Field of the invention

The invention concerns hygiene, sanitary and medicine, in particular methods for estimation of influence of nano-components on sanitary-chemical properties of polymeric materials, for prognostication of their safety towards toxicity of volatile organic compounds.

State of the art

Polymeric materials concern a class of complex multi-component structures, preferably on the basis of thermoplastic and thermosetting materials, various fillers, softeners, dyes, curing accelerators, stabilizers and other additives. Unique physical and chemical, mechanical and operational properties of polymeric materials are conditional to their wide application in various branches and spheres of human life: in the industry and construction, in transport, in medicine, in household use and so on.

Industrially produced polymeric materials are subjected to complex tests and controls on the following aspects:

- sanitary-chemical properties for definition of migration of harmful (toxic) organic volatile compounds into the mediums coming into contact with the polymeric material;

- physic-mechanical properties for definition of their mechanical, thermal, electrical characteristics etc.;

- hygienic and microbiological properties for definition of influence of the given materials on growth of microflora;

- other tests depending on technological requirements, which are brought on the given materials for their application in systems of environment or in an alive organism.

A shortcoming of polymeric materials may be a process of release of toxic volatile organic compounds, migrating in the air environment. This process is intensified by influence of thermal, thermal-oxidative, light, ozone, radiating and other factors of environment that limits the opportunities of wide application, especially in closed premises.

In view of what above, polymeric materials are tested on sanitary-chemical properties for estimation of toxicity of volatile organic compounds. Toxicity classification is established by the World Health Organization (WHO). According to it phenol-, methanol-, toluene-, amino-containing substances and other harmful organic compounds are subjected to the sanitary-chemical control.

The methods of gas and liquid chromatography are preferably used for estimation of sanitary-chemical properties of polymeric materials. They allow effectively identifying and analyzing volatile organic compounds (VOC), which are released from polymeric materials.

At present the following methodical standards are used for analysis of VOC released from materials, including polymeric materials:

National Standard of the Russian Federation GOSTRISO 16000-6-2007 «Closed air space. Part 6. Determination of volatile organic compounds in the air of closed rooms and the test cell by active sampling on Tenax TA sorbent with subsequent thermal desorption and gas chromatographic analysis using MSD / FID» (28 March 2007).

MI 4.1.618-96 «Methodical instructions on gas chromatography-mass spectrometric determination of volatile organic substances in the air» (31 October 1996).

Methodical instructions MI 4.1.994-00 «Sanitary and chemical evaluation of polymeric materials intended for use in video display terminals, personal computing machines and cell systems based on them» (29 October 2000).

State standard «Building materials and products based on polymer finishing PVC. Method of sanitary-chemical evaluation* (No. 332, 1 January 1985).

Methodical instructions MI2.1.2.1829-04 «Sanitary-hygienic assessment of polymeric and polymer-containing building materials and designs that are intended for use in construction of residential, public and industrial buildings» (6 January 2004).

ISO 14624-3 A Space systems - Safety and compatibility of materials - Part 3: Determination of offgassed products from materials and assembled articles. The given international technique is applied to estimation of safety of gas evolutions from materials and equipment in closed spaces, premises for spacecrafts and systems.

According to the specified methodical standards the purpose of sanitary-chemical researches is qualitative identification and quantitative determination of chemical substances released from materials, including from polymeric materials, in the environment. Test of samples of polymeric materials for modeling laboratory conditions, are carried out in heat chambers (climatic chambers). The heat chamber is tight; it has means for maintenance and control of temperature and humidity. Sampling from heat chambers is made with the help of OTC products. Procedures of test preparation and methods of analysis are chosen depending on the kind of tested materials.

Means of measurement, auxiliary equipment, chemical reactants and laboratory glassware are chosen according to techniques of the analysis of harmful volatile chemical substances.

The following equipment is used for carrying out of gas and liquid chromatography of VOC: a heat chamber; extractor device, the pump for sampling, a flowmeter (for calibration of a gas stream), sorption tubes (for concentration of VOC on a solid polymeric sorbent), gas chromatographic capillary columns (for separation of analyzed substances), the device for thermal desorption of VOC from sorption tubes, GLC with the flame ionization detector (FID) and-or with the mass-spectrometric detector (MSD).

Measurement of concentration of VOC is based on their concentration from the gas test on a solid polymeric sorbent, with the subsequent thermal desorption, cryogenic focusing (catching) in a capillary, gas chromatographic separation on the glass capillary column with identification of volatile organic compounds using FID and/or MSD.

MSD can be used both for identification and for quantitative determination of VOC while signals of FID are used only for quantitative determination of VOC.

For authentic identification and quantitative determination of the chemical substances migrating from a polymeric material test of samples of materials, in simulated laboratory conditions, are carried out after the technological exposition in natural conditions, within the long period, i.e. 2-6 months. That is necessary for stabilization (normalization) of processes of gas evolution from polymeric materials. However the technological exposition decreases efficiency and limits opportunities of use of known methods of analysis (including GLC) for designing new polymeric materials, including materials containing nano-components (nano-particles) whose presence requires an estimation of safety of their application and influences prediction of sanitary-chemical properties of tested materials.

It is known that improvement of properties of polymeric materials, including ability to inhibit release of volatile organic compounds (VOC), is provided with use of modifying mineral additives on the basis of micro and nano-components (for example, take a look through the article «Monitoring system of quality of polymeric materials in modern building technologies* by T.P. Zubkova et al, Bulletin TGASU, N. 1, 2007, page 191- 196). This is the nearest art to the present invention.

The estimation of sanitary-chemical properties of polymeric materials in the given technical publication consists in the gas chromatographic analysis of volatile organic compounds from the gas tests selected from the heat chamber, when testing samples of polymeric materials modified by mineral additives.

Polymeric materials with mineral additives which are ecologically safe and minerals used in medicine and sanitation, for example talc, are used for testing.

It follows from the given technical publication that processes of inhibition of volatile organic compounds from tested polymeric materials are caused by sorption efficiency of the given mineral additive.

At the same time the resulted tests testify that sorption activity of the given additives decreases during long time operations. What worsens sanitary-chemical properties of a polymeric material.

According to standard techniques for identification and determination of release of volatile organic compounds, the tested samples are withstood under normal conditions for a long time for stabilization (normalization) of processes of gas evolution. As a result technological opportunities and prognostic efficiency of sanitary-chemical properties on gas evolution from new polymeric materials, including materials with nano-components, are limited. Reliability of estimation is reduced.

Summary of the invention

The technical result of the present invention consists in expansion of technological opportunities for estimation of sanitary-chemical properties on gas evolution and in increasing reliability of estimation of predicted sanitary-chemical properties, on gas evolution from new polymeric materials with nano-components.

A method of estimation of influence of nano-components on sanitary-chemical properties of the polymeric materials, consisting in the gas chromatographic analysis of volatile organic compounds from the gas tests, selected from the heat chamber at testing of samples of polymeric materials, modified with mineral additives, is described with the present application as a solution of the put technical problem. Thus, before testing in the heat chamber, the samples of polymeric materials are activated by ultraviolet radiation in a range of lengths of wave 248-365 nm within 3-30 min., at density of power of radiation of 1-15 mW/cm . The analysis of volatile organic compounds is carried out by comparison of the chromatograms of the gas tests, selected from the heat chamber, by testing samples of polymeric materials with modifying additives on the basis of a nano-structured powder of bentonite and a nano-structured powder of bentonite intercalated by ions of the following metals: magnesium (Mg ²⁺ ), scandium (Sc ³⁺ ), chrome(Cr ³⁺ ), manganese (Mn ²⁺ ), iron (Fe ²⁺ ), cobalt (Co ²⁺ ), nickel (Ni ²⁺ ), copper (Cu ²⁺ ), zinc (Zn ²⁺ ), tin (Sn ²⁺ ), cerium (Ce ³⁺ ) or a mix of powders of bentonite intercalated by ions of the named metals. Influence of nano- components on predicted sanitary-chemical properties of new polymeric materials is estimated according to the results of comparison of chromatograms of gas tests.

In the present invention polymeric materials on the basis of polyvinylchloride, polyurethanes and silicons, in the presence of nano-structured additives in an amount of 0,3-5% b.w. (by weight), are used for testing.

In the present invention, sampling of the gas environment from the heat chamber for testing polymeric materials, was carried out at temperatures of 25-28°C and 40-50°C and the process was carried out within 2-15 days with the subsequent received chromatograms for corresponding temperatures.

In the present invention a semi-finished product, i.e. bentonite, which is preliminary enriched with ions of sodium, by processing with a 3-10% water solution of sodium chloride and subsequent cleaning from chloride anions, intercalation with 0,3 - 20% water solution of inorganic salts of metals, cleaning from salts of sodium, drying and grinding, is used for obtaining nano-structured bentonite (montmorillonite) intercalated by ions of the following metals; magnesium (Mg ²⁺ ), scandium (Sc ³⁺ ), chrome(Cr ³⁺ ), manganese (Mn ²⁺ ), iron (Fe ²⁺ ), cobalt (Co ²⁺ ), nickel (Ni ²⁺ ), copper (Cu ²⁺ ), zinc (Zn ²⁺ ), tin (Sn ²⁺ ), cerium (Ce ³⁺ ).

In the present invention a mix of powders of bentonite, intercalated with ions of cerium and ions of copper, nickel, iron, in a weight ratio of (5-10): 1, is used as modifying nano-component.

In the present invention 0,3-2,0% water solution of nitrate salt of cerium

Ce(N0 ₃ ) ₃ -6H ₂ 0 is preferably used for intercalation of a semi-finished product of bentonite enriched with cations of sodium. In the present invention the weight rate bentonite : water solution of metal salt, of 1 : (10-40) is used for enriching bentonite with cations of sodium and for intercalation of the obtained semi-finished product.

In the present invention polymeric materials with nano- structured mineral additives, with a size of the particles of no more than 150-200 nm, are used.

At realization of the present invention, technological opportunities and reliability of results referred to influence of modifying mineral nano-components on predicted sanitary- chemical properties at release of volatile organic compounds, from new realized polymeric materials, are expanded. This result is explained by the following:

- use a method for simulating a technological exposition of polymeric materials to stabilization (normalization) of processes of gas evolution in them, for estimation of sanitary-chemical properties of the same;

- use of the method of activation of polymeric materials by ultraviolet radiation for imitation of their technological exposition. UV-radiation power promotes dissociation of weak bonds in polymers, with release of a part of volatile organic compounds that stabilizes (normalizes) the process of gas evolution and provides reliability of identification and quantitative determination of the chemical compounds released from polymeric materials, when tested in the heat chamber;

-the comparative analysis of chromatograms of the gas tests received at thermal processing of tested samples of polymeric materials with used nano-components, which confirm their influence on gas evolution and provide reliability of prognostication of sanitary-chemical properties on gas evolution of polymeric materials;

- use of samples of polymeric materials with chosen nano-components on the basis of bentonite (montmorillonite) intercalated by ions of the named metals, providing inhibition of oxidizing processes in polymers, owing to influence of ions of metal on peroxide or alkyl radicals. What allows increasing reliability of prognostication of sanitary- chemical properties of new produced polymeric materials;

- use of polymeric materials on the basis of polyvinylchloride, polyurethanes and silicons for an estimation of sanitary-chemical properties. They are widely used in various industries, including in medicine, and for them there is heavy demand for prediction of their sanitary-chemical properties. Analysis of the available art did not reveal technical publications with the set of characteristics corresponding to the declared invention and realizing the above described result.

The analysis of available art testifies about conformity of the present application to criteria of "novelty" and "degree of inventiveness".

The declared invention can be industrially realized with use of known technological processes, equipment and materials, including use for an estimation of influence of nano- components on sanitary-chemical properties of polymeric materials.

Brief description of the drawings

The essence of the present invention is explained by figures and tables.

Figures la and lb show the results of the gas chromatographic analysis of release of volatile organic compounds from tested samples of polymeric materials on the basis of silicone;

Figures 2a- 2b and 3a-3b show the results of the gas chromatographic analysis of release of volatile organic compounds from tested samples of polymeric materials, on the basis of polyvinylchloride;

Figures 4a and 4b show the results of the gas chromatographic analysis of release of volatile organic compounds from tested samples of polymeric materials, on the basis of polyurethane.

Detailed description of the invention

The following materials were used for realization of the process.

Polymeric materials as follows:

- silicons RTV 4408«A» and RTV 4408«B», manufacturer Bluestar Silicones, France; the given production is intended for products of medical purpose, in particular for exo-and ortho-prosthesis and for products of household purpose;

- plastisol (polyvinylchloride + softeners) typeD-23M, Russia;

- polyurethane; polyol component - preparation Voralux™ HK 490 (Dow Chemical Company) and isocyanate component - preparation Specflex™ NE 371 (Dow Chemical Company) were used for its manufacturing by the method of formation which uses reactionary-injection.

The given materials are widely used in various industries and spheres of human life, including in medicine. Process of ageing and destruction of polymeric materials, intensified and/or influenced by various factors of environment, is accompanied by release of toxic compounds from them.

At the present stage of designing materials, improvement of their operational characteristics is achieved, including characteristics due to use of modifying nano- components (nano- structured additives). Their influence on a new material must be determined for correctly estimating its possibilities.

In the present invention, influence of nano-components on the basis of nano- structured bentonite in Na-form (montmorillonite) on new polymeric materials is estimated. Its choice is optimal for modification of polymeric materials.

The natural layered mineral bentonite (montmorillonite) concerns a class of alkaline bentonites (bentonite of Na-form) in which the content of montmorillonite is 75-85% by weight. The given mineral component is most effective for modification of polymeric materials, owing to its ecological safety, sorption activity and capacity of cation exchange (up to 150 mg.ev/lOOg).

The following compounds and products according to the examples are used for modification of the chosen polymeric materials (on the basis of the above mentioned materials - silicone, polyvinylchloride, polyurethanes):

Example 1.

A nano-structured powder of bentonite (montmorillonite) is dried and grinded (for example in a jet mill) up to a size of the nano-particles of powder of no more than 150-200 nm. The powder formed by grinding the given mineral, possess significant superficial energy and adsorption activity. The properties of the given mineral have determined expediency of its use for modification of new polymeric materials and for prognosis of their sanitary-chemical properties, in case of gas evolution.

Example 2.

Obtaining a semi-finished product of bentonite enriched with ions of sodium.

Bentonite in Na-form is enriched with cations of Na ⁺ by its processing with 3-10% water solution of sodium chloride and subsequent cleaning from chloride anions.

A 5% water solution of sodium chloride is preferably used. Bentonite is added to this solution, then is decanted (repeatedly) and is washed in deionized water with pH = 7 (for cleaning from chloride anions), is grinded with use of the supersonic dispersant Sonopuls HD-2070 (company Bandelin) and dried. The size of the particles of powder is no more than 150-200 nm.

500 g of bentonite according to Example 1 were used for obtaining a semi-finished product of bentonite enriched with ions of sodium.

Example 3.

Obtaining a nano-structured powder of bentonite intercalated by ions of metals - magnesium (Mg ²⁺ \ scandium (Sc ³⁺ \ chrome (Cr ³⁺ \ manganese (Mn ²⁺ ), iron (Fe ²⁺ ), cobalt (Co ²⁺ ), nickel (Ni ²⁺ ), copper (Cu ²⁺ ), zinc (Zn ²⁺ ), tin (Sn ²⁺ ).

A semi-finished product according to Example 2, modified (intercalated) by means of 0,3-20 % water solutions of inorganic salts of magnesium, scandium, chrome, manganese, iron, cobalt, nickel, copper, zinc or tin, is used for manufacturing the given powders of bentonite.

15% water solutions of salts of metals, for example copper sulfate (CuS0 ₄ ), iron sulfate (FeS0 ₄ ), zinc sulfate (ZnS0 ₄ ) or ZnCl ₂ are preferably used as inorganic salts for intercalation.

Example 4.

Obtaining a nano-structured powder of bentonite intercalated by ions of cerium (Ce ³⁺ ) (bentonite in Ce-form).

The given product is obtained by modifying the semi-finished product according to Example 2 with 0,3-2,0 % water solution of nitrate salt of cerium Ce(N0 ₃ )3-6H ₂ 0.

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

For the choice of the given product it was taken into consideration that cerium (metal of variable valency) is the most effective metal on electrochemical activity. Cerium interacts with oxygen with formation of cerium dioxide (Ce02).

Ions, nano-particles of cerium and cerium dioxide reveal antioxidant properties and show inactivating and blocking influence on oxygen-containing compounds, peroxide and hydroperoxide radicals generated due to oxidizing processes in technical materials (including polymeric materials) and also in biological materials and tissues.

In particular, a 0,5 % water solution of cerium nitrate Ce(N0 ₃ )3-6H ₂ 0 is used for obtaining bentonite intercalated by ions of cerium. A powder of bentonite obtained after intercalation, cleaning and grinding, contains cerium in amount of no more than 0,5% b.w.. The size of the particles of the powder of bentonite in cerium form, is no more than 200 nm.

50 g of Ce(N0 ₃ ) ₃ -6H ₂ 0 were used for realization of the given example.

Weight ratio bentonite : water solution as 1 : (10-40) and preferably as 1 : 20 is used for realization of Examples 2-4.

The contents of metals in nano-structured powders of bentonite (Examples 3, 4), intercalated by ions of the named metals, is determined by the method of the plasma analysis (ICP-MS).

Amount of cerium in the product according to Example 4 was 1,5% b.w..

Amount of copper in a nano-structured powder of bentonite, intercalated in particular with ions of copper, was 2% b.w..

The method of electronic microscopy was used for estimation of the size of the particles of bentonite powders, according to Examples 1, 2, 3, 4. The size of particles of tested nano-structured powders is no more than 150-200 nm.

It is supposed that cerium possesses synergistic activity with other metals

(including copper, nickel, iron) in this application.

It is possible to use a mix of nano-structured powders of bentonite intercalated by ions of cerium and other metals (for example, copper, nickel, iron).

It is possible to use mixes of nano-structured powders of bentonite intercalated by ions of cerium and other metals (for example, copper, nickel, iron) in a weight ratio of (5- 10) : 1 for the purposes of the present invention. That is optimal on predictable sanitary- chemical properties of new produced polymeric materials.

The metals used in nano-structured powders of bentonite under the present invention possess biological compatibility and electrochemical activity (look through a line of electrochemical activity of metals).

Nano-structured powders of bentonite in amount of 0,3-5,0% b.w. are used for realization of the present invention, to produce new modified projected compositions of polymeric materials.

The specified charge of powders of bentonite for modification of polymeric materials is optimum. Decrease in the quantitative contents of intercalated bentonite added in the produced compositions of polymeric materials, does not improve their sanitary- chemical properties on gas evolution. The increase in the quantitative contents of bentonite in polymeric materials raises costs and worsens process of dispersion of bentonite powders in polymeric matrixes of the new materials.

Polymeric materials according to the following examples were used for estimation of the influence of nano-components on sanitary-chemical properties.

Example 5.

Liquid thermosets on the basis of silicons, for example type RTV 4408«A» and RTV 4408«B», at the ratio 1: 1, in amount of 100,0 +0,1 g.

A nano-structured powder of bentonite according to Example 4, in amount of 1,5% b.w., was dispersed in the obtained composition with the help of an ultrasonic dispersant.

Example 5.1.

The same liquid thermosets according to Example 5 and a nano-structured powder of bentonite according to Example 1, herein dispersed in the amount of 3% b.w., were used as the components.

Vessels with the prepared mixes according to Examples 5 and 5.1 were heated under vacuum up to full removal of gaseous products. The obtained polymeric masses were vulcanized (cured). After cooling polymeric materials have been cut in samples of the size of 4x3 cm; 6 samples (of 15 g weight) for each example were manufactured.

Example 6.

The following components were mixed up in a vessel: plastisol of polyvinylchloride D-17I, in amount of 100,0+0, lg, and a powder of bentonite intercalated by ions of cerium (Example 4), in amount of 1,5% b.w. in respect to the mass of plastisol. The obtained composition was mixed up and dispersed with the help of an ultrasonic dispersant. The vessel with the prepared composition was put under vacuum up to full removal of gaseous products. The polymeric mass was vulcanized (solidified) and cooled after treatment under vacuum.

The samples with the size 4x3 were manufactured from obtained polymeric material on the basis of polyvinyl chloride; 6 samples were manufactured (weight 15 g).

Example 6.1

The same technological process of obtaining a polyvinylchloride, according to Example 6, was used, but a nano-structured powder of bentonite according to Example 1, in amount of 3% b.w. was used as a component dispersed into the plastisol of polyvinylchloride . Example 7.

A polyol component - product Voralux™HK 490 (Dow Chemical Company) and an isocyanate component - product Specflex™NE 371 (Dow Chemical Company), were used for manufacturing polyurethane by using the method of reaction-injection. A mix of nano- structured powders of bentonite intercalated by ions of copper (Cu ²⁺ ) and ions of cerium (Ce ³⁺ ), in amount of 3% b.w., was injected in a liquid polyol component; the weight ratio was 1 : 8; the weight rate of polyol component : isocyanate component was 2,6: 1,01; charge: 1,085 kg - polyol component and 0, 421 kg - isocyanate component.

Polyol and isocyanate components were injected in the specialized form under pressure; the form was closed after foaming. The generated product was dried. An elastic product was obtained with weight 1,4 kg; width 34 cm; length 50 cm, thickness of the piece (min) 7,0 cm. The samples of tested materials were manufactured with the size 3x4 cm in amount of 6 pieces.

Example 7.1

The same technological process of obtaining a polymeric material on the basis of polyurethane, according to Example 7, was used, but a nano- structured powder of bentonite according to Example 1, in amount of 3% b.w. was used, as an additive dispersed into the polyol component.

Samples of the polymeric materials on the basis of silicone, polyvinylchloride and polyurethane(Examples 5-7.1) were tested to determine the influence of the used mineral nano-components in predicting sanitary-chemical properties on gas evolution.

The process of testing samples of polymeric materials was carried out as follows: I step - Reproduction of conditions for stabilizing polymeric materials and measuring gas evolution in them.

For the purposes of the present invention and for imitation of technological exposition of samples according to Examples 5-7.1, they were activated with UV-radiation in a range of lengths of wave 248-365 nm with an exposition of 3-30 min., at density of power of radiation of 1-15 mW/cm under normal conditions.

The modalities of activation of polymeric materials, specified in the present invention are optimal for stabilization (normalization) of processes of release of volatile organic compounds from polymeric materials. That is necessary for the subsequent gas chromatographic analysis. UV-radiation in a range of lengths of wave of 248-365 nm corresponds to the absorption spectrum of the polymeric materials chosen for the test. At the chosen density of power of radiation there is an irradiation of superficial layers of the tested polymeric materials, in which the processes of release of low-molecular volatile organic compounds are initiated. For the purposes of the present invention, the mode of UV-radiation allows a simulation of exposition of polymeric materials for the subsequent estimation of their sanitary-hygienic properties with respect to gas evolution. Change of the mode of UV-radiation will lead to strengthening processes of destruction of polymeric materials and to change their physico- mechanical properties.

The mode of imitation of exposition of polymeric materials for stabilization (normalization) of processes of gas evolution from them, for the samples of polymeric materials according to Examples 5-7.1, was carried out at UV-radiation with length of wave 253 nm, time of exposition of 10 min., density of power of radiation of 10 mW/cm .

For example, X-excilamp, of the barrier category, with a radiator and a power supply was used in one case as the source of radiation.

II step - Analysis of volatile organic compounds released from tested samples of polymeric materials, at their exposition in the heat chamber.

Samples of polymeric materials according to Examples 5-7.1, were tested for influence of chosen nano-structured powders of bentonite on release of volatile organic compounds. The obtained results were analyzed for prognostication of sanitary-chemical properties of new polymeric materials with the named modifying additives.

The method of thermal desorption in gas chromatography-mass spectrometry, based on placement of samples of tested polymeric materials in heat chambers of corresponding examples, on selection of gas samples on a sorbent with subsequent thermal desorption, and on GLC analysis of volatile organic compounds, was the method used for the research.

The analysis of samples of the evolved gas was carried out by the method of gas chromatography/mass spectrometry according to the technique GOSTRISO 16000-6-2007 «Closed air space. Part 6. Determination of volatile organic compounds in the air of closed rooms and the test cell by active sampling on Tenax TA sorbent with subsequent thermal desorption and gas chromatographic analysis using MSD / FID».

Sampling of the gas environment from the heat chamber was carried out testing samples at temperatures of 28°C and 50°C and at an exposition of the samples in the heat chamber within 10 days according to the accepted modality. The accepted temperatures and time of exposition are optimum for imitation of ageing of polymeric materials in the natural climatic conditions, providing formation of the gas environment in closed rooms.

Tests of gases from the heat chamber were performed on samples selected with adsorption tubes "Gerstel", manufactured by the company «Gerstel GmbH &Co KG» (Germany) with a layer of sorbent Tenax TA. The sorbent has particles of size from 0,18 up to 0,25 mm, consisting of a porous polymer on the basis of 2,6 diphenylene oxide.

Samples of gas were subjected to thermal desorption in the thermal desorber Gerstel TDS, at a temperature of 280°C, with simultaneous cryogenic catching of volatile components at -30°C and subsequent chromatographic separation in the capillary column HP-5MS, with detecting by a quadrupole mass-analyzer of ions of electronic impact (energy of ionization 70 eV) in a range m/z 2-500.

Calibration of the mass-spectrometer Agilent GC 5973 MSD, by the company «Agilent Technologies* (USA), with the integrated systems of desorption and letting Gerstel TDS3 and CIS4, was carried out with the use of solutions of target reference compounds, manufactured by "Sigma-Aldrich" (USA, Switzerland). The limit of detection of identified compounds was 5x10 - ^" 12 g/m 3 by selecting 0,5 litres of gas from the chamber.

The results of the gas chromatographic analysis of released volatile organic compounds (VOC) from tested samples on the basis of silicone, are submitted in Figures la and lb and in Table 1.

Table 1

Example of silicon Example of silicon

(example 5.1) (example 5)

At 28 C At 50 C At 28 C At 50 C

Volatile organic mg/m ² mg/m ² mg/m ² mg/m ² compounds (VOC)

Trimethylsilylaceticacid 23,8 57,6 1,4 2,1

Trimethylsilanol 16,9 48,9 2,2 3,9

Trimethylmethoxysilane 8,1 19,6 0,4 1,7

Dokoziltrichlorosilane 6,8 35,5 0,3 3,4

Oxabicyclohexanol 10,4 32,6 1,7 2,9 Chromatograms (a) and (b) of a full ionic current of volatile organic compounds, released from tested samples on the basis of silicone, according to Example 5.1 (a) and Example 5 (b), at a temperature of 28°C, are submitted in Figures la and lb.

X-axis (time) is time of keeping VOC.

Quantitative comparison of the basic chromatographic peaks of volatile organic compounds, i.e. products of release of VOC from tested samples on the basis of silicone according to Examples 5.1 and 5, results from Table 1.

The results of the gas chromatographic analysis on release of volatile organic compounds (VOC) from tested samples, on the basis of polyvinylchloride, are submitted in Figures 2a-2b and 3a-3b and in Table 2.

Chromatograms (a) and (b) of a full ionic current of the volatile organic compounds released from tested samples on the basis of polyvinylchloride, according to Example 6.1 (a) and to Example 6 (b), at a temperature of 28°C, are submitted in Figures 2a and 2b.

X-axis (time) is time of keeping VOC.

Chromatograms (a) and (b) of a full ionic current of volatile organic compounds, released from tested samples on the basis of polyvinylchloride according to Example 6.1 (a) and Example 6 (b), at a temperature of 50°C are submitted in Figures 3a and 3b.

X-axis (time) is time of keeping VOC.

Quantitative comparison of the basic chromatographic peaks of volatile organic compounds, i.e. products of release of VOC from tested samples on the basis of polyvinylchloride according to Examples 6.1 and 6, results from Table 2.

Table2

The results of the gas chromatographic analysis on release of volatile organic compounds (VOC) from tested samples on the basis of polyurethane are submitted in Figures 4a and 4b.

Chromatograms (a) and (b) of a full ionic current of the volatile organic compounds, released from tested samples on the basis of polyvinylchloride, according to Example 7.1 (a) and Example 7(b), at a temperature of 28°C, are submitted in Figures 4a and 4b.

X-axis (time) is time of keeping VOC.

Influence of nano-components on predicted sanitary- chemical properties of new polymeric materials, is estimated by comparison of received chromatograms of the gas tests selected from the heat chamber with tested samples with chosen additives on the basis of a nano-structured powder of bentonite (Example 1), a nano-structured powder of bentonite intercalated by ions of cerium (Ce ³⁺ ) (Example 4) and mixes of powders of bentonite intercalated by ions of copper (Cu ²⁺ ) and ions of cerium (Ce ³⁺ ).

The comparative gas chromatographic analysis (at temperatures in the heat chamber of 28°C and 50°C) of VOC released from tested samples on the basis of silicone (organosilicon polymer), polyvinylchloride and polyurethane modified by the chosen additives on the basis of a nano-structured powder of bentonite in Na-form (Example 1), on the basis of a nano-structured powder of bentonite in Ce-form (intercalated by ions of cerium Ce ³⁺ ) (Example 4) and a mix of powders of bentonite in Ce-form and Cu-form (Examples 3, 4), has shown that use of additives according to Example 4 and to Examples 3, 4 leads to decrease (of 1-2 order of magnitude) in amounts of released VOC and mainly of the mono measured residues.

Modification of polyurethane with the additive (Example 7, Figures 4a and 4b) has led to decrease in release of aromatic nitrogen compounds, including acrylonitrile and propylene oxides, of 6-8 times, except for aromatic hydrocarbons (toluene, trimethylbenzene) .

The qualitative composition of volatile organic substances practically has not changed at increase up to 50°C of temperature control of polymeric samples.

The analysis of samples of polyurethane (Examples 7 and 7.1) on release of formaldehyde by the method of highly effective liquid chromatography on the chromatograph Agilent 1200, with the UV-detector working at a wave length of 360 nm, was carried out in addition. Tests of air from the heat chamber were selected on cartridges for sampling LpDNHP S 10, Supelco, Inc., USA. Then tests were eluted with acetonitrile for chromatography and were injected with the injector syringe into a separation column with ZORBAX Eclipse XDB-C18, with subsequent determination on the UV-detector. Calibration of the chromatograph for the subsequent quantitative estimation of formaldehyde, was carried out with the help of just prepared solutions of DNPH-derivative of formaldehyde (2,4-dinitrophenylhydrazine).

Modification of polyurethane with the additive on the basis of a mix of nano- structured powders of bentonite in Ce-form and Cu-form (Example 7) has led to decrease in release of formaldehyde, practically in 2 times, and has given the sample according to

Example 7.1 - 0,026 mg/m 3 and the sample according to Example 7 - 0,014 mg/m 3.

Thus, the tests carried out confirm influence of chosen modifying mineral nano- components on sanitary-chemical properties at release of volatile organic compounds from tested polymeric materials, and authentically estimate prognostication of these properties for new produced polymeric materials.