related to the method of producing nanocomposite material and it can be used in packaging, wire (non-flammable insulation of electrical wires) and other industries. The method includes melt mixing of low density polyethylene and layered silicate. As layered silicate, natural montmorillonite is used being modified with quaternary ammonium salt. Before melt mixing, low density polyethylene is preliminarily shearly degraded at high temperature in a single screw dispergator with three temperature zones.

EFFECT: pre-treatment of the polymer helps to overcome incompatibility of the filler and material polymer base and, consequently, to significantly enhance the mechanical properties of the nanomaterial being produced.

1 dwg, 4 tbl

FIELD: chemistry.

SUBSTANCE: method of producing hybrid organic-inorganic material comprises the following steps: (a) peptisation of material of inorganic particles selected from oxides, sulphides, sulphates, phosphates, arsenides and arsenates of noble metals and mixtures thereof, in anhydrous sulphuric acid or hydrogen fluoride, to obtain a solution of material of inorganic particles; (b) fractionation of the solution obtained at step (a) to obtain a solution of inorganic particles having particle size ranging from 5 nm to 100 nm; (c) mixing the fractionated solution obtained at step (b) with an organic solvent; (d) reacting the mixture from step (c) with a solution of a reactive organic monomer with silane functional groups in an organic solvent.

EFFECT: method of obtaining hybrid organic-inorganic monomer material enables to obtain monomer materials which combine desired products of material of inorganic particles and an organic monomer, in addition to unique nanoparticle properties.

15 cl

Polymer composition // 2458086

FIELD: chemistry.

SUBSTANCE: composition contains the following (pts.wt): epoxy resin ED-20 - 20-30; epoxy resin DEG-1 21-28; polyether - 12-20; filler - 17-25; hardener - stabilised liquid mixture of aliphatic and aromatic amines - 15-20; curing accelerator - either resorcin or hydroquinone or pyrocatechol 3-5, plasticiser - either a polyether based on diethylene glycol, butyl alcohol and maleic anhydride, or a polyether based on adipic acid, diethylene glycol and butyl alcohol.

EFFECT: invention enables to obtain polymer compositions with low viscosity, longer life, high rate of cure and high strength and adhesion to different types of highly filled polymer compositions.

3 tbl, 8 ex

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