Polyurethane system for making elastic articles with improved sanitary properties

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.

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The invention relates to the chemistry of polyurethanes, in particular polyurethane system designed for the manufacture of elastic products, preferably medical devices such as orthopedic: anti-bedsore mattresses, seat cushions, anatomical pillows under his back, under the head insoles - arch supports, orthopedic corsets, knee pads, bandage products, shoes for different types of flatfoot and defects of the feet and other technical parameters which have improved hygienic properties that meet the requirements of their operation. This invention can be used to obtain a polyurethane foam wound dressings.

The process of obtaining a polyurethane foam product is traditionally based on the use of liquid polyurethane reactive systems, components which are mixed and poured into a mold at low pressure or molding carry out the reaction-injection method (RJM technology). Depending on the requirements of the final product requirements (density, strength, elasticity, heat resistance, etc.) select appropriate polyurethane reactive system. The backbone of the polyurethane systems use compositions containing:

polyol as one compound (component (A)), intended to structure and prerelease molecular weight polyurethanes, density vulcanizing grid, the transverse structure of chemical bonds, i.e. the complex properties of polyurethanes and their purpose;

isocyanate compound (component (B)), determine the speed retinoblastoma, strength indicators, light and radiation resistance, and hardness of polyurethanes.

As the isocyanate compounds used prepolymers, as based etilendiamindisuktsinatov (prepolymer - MDI), and colordistance (prepolymer - TDI).

As a polyol as one of the connections use of complex and polyethers.

For example, for the manufacture of products from flexible foams (EP 111121) proposed polyurethane system based diphenylmethanediisocyanate, polyol and polymethylenepolyphenylisocyanate (polymeric MDI).

In the patent EP 392788 elastic polyurethane products are produced by the interaction of polypropoline or prepolymers with reactive towards isocyanate composition containing a large amount of water.

In the technical solution of the EP 439792 proposed the use of polyisocyanate compounds based on MDI and TDI, in the presence of the polyurethane composition prepolymer - TDI in the number 21-95% to improve tensile strength.

In the technical solution of the EP 679671 it was proposed to use a mixture of polymeric MDI and TDI, containing 320% TDI, to obtain a polyurethane foam with a low density, having improved toughness, improved residual deformation under compression.

The above polyurethane system to obtain polyurethanes based on MDI interaction, one or more simple polyether polyols and water that is not effectively steam formation. This increases the density of the resulting polyurethane foam is deteriorating, such factors as sufficient resistance to loads.

To obtain products with improved properties proposed use in polyurethane systems polymer-polyols based on:

dispersions of polyacrylonitrile, polystyrene (SAN polymer polyols);

polyols with a dispersion of a polyurea (PHD polyols);

polyisocyanate polyols with polydopamine (PIPA - polyols) - dispersion of polyurethane and other copolymer-polyols.

In the technical solution of the EP 418039 describes a method of obtaining RE-polyol and method for producing flexible foams with improved properties such indicator as sufficient resistance to loads with the use of the PIPA-polyol. In this technical solution is proposed using PIPA particles with size ranging from 100-700 nm.

In the technical solution of the EP 555721 proposed polyurethane system for producing flexible polyurethane foam is in, where the amount of polyol used with a high content of oxypropylene relatively high, while the number of used MDI relatively low.

It follows from the above that a variety of source components for polyurethane systems, chemical reactions accompanying their synthesis, provides the ability to create a variety of materials with desired physico-chemical properties. In this regard, continuously developed new opportunities for the use of polyurethane systems to obtain products with improved properties of their technical characteristics.

For example, in the technical solution according to the patent RU No. 2040530 proposed polyurethane system to obtain products with improved properties based on compositions containing polyetherpolyols (component (A)), the polyisocyanate (component (B)) and the component (C)dispersed in the component (A).

In this technical solution as component (C) use particles penografit, which is dispersed in part of polyetherpolyols, and the remaining portion polyetherpolyols mixed with other agents, including activator, accelerator, etc. are used in the polyurethane system of particles penografit, as well as an additional agent, as the casein in powder form, provides the elastic prop is lauretana with improved properties in terms of non-products from this material.

In the technical solution of the EP 2007/057405, publ. 18.07. 2007 (RF application No. 2009105824, publ. 27.08.2010 g, claim US No. 2009/0326148, publ. As of 31.12.2009) features a polyurethane system containing compounds based polyol as one compounds And isocyanate compounds and mineral agent, which is dispersed in the polyol as one connection.

Polyol as one connection And contains dispersed therein an agent-based aluminosilicate mineral.

According to this invention in a polyol as one compound (A) dispersed and other agents (D), including metal catalysts, thixotropic agent in the form of silicon dioxide with a specific surface area of 150 m2/g or more.

Dispersed in the polyol as one compound (component (A)) agent-based aluminosilicate mineral has an average particle size of 100 μm with a pore size from 2 to 5 Å. Polyurethane composition contains 1, 2-2 wt.% agent C. Use in polyurethane compositions called aluminosilicate mineral (agent (C)) provides the adsorption of water in the formation of urethane links and in the presence of the polyurethane catalyst helps to regulate the rate of interaction isocyanate groups with the hydroxyl-containing oligomers and water.

In this technical solution as a component of the (A) use of polyester polyols, preferably, polyester polyols, or a mixture of polyether polyols, related to the high molecular weight elastic polyols and having a molecular weight in the range of from 1500 to 10000. As connections In use, preferably, the prepolymers - MDI or a mixture of polymer - MDI, with the number of isocyanate groups (NCO) from 15 to 40% of the total weight of prepolymer.

It is also known technical solution (see patent RU No. 2379060, publ. 10.09.2007 BC), according to which the polyurethane system comprises a composition based polyol as one compounds And isocyanate compounds and the agent, which is dispersed in the polyol as one connection A.

The technical solution is intended for use in surgery and traumatology for the closure of wounds of different etiology.

In the polyurethane system according to this invention as a polyol as one connection use high polyetherpolyols containing dispersed therein the activation of the additive, namely: catalyst retinoblastoma on the basis of a mixture of tertiary amines and ORGANOTIN compounds, the chain extension of the polyurethane blowing agent, pootkryvali and periotoneal. As the isocyanate compound In a mixture of prepolymers MDI.

However, as returned by this invention wound dressing ineffective antimicrobial effects on wound RA is personal etiology.

Technical solution (RF application No. 2009105824) the aggregate used in the polyurethane system components is the closest analog of the claimed invention.

This polyurethane system designed for the manufacture of products used in the automotive industry, in particular for the manufacture of seats, instrument panels, consoles, cabinets and parts of the inner or outer road facing.

However, the polyurethane system does not meet the technological requirements for production on the basis of products with improved sanitary and hygienic properties of the operation that apply to medical devices, including: anti-bedsore mattresses, seat cushions, anatomical pillows under his back, under the head insoles - arch supports, orthopedic corsets, knee pads, shoes for different types of flatfoot and defects stop, and when it receives a polyurethane foam wound dressings.

The present invention was to create a polyurethane system for the manufacture of products with improved hygienic properties during their operation, as by reducing contamination of products by microorganisms and by improving their chemical stability due to the reduction of outgassing of volatile toxic organic is connected to the th, occur during operation of the products, i.e. under the influence of temperature, light, mechanical stress, and other factors that lead to the destruction of polymeric materials.

To solve the problem proposed polyurethane system for the manufacture of products with improved hygienic properties, compositions containing based polyol as one compounds And isocyanate compounds and mineral agent, which is dispersed in the polyol as one connection And, at the same time as isocyanate compounds In use prepolymers of etilendiamindisuktsinatov MDI, and as a mineral agent, dispersed in a polyol as one connection And use a mixture of nanostructured powder of bentonite intercalated by ions of silver Ag+and ions of cerium CE3+when their ratio in the mixture, as 1: (5 -10) (parts), for the manufacture of products using polyurethane system, with the following content, wt.%:

polyol as one connection And -40,0-75,0
isocyanate compound In -25,0-60,0
a mixture of nanostructured powders of bentonite
from the General to whom icesta polyol as one of the compounds A - of 0.1-0.5.

According to the invention nanostructured powder of bentonite intercalated by ions of cerium (CE3+), is obtained by modification of 0.3-2.0% aqueous solution of nitric acid salt of cerium CE(NO3)3·6N2O prefabricated bentonite obtained after enrichment cations sodium (Na+) when processing 3-10% aqueous solution of sodium chloride, followed by purification of chlorine anions, and after intercalation bentonite cleaned from salts of sodium and then crushed bentonite.

According to the invention as a polyol as one connection And, preferably, is used as a compound with a hydroxyl number mg(KOH)/g - 66,0-77,0, water content 2, 0-4 wt.%.

According to the invention, the connection-based etilendiamindisuktsinatov MDI is the number of isocyanate groups of the NCO 23, 8 to 40.0% of the total weight compounds and, preferably, not more than 30% of the total weight of the connection.

According to the invention polyol as one compound and isocyanate compound In the formation of polyurethane systems for the manufacture of products have the relation (2-3):(1-3) (parts).

According to the invention as a polyol as one connection And, preferably, use a simple high polyetherpolyols derived from propylene oxide or ethylene oxide, with a molecular mass of 3000-10000,the water content of 2.0 to 4.0 wt.%.

According to the invention, high molecular weight polyetherpolyols based on propylene oxide or ethylene oxide optionally contains dispersed therein the activation of the additive, namely: catalyst retinoblastoma on the basis of a mixture of tertiary amines and ORGANOTIN compounds with a ratio of 1:1, the chain extension of the polyurethane blowing agent, pootkryvali and periotoneal, the next time their content, wt.%:

the expander2,0-4,0
catalyst retinoblastoma0,05-0,5
the chain extension0,2-1,5
pootkryvali0,2-1,5
periotoneal0,2-1,5

According to the invention as the isocyanate compound In a mixture of MDI prepolymers, one of which is obtained from a mixture of 4,4'-, 2,4'- and 2,2'-isomers of etilendiamindisuktsinatov with the introduction of low molecular weight polyol of propylene oxide with molm 240-250-unit, and the second prepolymer synthesized by heat treatment of this mixture of isomers of etilendiamindisuktsinatov.

According to the invention polyol as one connection And oxide p is cut or ethylene oxide and isocyanate compound In based on the above-mentioned mixture of the prepolymers in the formation of polyurethane systems have the relation (2-4):1 (parts).

When implementing the present invention inhibited the growth of microorganisms, reduces the emission of volatile toxic organic compounds in the operation of the products, which greatly improves consumer properties of elastomeric medical products based on polyurethane systems according to the invention.

This result explains:

the presence of the polyurethane system nanostructured powder of bentonite intercalated by ions of silver (Ag+), which has activity against many types of microorganisms (including aerobic, anaerobic bacteria) and prolongation of their antimicrobial and antifungal activities when contact of the product with the biological environment;

the presence of the polyurethane system nanostructured powder of bentonite intercalated by ions of cerium (CE3+), have an antimicrobial effect and improves the chemical stability of the obtained polyurethane foam product that is manifested in the reduction of outgassing of volatile toxic organic compounds in the operation of the products, i.e. the influence of factors such as temperature, light, mechanical stress, etc. these circumstances due to the high activity of cerium ions to inhibition of oxidative processes.

In the analysis of the prior art have not identified the technical solutions set of features, relevant to the claimed technical solution described above and provides the result.

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

The claimed technical solution can be industrially realized by using known manufacturing processes, equipment and materials intended for the manufacture of formulations of drugs for medical purposes.

The implementation of the invention

The invention is illustrated:

presents drawings, where figure 1 and figure 2 shows the total ion chromatogram current volatile organic compounds emitted from a polyurethane material, respectively in Examples 1 and 2;

used to implement components of the invention, examples of its implementation and the results of the tests.

To implement the invention using known pharmaceutical and medicine of the active substance and the polymer components intended for manufacturing of various structures and tools.

When implementing the present invention for producing polyurethane elastic products using polyurethane system containing polyol as one compound (component (A)and isocyanate compound (component (C), the choice of which is determined taking into account the technological process for the manufacture of elastomeric products and their purpose.

1. To obtain elastomeric products by molding method using RIM technology (reaction-injection method)is preferably used to obtain orthopedic products, such as anti-bedsore mattresses, seat cushions, anatomical pillows under his back, under his head, using the following components.

1.1. Polyol as one compound (component a) to the drug trade Voralux™ NC 490, with a hydroxyl number, mg(KOH)/g - 66,0-77,0 and water content of 2.16-2.54 per cent.

1.2. Isocyanate compound (component b) trade drug Specflex™ NE 371 related to the prepolymers etilendiamindisuktsinatov MDI, the number of isocyanate groups (NCO) in which from 28.8 to 30.8% of the total weight of prepolymer.

Named in claim 1. 1 and 1.2, the drugs most optimal to obtain elastomeric products by molding method using RIM technology (reaction-injection method)is preferably used to obtain orthopedic products.

Specified in the invention, the quantitative content in the polyurethane polyol as one system connection (component a) and isocyanate compound (component C) given their ratio is optimal. When reducing quantitative content the data components in the system and changing the weight ratio qualitatively deteriorating process retinoblastoma when molding or significantly change the technical characteristics of the products obtained on their density. This parameter is crucial in obtaining products orthopedic purposes above specified type and is preferably in the range from 80 to 100 kg/m3.

2. To obtain elastomeric products in the form of wound dressings according to the technique described in patent No. 2379060 at which the formation of bandages carried out directly on the wound surface after mixing components (a) and (b) polyurethane system to get it to use the following components.

2.1 polyol as one compound (component a) is a simple high polyetherpolyols derived from propylene oxide or ethylene oxide, with a molecular mass of 3000-10000 and a water content of 2.0 to 4.0 wt.%. This product has a trade name LAPROL 3003, 3603, 5003, 6003, the analogues of these products are trade names "Caracol" and "Desmophen".

2.1.1 Activation additives, namely, the catalyst retinoblastoma, the chain extension of the polyurethane, pootkryvali, periotoneal and the expander. As the foaming agent used low-boiling organic liquid such as N-pentan, isopentene, methylcyclopentene, etc. as a catalyst retinoblastoma used a mixture of tertiary amines and ORGANOTIN compounds with a ratio of 1:1 (parts by weight), for example, triethylenediamine and debutylation Mixtures of tertiary amines and ORGANOTIN compounds have a synergistic effect. As chain extension using alkanolamine.

As penitences use polymethylsiloxane, such as Dabco 2525 produced by the air producs or Agosta 8715 manufactured by Goldschmidt. For adjustable pootkryvali use of high molecular weight polyols.

The above activation additives dispersed in the polyol as one compound (component a) in subsection 2.1. Specified according to the invention the quantitative content of the activation additives on the conditions for effective polyurethane system designed for the manufacture of products in the form of bandages for closing wounds of different etiology, which is confirmed by the known technical solution according to the patent No. 2379060.

2.2. Isocyanate compound (component b) is a mixture of prepolymers, one of which is obtained from a mixture of 4,4'-, 2,4'- and 2,2'-isomers of etilendiamindisuktsinatov (diphenylmethanediisocyanate) with the introduction of low molecular weight polyol of propylene oxide with molm 240-250-unit, and the second prepolymer synthesized by heat treatment of this mixture of isomers diphenylmethanediisocyanate. Specified isocyanate compound (component b) has a trade name of Suprasec 2456 (firm huntsman) - see patent No. 2379060.

Selected for the implementation of the present invention, this isocyanate compound (component b), the quantitative content of the W in the polyurethane system, specified in the present invention the weight ratio between used it polyol as one and isocyanate components is optimal and meets the conditions of the manufacture of wound dressings with a given density resulting bandages from 44 kg/m3up to 100 kg/m3that is confirmed by the known technical solution according to the patent No. 2379060.

3. To implement the present invention for creating a polyurethane system designed for the manufacture of elastomeric products above their medical purpose, and regardless of their receipt of technological methods, in the polyurethane system is used dispersed in a polyol as one component (A) mineral agent (C) based on nanostructured powders of bentonite.

3.1. Nanostructured powder of bentonite intercalated by ions of silver (Ag+).

This antimicrobial agent obtained by known techniques described in patent RU No. 2330673.

To produce antimicrobial agent use natural mineral montmorillonite (bentonite, Na-form), which is treated with 3-10% aqueous solution of sodium chloride, followed by washing and filtration of the obtained semi-finished product to remove chlorine. Prefabricated bentonite then modify 10-20% solution of silver nitrate, to produce an extract of modified bentonite in asanam saline. The product obtained after the intercalation cleaned from salts of sodium, crushed to obtain powder of bentonite. The particle size of the powder of bentonite, preferably not more than 150 nm. Processing of mineral named salt solutions produced at a ratio of parts: bentonite: solution 1:(10-40). Depending on the amount of activating, modifying agents powder of bentonite intercalated by ions of silver, contains from 2 to 8 wt.% silver.

The specified amount of the above metal bentonite powders optimally. The increase in metal content leads to an increase in expenses for obtaining antimicrobial agent, and at lower reduced antimicrobial activity.

Specified in the present invention, the quantitative content of nanostructured powder of bentonite intercalated by ions of silver, optimally. When reducing the content of this antimicrobial agent in the composition of the polyol as one of the component (A) worse antimicrobial properties of the polyurethane system designed for receiving elastomeric products. The increase in the quantity of the contents of this antimicrobial agent increases the cost of manufacturing.

3.2. Nanostructured powder of bentonite intercalated by ions of cerium (CE3+).

This product is obtained by modification of 0.3-2.0% aqueous solution asotec is a layer of salt of cerium Ce(NO 3)3·6N2O prefabricated bentonite obtained after enrichment cations Na+when processing 3-10% aqueous solution of sodium chloride, followed by purification of chlorine anions. After intercalation bentonite cleaned from salts of sodium and then crushed bentonite, preferably to a particle size of not more than 150 nm. When choosing salt Ce(NO3)3·6N2O came from the fact that the cerium (metal of variable valence) interacts with oxygen to produce cerium dioxide (CEO2), which is an antioxidant, which is characterized by inactivating and inhibitory effects on the formation of peroxide, hydroperoxide radicals generated by oxidative processes. This metal refers to a biologically compatible material and is used in medicine, such as prosthetics, dentistry.

When implementing the present invention in the process of intercalation of prefabricated bentonite obtained after enrichment cations Na+used a 0.5% aqueous solution of cerium nitrate Ce(NO3)3·6N2O.

Received after intercalation, cleaning and grinding powder of bentonite contains cerium in an amount of not more than 0.5 wt.%.

Specified in the present invention, the quantitative content of nanostructured powder of bentonite, and Tertuliano ions of cerium (CE 3+), is optimal in terms of blocking free radicals, peroxides formed by the oxidation processes in the exploited products.

When reducing the content of this component reduces the overall activity of the interaction of cerium ions free radicals, and peroxides. Increasing the concentration of this component in the polyol as one component increases the expense of manufacturing.

At the stage of obtaining semi-bentonite enriched with cations of sodium, using a 5% aqueous solution of sodium chloride, and at the stage of nanostructuring of bentonite intercalated by ions of silver (Ag+or ions of cerium (CE3+), used ultrasonic disperser Sonopuls HD 2070, the firm Bandelin, power - 35-75 watts/cm2the frequency of 20-50 kHz.

To assess the particle size of the bentonite used the microscopy method.

Were obtained polyurethane systems according to the following examples.

Example 1

1.1. Manufacturer polyol as one of the component (A) polyurethane system for receiving elastomeric products by molding method using RIM technology (reaction-injection method). This method was used for the manufacture of polyurethane foam orthopedic pillows under his head. Just was made 163 epodoc. For the manufacture of cushions used were the special of the mold with the appropriate profile.

In the liquid polyol as one component (a) to the drug trade Voralux™ 490 NC, was introduced (by stirring for 2 hours at circulation under pressure) a mixture of nanostructured powder of bentonite intercalated by ions of silver (Ag+) ions and cerium (CE3+), while their ratio in the mixture of 1:8. Were used: 200 liters polyol and 0,192 kg mentioned mixture of nanostructured powders of bentonite.

200 l (~185 kg) polyol as one of the component (A) used the isocyanate component (B) trade drug Specflex™ NE 371 in the number 72,0 kg Ratio of polyol as one component And isocyanate component (C) was 2.6:1,01 (parts).

The obtained polyurethane system in the amount 1,085 kg of component (a) and (0, 421 kg of component (B) used to obtain profiled polyurethane cushion having the following approximate parameters: width - 34 cm, length 50 cm, profile thickness (min) - 7.0 cm, thickness profile (max) - 12,0 see the Approximate volume pillows: 0,016-0,017 m3.

A specialized form of two nozzles under pressure filed polyol as one component (a) and isocyanate component (B). After the start of aeration (start - 30 sec) uniform was covered with the lid. In General, the reaction retinoblastoma lasted 10 minutes Formed the pillow was removed from the mold and dried at room temperature. As a result of this breadboard the process, specified number used in the polyurethane system components were obtained elastic products (orthopedic pillows under your head) density of 87 kg/m3up to 90 kg /m3that meets the technological requirements for this type of products. Lots of pillows - 1,4-1,5 kg

Example 2 - control

This example was carried out in accordance with example 1, but in the absence of a polyurethane system dispersed in a polyol as one component (A) of the mineral component (C) based on a mixture of nanostructured powders of bentonite.

During the realization of this example were obtained elastic products (orthopedic pillows under your head) density of 80 kg/m3up to 83 kg/m3.

Example 3

Polyol as one component (A) (trade name LAPROL 3003) is prepared by thoroughly mixing: 100 parts by weight of the polyol and the following additives, parts by weight:

the expander2,0
catalyst retinoblastoma0,5
water3,0
the chain extension0,2
periotoneal0,5
pootkryvali 0,5

In polyol as one component (A)containing a named activation of the additive, in addition enter the mineral component (C) based on a mixture of nanostructured powder of bentonite intercalated by ions of silver (Ag+or ions of cerium (CE3+), while their ratio in the mixture of 1:8, and in the quantitative content of polyol as one component (A) is 0.1 parts by weight of

As the isocyanate component (C) used Suprasec 2456 company huntsman containing of 29.5 wt.% NCO-groups.

In the manufacture of polyurethane systems on 100 parts by weight of polyol as one of the component (A) is added to 33 parts by weight of isocyanate component (B).

Was carried out by mixing polyol as one of the component (A) with the isocyanate (B) in polyethylene containers 350-400 ml at room temperature (20°C). After 50-60 seconds after mixing the composition was applied to a model of the wound. After 3-5 minutes after application, the composition is transformed into a porous sponge, which is firmly held on the surface of the wound. The formation of polyurethane "sponge" (polyurethane headbands) is characterized by the following indicators:

start - 25 sec,

lift - 140 sec,

the density of the obtained polyurethane weight (product) - 63 kg/m3.

Example 4 control

This example was carried out in accordance with Example 3, but in the absence of polyol as one to which the component (A) dispersed mineral component (C) based on a mixture of nanostructured powders of bentonite.

During the realization of this example were obtained polyurethane product density of 60 kg/m3.

Example 5 control

This example was carried out in accordance with Example 3, but in the presence of polyol as one component (A) dispersed mineral component (C) based on nanostructured powder of bentonite intercalated by ions of cerium (CE3+) in an amount of 0.1 parts by weight of

During the realization of this example were obtained polyurethane product density of 63 kg/m3.

The efficiency of the used polyurethane systems to obtain products with improved sanitary and hygienic properties of Examples 3, 4 and 5 were evaluated for the presence of antiseptic properties obtained for these Examples of products.

Assessment antiseptic properties was examined by growing in a Petri dish colonies of microorganisms (S.aureus), then put in a Cup of samples of polyurethane foam products which are manufactured according to Examples 3, 4 and 5, kept them at room temperature for 5 to 7 days, after expiration of which the measured delay the growth of test organisms. Correlation was performed 4-5 experiments. The results showed:

the lack of growth of S.aureus colonies on samples of products (under the microscope)manufactured according to Example 3, on the 7th day;

the existence of growth of S.aureus colonies on the surfaces of the samples and the products (under the microscope), manufactured according to Example 4, on the 5th day;

the growth of S.aureus colonies on the surfaces of samples (under the microscope)manufactured according to Example 5, took place on the 5th day, but surface contamination by microorganisms amounted to 3% of the total surface contamination of the sample according to Example 4.

These studies confirm that the hygienic properties of the products obtained using polyurethane systems, the most effective in the presence of polyol as one component (A) a mixture of nanostructured powder of bentonite intercalated by ions of silver (Ag+) ions and cerium (CE3+).

The efficiency of the used polyurethane systems to obtain products with improved sanitary and hygienic properties of Examples 1 and 2 were evaluated for the presence of toxic outgassing of volatile organic compounds obtained from these Examples of products that characterizes the chemical stability of polyurethane systems used for the manufacture of elastomeric products for medical purposes.

The evaluation was carried out by the method thermodesorption gas chromatography / mass spectrometry (GOST R ISO 16000. "The air of closed rooms", part 6).

Health-chemical testing of polyurethane foam product manufactured using polyurethane systems according to Examples 1 and 2, is tableno:

when thermo-oxidative degradation of a polyurethane foam material the selection of highly toxic chemical compounds (volatile organic compounds, mainly Monomeric residues) when used in the polyurethane system according to Example 1 polyol as one of the component (A), the modified agent (C) based on a mixture of nanostructured powder of bentonite intercalated by ions of Ag+and CE3+on 1-2 order of magnitude less compared to the materials of the products are manufactured without the use of the specified agent (C), Example 2, which is confirmed by the Fig.1 and Fig.2, which shows the total ion chromatogram current volatile organic compounds emitted from polyurethane materials.

Thus, these studies generally confirm that when using polyurethane system according to the present invention for the manufacture of elastic products significantly improve their hygienic properties, both in terms of inhibiting the growth of microorganisms and reducing the outgassing of volatile toxic organic compounds in the operation of the products.

1. Polyurethane system for the manufacture of products with improved hygienic properties, compositions containing based polyol as one compounds And isocyanate compounds and mineral what about the agent, which is dispersed in the polyol as one connection And, at the same time as isocyanate compounds In use prepolymers of etilendiamindisuktsinatov MDI, and as a mineral agent, dispersed in a polyol as one connection And use a mixture of nanostructured powder of bentonite intercalated by ions of silver Ag+and ions of cerium CE3+when their ratio in the mixture, as 1:(5-10) parts, for manufacture of products using polyurethane system with the following content, wt.%:

polyol as one component (A)40,0-75,0
isocyanate component (B)25,0-60,0
a mixture of nanostructured powders of bentonite
from the total amount of polyol as one connection And0,1-0,5

2. Polyurethane system according to claim 1, characterized in that the nanostructured powder of bentonite intercalated by ions of cerium CE3+get in the modification of 0.3-2.0%aqueous solution of nitric acid salt of cerium CE(NO3)3·6N2O prefabricated bentonite obtained after enrichment cations of Na+when processing 3-10%in denim solution of sodium chloride, followed by purification of chlorine anions, and after intercalation bentonite cleaned from salts of sodium and then crushed bentonite.

3. Polyurethane system according to claim 1, characterized in that as a polyol as one connection And preferably used as a compound with a hydroxyl number, mg(KOH)/g - 66,0-77,0, the water content of 2.0 to 4.0 wt.%.

4. Polyurethane system according to claim 1, characterized in that the connection on the basis of etilendiamindisuktsinatov MDI is the number of isocyanate groups of the NCO from 23,8 up to 40.0% of the total weight of the compound and preferably not more than 30% of the total weight of the connection.

5. Polyurethane system p and 4, characterized in that the polyol as one compound and isocyanate compound In the formation of polyurethane systems for the manufacture of products have the relation (2-3):(1-3) parts

6. Polyurethane system according to claim 1, characterized in that as a polyol as one connection And preferably use a simple high polyetherpolyols derived from propylene oxide or ethylene oxide, with a molecular mass of 3000-10000, the water content of 2.0 to 4.0 wt.%.

7. Polyurethane system according to claim 6, characterized in that the high molecular weight polyetherpolyols based on propylene oxide or ethylene oxide optionally contains dispersed therein the activation of the additive, namely: catalyst retinoblastoma on the basis of a mixture of tertiary am the new and ORGANOTIN compounds with a ratio of 1:1, the chain extension of the polyurethane blowing agent, pootkryvali and periotoneal the next time their content, wt.%:

the expander2,0-4,0
catalyst retinoblastoma0,05-0,5
the chain extension0,2-1,5
pootkryvali0,2-1,5
periotoneal0,2-1,5

8. Polyurethane system according to claim 1, characterized in that as the isocyanate compound In a mixture of MDI prepolymers, one of which is obtained from a mixture of 4,4'-, 2,4'- and 2,2'-isomers of etilendiamindisuktsinatov with the introduction of low molecular weight polyol of propylene oxide with molm 240-250 unit, and the second prepolymer synthesized by heat treatment of this mixture of isomers of etilendiamindisuktsinatov.

9. Polyurethane system according to claims 7 and 8, characterized in that the polyol as one connection And based on propylene oxide or ethylene oxide and isocyanate compound In based on the above-mentioned mixture of the prepolymers in the formation of polyurethane systems have the relation (2-4):1 parts



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to a sealing compound containing polythioether, where the sealing compound (a) essentially does not contain volatile organic compounds; (b) can be applied via pulverisation and (c) is fuel-resistant, where the polythioether contains polythioether-polyurethane and/or -polythiourethane with functional isocyanate groups and polythioether with functional amino/hydroxy groups. Described also is a multi-component sealing compound containing (a) a first component which contains polythioether-polyurethane and/or -polythiourethane with isocyanate functional groups, and (b) a second component containing polythioether with terminal amino/hydroxy groups. The invention also describes an aerospace vehicle having a hole which is at least partly sealed by said sealing compounds, and the hole itself, which is at least partly sealed by said sealing compounds.

EFFECT: obtaining sealing compounds which essentially do not contain volatile organic compounds, which are fuel-resistant, can be applied via pulverisation and harden fast in ambient conditions, and have good elasticity at low temperature.

20 cl, 4 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: polyurethane composition contains the following in pts. wt: 100 - polyether having molecular weight of 1000-2000; 150-350 2,3-toluene diisocyanate, 1-95 amine hardener, 10-35 plasticiser, 1-20 fluorooligomeric alcohol with molecular weight of 1000-5000 and 5-100 polyol with molecular weight of 1200-3500. Content of NCO- groups in the composition equals 4.09-6.5%.

EFFECT: elastomers obtained from said composition have high durability, good strength properties and high frost resistance, which enables use of articles made from the said composition under heavy loads, in conditions with large differential temperature and in aggressive media.

8 cl, 1 tbl

FIELD: chemistry of polymers, covers.

SUBSTANCE: invention relates to compositions of film-forming polyurethane compositions. Invention describes a composition for covers comprising the following components, mas. p. p.: polyoxypropylenetriol of molecular mass 3000-5000 Da, 80-95; 4,4'-diphenylmethanediisocyanate-base polyisocyanate, 100-200; ethyl acetate, 35-40; butyl acetate, 30-40; toluene,20-35; concentrated hydrochloric acid, 0.05-0.1, and ethylene glycol, 5-20. Invention provides enhancing adhesion to metal by 2-2.5-fold (up to 8.2 MPa) and enhancing cover hardness by 1.5-1.6-fold (up to 0.85 a. u. by method M-3). Invention can be used in preparing a protective cover for wood, concrete, glass, metal.

EFFECT: improved and valuable technical properties of composition.

1 tbl, 29 ex

FIELD: petrochemical processes.

SUBSTANCE: invention relates to a method for production of bitumen-polyurethane compositions designed mainly for manufacturing road, protective, insulation, and anticorrosive coatings. Modification of bitumen comprises interaction of bitumen bulk with prepolymer preliminarily prepared from components containing polyol and isocyanate groups, interaction being carried out at 60-140°C for 0.25-1 h, said components with polyol groups being polyethers and groups of polyuoxypropylene glycols and polyethylene(butylene) glycol adipates with functionality at least 2, whereas components with isocyanate groups are 2,4-tolylene diisocyanate, provided that molar ratio OH/NCO is 1:2 and amount of prepolymer corresponds to 1-10 wt % of the weight of bitumen.

EFFECT: achieved production of material with lowered brittleness temperature and water absorption, raised softening temperature, increased adhesion and elongation strength, and enhanced corrosion resistance.

2 tbl, 28 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to polyurethane foams and urethane rubbers, in particular to compositions for manufacturing cushioning polyurethane foams containing: at least one polyetherpolyol having average molecular mass between 10 and 20 thousands; aromatic polyisocyanate; tackiness-enhancing resin; surfactant; and optionally plasticizer in amount between 0.1 and 10 wt parts per 100 wt parts polyetherpolyol. Such polyurethane foams are non-soft cushioning polyurethane materials showing low elasticity and having a wide application area. Urethane rubbers obtained from at least two polyetherpolyols, tackiness-enhancing polymeric resin, aromatic polyisocyanate, and at least one catalyst also show low-elasticity properties and can be employed to manufacture of medicinal and orthopedic articles. A method for manufacturing such rubbers is proposed.

EFFECT: increased assortment of useful polyurethane foams.

4 cl, 8 tbl

FIELD: polymers.

SUBSTANCE: invention relates to polyurethane compositions designated for making abrasion-resistant articles possessing antifriction properties. The composition comprises polyoxytetramethylene glycol with molecular mass 1000 Da, 2,4-toluylenediisocyanate, liquid hardening agent as solution of 3,3'-dichloro-4,4'-diaminodiphenylmethane in polyoxytetramethylene glycol with molecular mass 1000 Da and low-molecular silicon rubber SKTN (7-10%). Invention provides preparing elastoplastics possessing the low friction coefficient (0.22-0.24) and high physical-mechanical indices.

EFFECT: improved and valuable properties of composition.

2 tbl, 5 ex

FIELD: special-destination polymer materials.

SUBSTANCE: invention relates to elastic vibration-absorbing polymer materials designed to provide antivibration protection to various structures in aircraft construction, motor-car construction, and other technical fields. Provided are a polymer composition containing polyurethane polymer based on aromatic diisocyanate, 1,4-butanediol, and polyalkylene-ether-glycol; carbon filler; antioxidant; melamine phosphate; and also laminated elastic vibration-absorbing material composed of outside and intermediate layer, at least one of which is made on the base of polyurethane. One of above-mentioned outside layers is made from indicated polyurethane-based polymer composition, intermediate layer is made from polyvinylacetate film, and the other outside layer from foil-clad glass grid, ratio of corresponding thicknesses being (2÷4):(2÷4):1. Alternatively, laminated vibration-absorbing material may contain polyvinylacetate film and foil-clad glass grid layer in alternate disposition, wherein ratio of thickness of outside layer made from polymer composition to total thickness of alternate layers is 1:(1.5÷3). Polymer composition and elastic laminated vibration-absorbing material based thereon provide effective vibration absorption within temperature range between -60°C and +60°C (tgδ≥0.1).

EFFECT: reduced vibration and noise in vehicles and improved their acoustic comfort.

2 cl, 7 tbl

FIELD: polymer materials.

SUBSTANCE: invention relates to compositions of molded polyurethane elastomers showing high physico-mechanical characteristics and providing high cyclic stability of products at alternate loadings within a wide operation temperature range. Invention may be used in rubber industry to manufacture cast tires and rolls for monorail vehicles. Composition according to invention contains polyoxytetramethylene glycol, mixture of 2,4-tolylenediisocyanate and 1,6-hexamethylenediisocyanate at molar ratio (0.8-0.9):0.1, and 3,3'-dichloro-4,4'-diaminodiphenylmethane in the form of solution in polyoxytetramethylene glycol at molar ratio (0.67-0.7):(0.29-0.30) as liquid hardener.

EFFECT: enabled use of polyurethane composition for molded elastomers.

2 cl, 2 tbl, 11 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to matrix resin composition for carbon fiber-reinforced plastic capable of acquiring desired shape. Composition contains bifunctional or trifunctional liquid diisocyanate, bifunctional polyol, and bifunctional chain elongator containing group with active hydrogen atom at molar ratio of functional groups of diisocyanate, polyol, and elongator (5.0-1.0):1.0:(4.0-0.2), respectively. Method of preparing carbon fiber-reinforced plastic is also claimed. Invention related to shape-memory composite materials and can be used in space engineering.

EFFECT: enlarged assortment of shape-memory plastics.

4 cl, 3 tbl, 3 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to polyurethane elastomers suited to manufacture polyurethane articles. Composition according to invention contains (i) 70.6-74.8% polyfurite urethane prepolymer prepared by reaction between 2.1 mile 2,4-tolylenediisocyanate and 1.0 mole poly(oxytetramethylene glycol) with molecular weight 1500 and (ii) liquid curing agent (to 100%), which is a mixture of 3,3'-dichloro-4,4'-diaminodiphenylmethane and poly(oxytetramethylene glycol) with molecular weight 1000 at their molar ratio 1:1. Thus obtained polyurethane elastomers show Shore hardness al a level of 93 relative units, breaking point (23°C) at a level of 38 MPa, elongation on fracture 712%, and abrasion resistance 27 mcm (according to Russian standard GOST 11529-86). Articles manufactured from these elastomers may find use for in-tube flaw inspection of oil and gas mains as well as oil storage tanks.

EFFECT: enlarged assortment of industrially useful elastomers.

4 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to silicon dioxides having a modified surface, a method of producing said dioxides and use thereof as filler material in silicone rubber compositions. Pyrogenic silicon dioxide has the following characteristics: BET surface area 25-400 m2/g, average size of primary particles 5-50 nm, pH 3-10, carbon content 0.1-10 wt %, potassium content in terms of potassium oxide 0.000001-40 wt %. According to the invention, silicon dioxide is obtained by modifying the surface of pyrogenic silicon dioxide doped with potassium oxide.

EFFECT: high transparency of the silicone rubber.

4 cl, 4 tbl, 1 ex

Conductive filler // 2199556
The invention relates to electrically conductive filler for conductive synthetic material for use as a shielding seal

The invention relates to polymeric compositions for non-asbestos friction materials used in mechanical engineering for the manufacture of brake linings disc and drum brakes

The invention relates to the field of production of asbestos-free friction materials for brake pads, working in heavily loaded friction units (motor vehicles and lifting-transport machines)

The invention relates to methods for vulcanization activators for the rubber industry

Polymer composition // 2067104
The invention relates to the field of polymeric materials and can be used in the manufacture of molded products

FIELD: process engineering.

SUBSTANCE: invention relates to foaming foam polystyrene granules containing pentane and isopentane and may be used in construction, production consumable patterns and moulding of articles and packages. Besides it may be used for both premary foaming and additional foaming of granules after primary foaming. Proposed method comprises proportioning initial granules, foaming them by steam treatment in foaming chamber, drying in drying chamber, cooling in cooling chamber, and storing foamed, dried and cooled granules in bins. Foaming is performed in microwave field in vertical waveguide chamber during steam treatment. Steam is generated in entire volume between loaded granules due to evaporation in microwave irradiation of water kept in microwave chamber in two sources, limited and recoverable sources. Limited source is made up of water film applied on granules in loading to envelop every granule. Recoverable source consists of steam generator working body saturated with water made up of porous deliquescent material arranged in waveguide chamber zone with maximum intensity of microwave radiation electric field.

EFFECT: no external steam source, lower residual moisture content, smaller overall dimensions.

4 cl, 1 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to production of packages. Proposed method consists in heating foamed polystyrene sheet to plastic deformation temperature and feeding it onto made die, moving said sheet toward female die and evacuating cavity between said dies. Sheet material outer layers have close pores while layer located between said layers has open intercommunicated pores. Evacuated cavity features vacuum between male die and sheet smaller than that between female die and sheet and equals the force corresponding the beginning of plastic deformation of sheet material layer between layers with close pores. Proposed method consists in heating foamed polystyrene sheet to plastic deformation temperature and feeding it onto made die, moving said sheet toward female die and evacuating cavity between said dies. Proposed device comprises appliance to implement above described method.

EFFECT: lower weight of thick-wall package.

3 cl, 3 dwg

FIELD: chemistry.

SUBSTANCE: the invention relates to fire-proofing agents for geofoams. The fire-proofing agent contains an aromatic group bromine and an olefin. The olefin is an inner olefin. The preferable means can be taken from the compounds of the formula (1) where R1 is C1-C6 and may contain a heteroatom or a olefin; R2 is C1-C6 and may contain a heteroatom or an olefin; and R3-R12 is H, C1-C6 (which may contain a heteroatom) or a halogen; and, furthermore, where the compound of the formula (1) is present in such conditions where the trans-isomer concentration is at least 50 percent. The fire-proofing agent can be chosen from the group comprising one of the folowing compounds:

According to the invention, the fire-proofing agent corresponds to the following formula “IV”: where R1 is a halogen, C1-C6 and may contain a heteroatom or an olefin; R2 is a halogen, C1-C6 and may contain a heteroatom or an olefin; R3-R12 is H, C1-C6 (which may contain a heteroatom) or a halogen, and R13-R14 are H or Br.

EFFECT: production of fire-proofing agents with necessary activity characteristics which are environmentally safe and retain good performance properties.

14 cl, 5 tbl, 5 ex

FIELD: generation of polymer particles.

SUBSTANCE: invention refers to the method and facility for generation of expanded or capable of expanding polymer particles. Expanded or capable of expanding polymer particles (10) are obtained from polymer melt (11) and recycle polymer melt (12). At least part of recycle polymer melt (12) is derived from recycle polymer particles containing expanding agent (5). Recycle polymer melt (12) is obtained at the stage of melting-down of recycle polymer particles containing expanding agent (5) in the side extruder (6) using the heating device (19). In this process the expanding agent is removed from the recycle polymer melt (12) in the degasser (13). After that the recycle polymer melt (12) and polymer melt (11) to which liquid expanding agent is added (2) are mixed into one polymer melt (24), dispersed and homogenized in the mixing device (7), and then is processed until expanded or capable of expanding polymer particles are obtained.

EFFECT: more efficient reutilization of polymer particles containing expanding agents, regardless of their size and form, for further preparation of polymer particles capable of expanding and having particle-size distribution conforming to desired technical specifications.

9 cl, 1 dwg

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