Method of producing polymer material

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing polymer material, enriched with phosphorus, which is used as a fireproof additive. A method is described for producing fireproof polymer material in two stages by reacting initial reagents in a reactor. The first stage involves reacting anhydrous phosphorous pentoxide with a second reagent, chosen from a group consisting of (a) diol, which is 1,3-propanediol and 1,4-butanediol, and (b) a mixture of cyclic ether and alcohol, obtaining polymer precursor material. The second stage involves reacting polymer precursor material with cyclic ether, for example ethylene oxide, propylene oxide and/or glycidol, obtaining the final product. Described also is a fireproof composition, which contains polymer material in form of a salt, obtained by reacting phosphoric ester with an amine, chosen from melamine and polyethylenimine.

EFFECT: obtaining water-insoluble intumescent polymer material which promotes reduction of flammability.

47 cl, 3 dwg, 5 tbl, 13 ex

 

The technical field

The present invention relates to methods for polymeric materials and materials obtained in accordance with the specified methods. More specifically, but not exclusively, the invention relates to methods for preparing polymers enriched with phosphorus, and to a method of preparing esters of phosphoric acids, such as partial esters of phosphoric acids.

The level of technology

Swelling (intumescence) is a process in which a solid under the influence of heat is transformed into a relatively rigid foam foam material. This foam, which this extension has a much lower conductivity than the source material, is used as a flame retardant means. Swelling (intumescent) products put in their usual form on the surface of materials and structures, which need to be protected from fire.

Swelling coal consists of amorphous carbon or carbon and graphite, and condensed phosphoric acids. By itself, this coal is not flammable. The basic principle is that if the polymeric material may be modified so that it is subjected to thermal decomposition as well as the intumescent material, it thus becomes non-flammable.

The presence of structures vos is lamanauskas substances, such as wood, plastics, fiberglass reinforced plastics, increases the rating of the site or allow flames to spread along the surface of the material, resulting in a fire captures space located away from the fire.

There are two ways to reduce fire danger. First, the materials can be added flame retardants. Most flame-retardant additives are expensive, and in addition they in many cases worsen the properties of the base material.

In the alternative case, the surface material may be applied non-flammable coating. It works satisfactorily, provided that the shooting mode is limited. If the film coating does not have insulating properties, heat is distributed through the film and reaches a flammable substrate, which begins to emit gas or warp, breaking the film and come to the surface where it is exposed to fire (fire mode). As intumescent coating for the fire expanded, forming an insulating layer, they prevent the supply of heat to the substrate. It is known that, for example, by burning wood fire spread is limited charred layer formed during combustion.

To provide fire protection to the surface of the mother of the crystals and designs, require such protection, often covered with paint or other coatings, including compositions containing intumescent flame retardant substances. Under the action of heat compositions containing intumescent flame retardant substances act, forming a foam/charred layer of relatively non-combustible material. This non-combustible layer serves as insulation and prevents easy access of oxygen to the material to which it is applied, thus reducing or slowing overheating and/or burning of the material. In addition, the intumescent material can be introduced into sealing compounds, such as sealing composition, and after expansion with the formation of a layer of foam/coal they act as a heat resistant demonopolize seal.

Intumescent fire retardant compositions may include:

(a) a source of non-volatile acids, usually ammonium polyphosphate,

(b) organic matter, such as carbonization polyol, which can decompose under the action of acid released from ammonium polyphosphate, with the formation of a carbon source, and

(C) a source of inert volatile gases that contribute to foam formation/coal, which is a foaming agent. Source of volatile gases may be, for example, melamine. Intumescent foam/coal intumescent systems catalyzed f is sbornymi acids, usually consists of amorphous carbon or carbon and graphite and condensed phosphoric acids.

The underlying principle of this work consists in the introduction of functional properties of catalyzed phosphate system in the polymer molecule, which has both the properties of polymer resins and properties of intumescent materials.

Since in this case there are no inefficient mobile groups and all functional groups are in contact at the molecular level, the problems of migration does not exist. For example, when the reaction in the traditional intumescent material catalyzed by phosphate present in the material polyol is subjected to dehydration under the action of released polyphosphoric acid.

Obviously, when dehydration carbonization substances with the formation of carbon must first be formed ester of phosphoric acid, which is the intermediate of this reaction. The specified ester of phosphoric acid immediately decomposes at the time of formation, since the reaction temperature is above the temperature of decomposition of the specified ether. However, if an ester of phosphoric acid originally present in the original substance, the reaction would start at a lower decomposition temperature specified complex ether, and not when the temperature is re decomposition of ammonium polyphosphate.

Combining the functional properties of the binder, foaming substances, carbonization of the substance and the catalyst contained in the traditional intumescent compositions, in one polymer molecule by creating a stable phosphate esters carbonization of polyols was carried out in the so-called "self-swelling polymers" (Intrinsically Intumescent Polymers, IIP). As proof of theory of molecular integration of functional properties that determine the ability to swelling, can be considered a statement about the behavior of IIP, obtained on the basis of salts of urea and phytic (insidestory) acid.

If you evaluate the behavior of traditional intumescent material and material based on IIP using this indicator as weight loss, which is observed when heating a material, the composition based on IIP upon receipt of these foam coal be 40% more efficient than traditional songs. Since the IIP begins at temperatures below 150°C, they provide protection from fire early in the firing mode, than compositions based on RDAs.

Developed a method of obtaining IIP, which allows reducing the synthesis of partial esters of phosphoric acids, without resorting to the traditional method used is in the synthesis of plasticizers based on criminology (1,3,5-benzotriazoles) acid (trimester plasticizers), in which the source material is phosphorus oxychloride or trichloride phosphorus. These methods are not suitable for polymeric materials having high viscosity. IIP on the basis of partial esters of phosphoric acid is produced by a unique method of direct esterification.

In the US A-2272668 described partial esters of phosphoric acid and methods for their preparation.

In the US A-4458035 described polyurethane foam containing a flame retardant oligomeric ester.

In DE 10112155A described derivative salt of the ester of phosphoric acid or an adduct of an ester of phosphoric acid or mixtures thereof, the method of their derivation and application.

In DE 19540861 A1 describes a method for mixtures of oligomeric phosphoric esters and their use as flame-retardant agents in polyurethane foams.

The invention

Can be obtained polymeric material described by the following General formula:

where R1is alkylene, R2and R3selected from the group comprising H+alkylene, alkyl, simple allylglycidyl ether, and N ranges from 0.75 to 10.

In the present description mentioned carbonization substances and carbonization polyols. Carbonization polyols are polyols, which under anaerobic pyrolysis under the action of oxidizing acids into the plastics technology : turning & the d and not in the gaseous products. Assume that if the majority of the carbon skeleton of the polymer is in the form of potentially carbonization groups, this polymer pyrolized to carbon and not to combustible fragments.

In patent literature carbonization substances usually referred to as polyols, in which more than 40% of the mass of the molecule comprise hydroxyl groups. In traditional methods, a number carbonitrides polyols limited to pentaerythritol, its dimer and trimer, glycerin, and sucrose.

However, in accordance with the present method carbonization polyols may include ethanediol, 1,3-propandiol, glycerol, pentaerythritol and trimethylolpropane. Ethanediol and propandiol, related in the form of esters of phosphoric acid, in this system behave as carbonitrides polyols, while in traditional systems, they are volatile state before decomposed.

However, this definition of "carbonization substances, derived from earlier works in this field of technology is not adequate. The structure, which is transformed into carbon in the presence of a dehydrating acid may best be described by the sequence of links", in which any of the carbon atoms is not more than two carbon atoms from the carbon atom carrying either hydroximino group, or ester group, or a group dehydrating inorganic acid or nitrogen linked to another carbon atom.

Such compounds as 1,2-propandiol, Inositol, glucose or any other saccharide, though, and correspond to the standard definition of carbonization polyols, however, are subjected to the esterification of different ways. Any polyol containing 40% of hydroxyl groups, among which there is a secondary alcohol group, is decomposed under the action of a system designed for direct esterification. Thus, the definition given in the patent literature, is wrong with another point of view. When describing esters carbonitrides polyols preferred definition of active materials is the following: "the polyols, in which the mass of the primary hydroxyl groups is 40% of the molecular mass.

In accordance with another aspect of the present invention, a method for obtaining a flame-retardant polymeric material comprising the first reaction, in which the polymeric material precursor containing ester of phosphoric acid, and a second reaction in which the polymer material of the precursor to receive fire-resistant polymer material, while the first reaction involves reacting a first reagent containing anhydrous pentoxide FOS is ora, with the second reagent, characterized in that it is chosen from the group consisting of (a) a diol and (b) cyclic simple ether and alcohol, and the diol is selected from one or more substances, which represents a 1,3-propandiol and 1,4-butanediol, and cyclic simple ether selected from one or more substances that represents tetrahydrofuran, and tetrahydropyran, the polymeric material precursor, derived from the diol group (a)has a structure represented by the formula:

where R is alkylene having 3 or 4 carbon atoms.

The method may include the reaction of the first reagent containing material is a source of phosphorus, with the second reagent, and the specified second reagent includes or is capable of generating carbonitrides polyol or a functional equivalent of the polyol.

The alcohol used in the present method may include alcohol having one hydroxyl group, or a polyol such as a diol. Cyclic simple ether may include ethylene oxide and/or propylene oxide and/or tetrahydrofuran, and/or tetrahydropyran. Preferably cyclic simple ether include tetrahydrofuran.

In the first embodiment of the method of the first and second reagents can react with each other with the formation of the polymer material of the precursor. It is desirable that emery material-precursor contained ester of phosphoric acid, preferably a partial ester of phosphoric acid.

The reaction according to the first variant implementation of the invention can be represented by the following equation:

The alcohol used for this reaction may be a polyol such as a diol.

The polymer material of the precursor obtained in the reaction in accordance with the first variant execution can be represented by the following General formula:

In one embodiment, the polymer material of the precursor obtained in the first reaction, R1 represents alkylene in which the number of atoms is 3 or 4, N is 1, a, R2 and R3 represent H+.

In another embodiment, the polymer material of the precursor obtained in the first reaction, R1 represents n-butylene, R2 represents H+, R3 represents n-butyl or isobutyl, isopropyl, or any combination of these radicals, and N is from 0.75 to 4.

In the following embodiment, the polymer material of the precursor obtained in the first reaction, R1 represents n-butylene and/or 2,2-dimethylpropylene in a molar ratio greater than 3:1, R2 and R3 are ethyl, N+and/or chain, just what about ethylglycol ether, having an acid value of 30 to 70 mg KOH/g, and N ranges from 2 to 10.

In the following embodiment, the polymeric material obtained in accordance with the first response, R1 represents n-butylene, R2 and R3 are ethyl and/or chain simple ethylglycol ether, and N is from 2 to 10.

If the second reagent used to produce the polymer material of the precursor formed in accordance with the first response includes cyclic simple ether and alcohol, the alcohol can be an initiator of the reaction of the first reagent with cyclic simple ether. In addition, or alternatively, the alcohol can be an agent of breakage of the polymer chain in the polymer material of the precursor. Alcohol can be carbonatious material. Preferably carbonitrides material is converted into carbon when the obtained polymer material containing carbonization material reaches the activation temperature of the latter, i.e. the temperature at which begins the swelling of the product. Alcohol can be an alcohol with a short chain and/or a polyol, such as diol.

In the second embodiment of the method, the reaction may proceed as follows:

Preferably the carbon chain alcohol or diol used is of the second embodiment of the present method, contains four or less carbon atoms. This allows you to avoid the formation of inflammable substances under the action of the flame on the polymeric material, provided in accordance with the preferred implementation of the present invention. Alcohols suitable for use as the second reagent may include one or more of the following substances: methanol, ethanol, isopropanol, n-propanol, n-butanol, Isobutanol. Polyols suitable for use as the second reagent may include one or more of the following substances: pentaerythritol, glycerol, trimethylolpropane, ethanediol, 1,2-propandiol, 1,3-propandiol, 1,4-butanediol and glucose.

In the first embodiment of the method, which is a second aspect of the present invention, the diol can be placed in the reaction vessel. The first reagent may be introduced into the reaction vessel by means of the feeding device. Preferably the first reagent is kept in a cell for short-term storage, usually the feed chute, and it can be loaded into the reactor using the boot device, which may include pipeline. The pipeline can be installed specifies the mechanism for moving the first reagent along the pipeline. Specifies the mechanism may include a worm device, such as the Archimedes screw.

Preferably the boot device ends in the free space of the reaction vessel. To prevent reaction between the first and second reagent inside the boot device in the boot device may be filed with an inert gas. The inert gas may be nitrogen.

In the second embodiment of the method, which is a second aspect of the present invention, the reaction vessel may be placed in a simple ether, to which is then added to the first reagent and alcohol. Preferably the first reagent added to the reaction vessel by means of the feeding device. Preferably the first reagent is kept in a cell for short-term storage, preferably the feed chute, and it can be loaded into the reactor using the boot device, which may include pipeline. The pipeline can be installed specifies the mechanism for moving the first reagent along the pipeline. Specifies the mechanism may include a worm device, such as the Archimedes screw. Alcohol can be loaded into the reaction vessel using a device drip feed. Optionally, the reaction vessel may be placed in another alcohol.

Preferably the first reagent and, if necessary, diol or alcohol may be placed in the reaction vessel d is also as the temperature reaches the setpoint. When reaching a certain temperature, the loading of the first reagent and optionally alcohol stop.

For cooling of the reactants, the reaction vessel may include a cooling device. By reducing the temperature of the reactants below the setpoint, the cooling device may be disconnected, and the loading of the first reagent and, if necessary, the second reagent may be renewed.

Preferably the reactants are heated to a specified set temperature.

The desired temperature may be in the range from 25°C to 65°C. for Example, in one of the embodiments in which the polymeric material, the precursor is obtained from the first reagent and diol, the temperature may be in the range from 33°C to 37°C, more preferably to be essentially 35°C. In another embodiment, for example, where the polymeric material, the precursor is obtained from the first reagent and simple ether and alcohol, the desired temperature may be in the range from 25°C to 55°C, preferably in the range from 33°C to 37°C, more preferably to be 35°C.

Preferably, if the download of the first reagent and, if necessary, diol or alcohol may be stopped or slowed down when the temperature of the mixture reaches essentially 37°C. the Load R. the agents may be renewed, when the temperature drops essentially to 33°C. the Specified diol may include 1,3-propandiol.

In the alternative case, the preset temperature may be in the range of 43°to 47°C, more preferably to be essentially 45°C. the Loading of the first reagent and, if necessary, alcohol can be stopped or slowed down when the temperature of the reaction mixture reaches essentially 47°C. the Loading of the reagents may be resumed when the temperature drops essentially to 43°C. In this embodiment, the second reagent may include 1,4-propandiol.

After adding all the ingredients of the reaction mixture can be heated to a temperature in the range from 55°C to 75°C, more preferably essentially to 55°C or essentially to 75°C.

For mixing of reagents in the reaction vessel can be mounted mixing device.

The product obtained in accordance with the reaction of the first and second reagents may be introduced into reaction with the third reagent. The third reagent may include cyclic simple ether, such as ethylene oxide, propylene oxide and/or glycidol. The third reaction of the reagent with the specified reaction product can be represented as follows:

If the polymer material of the precursor on ucaut from the first reagent and diol, the reagents predominantly mixed in stoichiometric proportions.

If the polymer material of the precursor is obtained from the first reagent and simple ether and alcohol, the molar ratio of the first reagent to a simple ether may be in the range from 1:1 to 1.5:1, preferably between 1,1:1 and 1.2:1.

If the product of the reaction of the first reagent and simple ether and alcohol reacts with the third reagent, the molar ratio of the first reagent to a simple ether may be in the range from 1:1 to 2:1, preferably between 1,6:1 and 1.85:1. The reaction of the first reagent and simple ether to obtain the product of the reaction can proceed at a temperature in the range from 25°C to 55°C, preferably in the range from 43°to 47°C, more preferably essentially be 45°C. the Loading of the first reagent and, if necessary, alcohol can be stopped or reduced when the temperature of the reaction mixture reaches essentially 47°C. the Loading of the reagents may be resumed when the temperature drops essentially to 43°C.

The reaction of the above reaction product with a third reagent can proceed at a temperature in the range from 30°C to 60°C, preferably in the range of from 40°C. to 50°C.

Preferably the reaction of the above reaction product with the third reagent is performed in the second reaction vessel, to which that may include a vessel, provided with an insulating jacket, and may include a mixing device, such as a rotor. In the alternative case, the mixing device can create a funnel in the polymer material of the precursor.

Polymeric material, the precursor may be in the second reaction vessel, and can be installed supply device for supplying a fourth reagent. The feeding device may include a gas bubbler, which can be installed inside the second reaction vessel, so that the third reagent was barbotirovat through the polymeric material precursor. In the alternative case, the feeding device may include a device for gasification, such as the gasification column, by means of which the second reaction vessel to create an atmosphere consisting of the third reagent. Preferably the polymeric material, the precursor flows through the atmosphere of the third reagent. In the reaction vessel can be installed condensing device, which allows condensing the third reagent so that it fell in the form of droplets on polymeric material precursor. The polymeric material precursor may be at a temperature above the boiling point of the third reagent. If the polymer material of the precursor is maintained at this temperature, the third reagent Ave is in contact with the polymer material of the precursor passes into the gaseous state, and the resulting gas is admixed to the polymer material of the precursor using a mixing device.

The polymeric material precursor can be obtained by crosslinking oligomers dirtfoot diesters of 1,4-butanediol containing four or more phosphorus atoms, which are obtained by reaction of phosphorus pentoxide with tetrahydrofuran and any primary or secondary alcohol or diola containing four or less carbon atoms, or the reaction of phosphorus pentoxide with 1,3-propane diol or 1,4-butanediol.

The phosphorus pentoxide is preferably an anhydrous phosphorus pentoxide.

To obtain branched oligomers part of alcohols or diols may be replaced by pentaerythritol and/or trimethylolpropane.

Then the oligomers can be modified by reaction of the residual acid orthophosphate groups with cyclic ethers selected from the group consisting of ethylene oxide, propylene oxide or glycidol.

Unfused pyrophosphate group can remain in the skeleton of the oligomer or under him.

In accordance with the following aspect of the present invention proposed intumescent and fire retardant paints, varnishes and coatings prepared from phosphorus-containing oligomers described above, cross-linked urea or melamine-formaldehyde resins.

Decree the nye paints paints and/or coatings can be prepared with water-based, i.e. the main ingredient in their composition is a water in which are dissolved or suspended, or distributed in any other way the rest of the ingredients.

In accordance with the following aspect of the present invention proposed the adhesives used for the manufacture of fire resistant particle boards, in which the adhesive comprises the above-described oligomers, cross-linked urea or melamine-formaldehyde resins.

In accordance with the following aspect of the present invention proposed castings, composites and foam from phenol-aldehyde polymers obtained by curing rezol phenolic resin under the action of the above-described acid oligomers.

In accordance with the following aspect of the present invention proposed intumescent and fire resistant film, and the casting obtained from the above-described modified oligomers, in which the residual acid groups orthophosphate stitched using cycloaliphatic epoxy resins.

In accordance with the following aspect of the present invention proposed intumescent and fire resistant film, and the casting obtained from the above-described modified oligomers, in which the residual acid groups orthophosphate stitched using polyfunctional of aziridines.

In accordance with the following aspect of the present invention proposed intumescent and fire resistant film and casting, derived from the above-described modified oligomers, in which the residual acid groups orthophosphate stitched using zinc-ammonia complex compounds.

In accordance with the following aspect of the present invention proposed fire retardant polyurethane film casting and fiber derived from the above-described oligomers having a pH value, reduced by means of ethylene oxide and/or propylene oxide to a value of less than 7 mg KOH/g, and then crosslinked with isocyanates.

Preferably the flame retardant polyurethane film casting and fiber can be obtained from other polyols, mixed with oligomers before crosslinking with isocyanates.

In accordance with the following aspect of the present invention proposed fire retardant rigid and flexible polyurethane foam obtained from the above-described oligomers, the pH of which is reduced by means of ethylene oxide and/or propylene oxide to a value of less than 7 mg KOH/g, modified water and crosslinked with isocyanates.

Preferably the flame retardant rigid and flexible polyurethane foam obtained from other polyols, mixed with oligomers before crosslinking with isocyanates.

In accordance with the following aspect of the present invention proposed fire retardant coating, film casting or fiber, in which the above oligomers, the pH value of which is reduced by means of ethylene oxide and/or propylene oxide to a value of less than 7 mg KOH/g, are mixed with other polymeric materials to impart these coatings, films and castings or fibers flame retardant properties.

In accordance with the following aspect of the present invention, a method for obtaining the above-described oligomers, in which the above reaction is carried out by spreading powdered phosphorus pentoxide to stir the reaction mixture, and the rate of addition govern in accordance with the temperature of the reaction mixture.

In accordance with the following aspect of the present invention proposed a method of reducing the acidity of the above-described oligomers and/or other partial esters of phosphoric acid by the contact of gaseous ethylene oxide and/or propylene oxide with esters of phosphoric acids.

In accordance with the following aspect of the present invention, a method for preparation of the material in the form of a polymer salt comprising the reaction of an amine with a complex ester of phosphoric acid obtained by the method described above.

The method of preparation of the material based on polymer salt may include another reaction of the reagent with the amine and phosphate. Specified reagent may include amine.

Specified or each and the Institute may include an organic amine. Preferably specified or every Amin includes polyamine and/or a polymer containing functional amino group. Preferably the polymer contains many functional amino groups.

Polyamine may include melamine.

The polymer containing functional amino groups, may include polyethylenimine.

In accordance with the following aspect of the present invention, a method for obtaining a polymer material, comprising the reaction of melamine, a complex ester of phosphoric acid obtained by the method described above, and polyethylenimine.

Ester of phosphoric acid may contain partial ester of phosphoric acid. Ester of phosphoric acid can be a product of the reaction of phosphorus pentoxide with 1,4-butanediol and/or 1,3-propane diol and/or 1,2-ethanediol and/or pentaerythritol.

Ester of phosphoric acid may be a reaction product of a condensed phosphoric acid with 1,4-butanediol and/or 1,3-propane diol and/or 1,2-ethanediol and/or pentaerythritol.

The polymeric material may include a polymeric salt, preferably a mixture of polymeric salts.

The advantage of the preferred alternative implementation is that the polymeric material comprises a mixture of polymeric salts, the phosphorus content of which depends on the ratio of melamine and polyethylenimine amine, the use of which has been created for the reaction with incomplete complex ester of phosphoric acid. At low ratio of melamine and polyethylenimine get a polymeric material with high content and low activation energy compared to the material obtained by using a high ratio of melamine to polyethylenimine.

In some embodiments, execution of the method of producing a material based on polymer salt, the reaction may be conducted at temperatures up to 100°C, preferably at a temperature of from 85°C. to 98°C.

In other embodiments, execution of the method of producing a material based on polymer salt, the reaction may proceed at a temperature in the range from 90°C to 150°C, preferably essentially at 135°C.

Ester of phosphoric acid may include orthophosphate.

Material based on a polymeric salt may be suspended and/or dissolved in water, creating a pH from 4 to 8.

The ratio of melamine to polyethylenimine may be such that 40% of acid functional groups neutralized melamine and 60% of the acid functional groups are neutralized by polyethylenimine. Preferably the ratio of melamine to polyethylenimine may be such that 5% of acid functional groups neutralized melamine and 95% of the acid functional groups are neutralized by polyethylenimine.

In accordance with the following aspect of the present invention proposed fire retardant to notice, including the above material based on polymer salt.

Material based on a polymeric salt may be included in a matrix of thermosetting or thermoplastic resin.

Brief description of drawings

Embodiments of the present invention, given solely for illustrative purpose will be described below using the drawings, which depict the following :

1 schematically shows an apparatus for carrying out the first operation of the method of obtaining a polymer material;

figure 2 schematically shows an apparatus for carrying out the second operation of the method of obtaining a polymer material and

figure 3 shows a generalized sequence of reactions for enriched in phosphorus polymers form 1.

A detailed description of the preferred embodiments

Figure 1 shows the first apparatus 10 to the method of obtaining the polymer material of the precursor. The first device 10 includes a first reaction vessel 12, in which, as will be discussed below, in the first variant of realization can be placed diatomic alcohol such as 1,4-butanediol, and the second variant of realization can be placed cyclic simple ether, such as tetrahydrofuran.

The first device 10 further includes a hopper 14, which is powdered anhydrous is the phosphorus pentoxide. The hopper 14 includes a mechanical mixing device in the form of flexible wires 16, made of PTFE (polytetrafluoroethylene). From the hoppers 14 departs boot tube 18, reaches the free space inside the reaction vessel 12. Boot tube 18 includes a feeder 20 in the form of an Archimedes screw for powdered anhydrous phosphorus pentoxide to the reaction vessel 12.

For nitrogen in the feed tube 18 that creates inside the loading tube 18 inert atmosphere, establish a supply 22 of nitrogen.

The reaction vessel 12 includes a mixer 24 for mixing the reagents in the vessel 12.

The vessel 12 has a hollow shell 26, which is attached boot tube 28 to the coolant, i.e. cold water into a hollow shell 26 to maintain the desired temperature inside the reaction vessel 12. To control the reaction temperature and the release signal to the controller that controls the flow rate of the coolant in the reaction vessel 12 is installed thermometer 30.

In the case of the second variant implementation of the invention, in which the reagent, for example tetrahydrofuran, at once placed in the reaction vessel 12, the inside of the reaction vessel 12 establish a distribution device 32 for distribution initiating and/or breaking a chain alcohol (on the example diol). The distribution unit 32 includes a funnel 34, from which departs elongated hollow tube 36, ending inside the reaction vessel 12.

Figure 2 shows a second apparatus 40, in which the reaction product is carried out in the first apparatus 10, is introduced into reaction with a third reagent, representing cyclic simple ether such as ethylene oxide.

The second apparatus 40 includes a second reaction vessel 42. The reaction product obtained in the first reaction (occurring in the first apparatus 10)may be placed in the second reaction vessel 42. The second reaction vessel 42 has a hollow shell 44, which through the loading tube 46 serves coolant, for example water. In the second reaction vessel 42 is installed the second distribution device for delivery of liquid ethylene oxide in the second reaction vessel 42. The second distribution device 48 includes a funnel 50 and an elongated hollow tube 52 extending from the funnel 50 and terminating within the second reaction vessel 42.

The upper portion 54 of the inner space of the second reaction vessel 42 is wound with the coil 56 of the capacitor, through the feed tube 58 is directed to the cooler. The refrigerant discharged from the coil through the discharge tube 60.

In the second reaction vessel 42 for mixing the reagents set the mixer 62. The second reaction is the first vessel can be provided with an insulating jacket 64.

For preparation of various structures of the ratio of the loaded reagents can be changed significantly, which can be calculated without resorting to any theory, from the following considerations.

We can assume that each mole of phosphorus pentoxide contains 6 links in the form of P-O-P.

Each mol fully reacted alcohol reduces the number of connections P-O-P into two, with the formation of a single RON+and one link POR.

Each mol fully reacted primary diol reduces the number of connections P-O-P to four, with the formation of two relations

POH+and two ties POR(O-P). (This designation indicates that both ends R reacted, forming ester groups with phosphoric acid).

Each mol fully reacted tetrahydrofuran reduces the number of links POH+for one, forming a link POR(O-P)and reduces the number of connections P-O-P into two with the formation of a single POH+and one link POR(O-P).

Thus, if the number of gram-moles of P2O5in the loading reaction W is:

the number of gram-moles of alcohol (or diols) is X

the number of gram-moles of 1,4-butanediol is Y

the number of gram-moles of tetrahydrofuran is Z

the average gram molecular weight alcohols is M

Then:

the number of relations is P-O (RHO O-Pin the remaining pyrophosphate links (based on the initial number of moles, R2About5), equal And can be calculated by the equation:

A=(6W-2X-4Y-Z)/W

The number of groups POH+in the calculation of the initial number of moles P2O5equal to V, can be calculated by the equation:

In=(X+2Y-Z)/W

The number of groups POR per initial number of moles, R2O5equal to S, can be calculated by the equation:

C=X/W

The number of groups POR(O-P)in the calculation of the initial number of moles, R2O5equal to D, can be calculated by the equation:

D=(2Y+Z)/W

The chain length (CL), determine, based on the average number of groups, lengthening the chain (i.e. POR(O-P)one atom P by the equation:

(A+D)/2W

If this number is equal to 2, the length of the endless chain. As the end group is always PO4then

Acid value (AV) can be calculated from the following equation:

AV=56000B/(142W+HM+90Y+72Z)

The phosphorus content (P%) can be calculated from the following equation:

6200W/(142W+HM+90Y+72Z)

The present invention allows to obtain various patterns of polymeric material, which can be defined on the basis of their subsequent application and mechanism of crosslinking of the polymer, as shown in the following examples.

Example 1

Enriched what Ostrom polymers (PRP). Form 1

Decomposition of phosphorus pentoxide to orthophosphate under the influence of alcohol produced equimolecular a complex mixture of di - and monoamino:

P2O5+3ROH→H2RPO4+HR2PO4

This method is used for making chemicals, water treatment. Thus, if alcohol is replaced with 1,4-butanediol and the reaction is carried out in the reactor/distributor of phosphorus pentoxide used to perform the operation 1, one can easily get the product, in the form of a pale brown resin with medium viscosity, the structure of which corresponds to the following formula:

Similar resins and their variants are designed for stitching with the help of aminecontaining resins to obtain cheap intumescent coatings.

In the primary reaction vessel (described above) load portions 3 gram-mole of 1,4-butanediol. In the hopper load similar portions 2 gram-mole of phosphorus pentoxide. The contents of the vessel are heated to 45°C. Include stirring.

Begin the process of adding phosphorus pentoxide. Set minimum speed stirrers, necessary for fast absorption powder phosphorus pentoxide, falling on the surface of the reaction mixture. The temperature controller must cease addition, if the temperature of reaction the th mixture reaches the maximum allowable value of 47°C, and start the flow of coolant in the jacket of the reaction vessel. When the temperature falls to the minimum allowable value of 43°With the addition of phosphorus pentoxide should be resumed automatically by the controller. By passing the reaction product becomes more viscous and the temperature may be raised to 60°C. After the addition of all of the phosphorus pentoxide temperature was raised to 75°C and maintained at this temperature for four hours to complete the reaction of dissociation.

Thus obtained partial ester of phosphoric acid has a pH value of 600 mg KOH/g Product is either part of a two-component material, either single-component material, curable under the action of heat. For the purposes of receipt of Form 1, the product can also be prepared similarly not from 1,4-butanediol, and 1,3-propane diol, with the following clarification of the composition of the following compositions in terms of acidity.

The composition obtained in accordance with example 1 (component content in mass parts)

2345
Form 1, as in asana above 100100100100100
Pre-subjected to the reaction of phosphoric acid55
Only105105
BIP W 33879816567
BIP W 970
BIP W 64095
Only1798116567195
the temperature of curing 80°CRoom100°CRoom90°C
The cure time15 min24 hours10 min1 hour15 min

Pre-subjected to the reaction of phosphoric acid is prepared by dissolving 15 wt.% aluminum hydroxide in commercially available 70% phosphoric acid.

W 338 (supplied by British Industrial Plastics Ltd (BIP)is a typical commercially available partially etherified melamine-formaldehyde resin.

W 970 (supplied by British Industrial Plastics Ltd (BIP)is a typical commercially available urea-formaldehyde resin.

W 640 (supplied by British Industrial Plastics Ltd (BIP)is a typical commercially available etherified urea-formaldehyde resin.

Composition 1 described in example 1, is a one component product, which gives a transparent and flexible intumescent film, cured by heating, which provide fire protection flammable substrate when applied on the specified substrate. The product can be painted and modificarea the water or methoxypropanol, used as a diluent.

Composition 2 is a two-component curing in air floor, which gives a transparent and flexible intumescent film, providing protection from fire of flammable substrates. The product can be painted and modified water or methoxypropanol used as diluent.

Composition 3 is a cured when heated glue to the chipboard. When using the above-mentioned mixture with a resin content of 11-15% instead of traditional binders for bonding wood fibers or chips during hot pressing get fire-resistant chipboard.

Track 4 is a two-component curing in air floor, which gives transparent intumescent fire retardant film on paper and cardboard or any flexible substrate, for which the necessary temporary protection.

Composition 5 is a one component coating, which is a flexible, flame-retardant coatings for fabrics and paper products. It was unexpectedly found that oligomeric partial esters of phosphoric acid under these conditions are blended with a component that represents this typical example of a butylated urea-formaldehyde resin./p>

A generalized sequence of reactions to Form 1 PRP is shown in figure 3.

Example 2

Enriched with phosphorus polymers (PRP). Form 2

Products of the Form 2 are curing and cross-linking agents for the audio record-phenolic resins; both the structure and chain length of these phenol-aldehyde hardeners can be modified to meet their specific requirements. While in Forms 3 and 4, described below, as alcohol, initiating and breaking a chain, it is preferable to use ethanol, oligomers Form 2 for this purpose use isopropanol or n-butanol. These alcohols reduce the viscosity of the oligomer and, consequently, the viscosity of the mixture of resins. Because the audio record-phenolic resin is usually applied to the composites reinforced with fibers, the low viscosity of these resins allows them to penetrate into the fibers and to moisten them. In addition, the structure of the main chain of the polymer is advisable to leave a small amount pyrophosphate relations, not subjected to decondensation. This allows you to fully cure the audio record-phenolic resin at room temperature, providing a constant level of acidity because pyrophosphate groups are decondensation (splitting) under the action of water formed by condensation of the resin. Resins cured with these products, is OCTI not painted, and the composites obtained by means of these products have a high tensile strength tensile.

Composition And obtained in accordance with example 2

Using the above apparatus. In the hopper for pentoxide phosphorus load several portions 2 gram-mole of phosphorus pentoxide. Charged to the reactor the same number of servings in 1 gram-pray 1,4-butanediol and 2 gram-mole of tetrahydrofuran. Through a separate funnel chamber connected with the reactor, download the same number of servings in 1 gram-pray isopropyl alcohol. The contents of the vessel are heated to 35°C. Include stirring.

Begin the process of adding phosphorus pentoxide. Set minimum speed stirrers, necessary for fast absorption powder phosphorus pentoxide, falling on the surface of the reaction mixture. The proportional controller should discontinue addition, if the temperature of the reaction mixture reaches a maximum value of 37°C, and start the flow of coolant in the jacket of the reaction vessel. When the temperature falls to the minimum allowable value of 33°With the addition of phosphorus pentoxide should be resumed automatically by the controller. By passing the reaction product is visually becomes more viscous, and to control the viscosity in the reaction mixture arr is make dropwise isopropyl alcohol.

After the addition of all of the phosphorus pentoxide and isopropyl alcohol, the temperature was raised to 55°C and maintained at this temperature for two hours to complete the reaction of dissociation.

The crosslinking phenol-aldehyde resins, cold-cured product of the Form 2 is added to water the audio record-phenolic resins, such as Borden Chemicals Cellobond J2033L, in concentrations from 5 to 25%, which corresponds to the curing time from 4 hours to 10 minutes at 20°C.

If, as described in the application GB 2291881 use non-aqueous phenol-rezol resin, then adding the product of Form 2 in concentrations from 10 to 30% leads to the curing time from 5 hours to 25 minutes at 20°C. the Physico-mechanical properties of the products obtained are listed in the table below.

Laminates cold pressing; the ratio of resin to glass 2:1, 5 layers, 60 g chopped strands of reinforcing fiber ("now strand mat)

ResinCuring systemThe limit tensile stress, PAThe modulus of tensile elasticity, PAElongation at break, %
Jet audio record-phenolic resin10% Phencat 106,0×107 of 1.86×10102,9
Jet audio record-phenolic resin15% of the Form 27,37×107of 2.28×10103,3
Nonaqueous the audio record-phenolic resin20% Phencat 382of 1.46×1084,78×10104,4
Nonaqueous the audio record-phenolic resin10% of the Form 21,71×1085,23×1010the 4.7
Nonaqueous the audio record-phenolic resin15% of the Form 2of 1.53×1088,53×10104,01
Nonaqueous the audio record-phenolic resin20% of the Form 21,40×108to 8.62×1010the 3.8

Phencat 10 is a conventional curing system based on phosphoric acid/para-toluenesulfonic acid. Phencat 382 is a partial ester of phosphoric acid, about what isany in the application EP 92309426.2.

The composition obtained in accordance with example 2

Used the above-described apparatus. In the hopper for pentoxide phosphorus load in several portions over 1.5 gram-mole of phosphorus pentoxide. Charged to the reactor the same number of servings in 2 gram-mole of tetrahydrofuran. Through a separate funnel chamber connected with the reactor, download the same number of servings in 2.5 gram-moles of Isobutanol or n-butanol. The contents of the vessel are heated to 35°C. Include stirring.

Begin the process of adding phosphorus pentoxide. Set minimum speed stirrers, necessary for fast absorption powder phosphorus pentoxide, falling on the surface of the reaction mixture. The proportional controller should discontinue addition, if the temperature of the reaction mixture reaches a maximum value of 37°C, and start the flow of coolant in the jacket of the reaction vessel. When the temperature falls to the minimum allowable value of 33°With the addition of phosphorus pentoxide should be resumed automatically by the controller. By passing the reaction product becomes more viscous, and to control the viscosity in the reaction mixture is added dropwise isopropyl alcohol.

After the addition of all of the phosphorus pentoxide and isopropyl alcohol, the temperature was raised to 55°C is kept at this temperature for two hours to complete the reaction of dissociation.

The product does not contain residual pyrophosphate groups, but has a low viscosity; the viscosity of the product prepared with Isobutanol, is less than 300 SP. The product prepared with n-butanol, provides an extremely fast curing of the audio record-of phenolic resins at low temperatures. However, using product, made with isobutyl alcohol, as a curing agent for the phenol-aldehyde resin network structure with very low strength; however, this product can be used for impregnation of combustible porous substrates such as wood, to give them excellent flame retardant properties.

The phenol-aldehyde foam is often used as a flame retardant insulation panels. However, they are usually very fragile and have poor mechanical properties when exposed to fire. When replacing traditionally used in the art compositions hardeners Form 2 receive insulating panels made of light flexible phenolic foam having sufficient flexibility so that they can be used as a structural basis for the layered lamination materials. In contrast to conventionally produced phenol-aldehyde foams phenol-aldehyde foam, cured by using Form 2, have excellent properties under the action of a flame, because they prakticheskie warp or shrink.

Example 3

Forms 3 and 4

Materials Form 3 are partial esters of phosphoric acid with a very low acidity, intended to receive intumescent films, adhesives and coatings. Molecules of partial esters of phosphoric acids Form 3 filed cross-links with the help of additional reactions of the acid groups of the organic phosphoric acids. Organic phosphoric acids behave like carboxylic acids and, therefore, for cross-linking in the polymeric esters of orthophosphoric acid with low acidity fit any system used for cross-linking of the resins with functional groups of carboxylic acids. Thus, as cross-linking agents can be used cycloaliphatic epoxides, polyfunctional aziridine, polycarbamide and ammonia complexes of zinc and zirconium at room and at elevated temperature, depending on the nature of the crosslinking agent and the pH value.

Materials Form 4 have a neutral pH and contain functional hydroxyl group. As such, they react with the isocyanates with formation of polyurethanes, forming, thus, non-flammable polyurethane products, which are non-flammable under normal test is H. Depending on the choice and amounts of isocyanate and polyols, with whom he mixed, from the materials of the Form 4 can be obtained foam, suitable for the production of non-flammable decorative fabrics for upholstery, or they can be introduced into the polyurethane fiber for the production of flame-retardant polyurethane fibers based on polytetrahydrofuran like supplied under the trademark LYCRA or ELASTANE, or they can be entered into a non-flammable, lightweight and durable polyurethane film.

Materials Forms 3 and 4 is obtained by reaction of the residual acid orthophosphate groups with cyclic ethers. This second stage does not change the structure of the main chain of the oligomer. The properties of the oligomer, as well as any polymer or film obtained from the oligomer, depend on the molecular structure of the precursor obtained in the first stage reaction, and the molar ratio of components, reacting at this stage. Neutral oligomers are mainly linear structure and, therefore, can be obtained flexible foam and film. In addition, the chain length of the linear oligomer defines the properties of the final polymer. Oligomer representing a chain of nine orthophosphate groups separated by eight groups of esters of 1,4-butanediol, after he fully penetrates deeply into the foreground regime) with cyclic ethers and is crosslinked molecules of the isocyanate forms a flexible foams and elastomers.

While for the production of rigid foams specified linear oligomers can be modified by the addition of polyols with a high hydroxyl number, for the manufacture of paint and varnish films needed branched oligomers. They are made by typing in the beginning of the reaction as initiating the chain alcohols or pentaerythritol, or trimethylolpropane together with tetrahydrofuran. This leads to coordination rays (ligand arms) at the time of growth of the chain molecule of pentaerythritol, which initiates the development of the four circuits, or from molecules trimethylolpropane, which initiates the development of the three chains of the oligomer.

In addition, any of the additional cross-linking agents that can be used for resins with groups of carboxylic acids, can be used for knitting products Form 3. However, acid orthophosphate have high reactivity, so the acid number should not exceed about 50 mg KOH/g to be at least bifunctional in relation to the acid groups of orthophosphate, the molecular weight of the oligomer Form 3 should be approximately 2000.

Composition And obtained in accordance with example 3

Using the above apparatus. In the hopper for phosphorus pentoxide download several and portions 6 gram-moles of phosphorus pentoxide. Charged to the reactor the same number of servings in 1 gram-pray pentaerythritol and the same number of servings in 8 gram-moles of tetrahydrofuran. Through a separate funnel chamber connected with the reactor, download the same number of servings in 6 gram-moles of ethanol. The contents of the vessel are heated to 45°C. Include stirring.

Begin the process of adding phosphorus pentoxide. Set minimum speed stirrers, necessary for fast absorption powder phosphorus pentoxide, falling on the surface of the reaction mixture. The proportional controller should discontinue addition, if the temperature of the reaction mixture reaches a maximum value of 47°C, and start the flow of coolant in the jacket of the reaction vessel. When the temperature falls to the minimum allowable value of approximately 43°C, the addition of phosphorus pentoxide should be resumed automatically by the controller. By passing the reaction product becomes more viscous, and to maintain control of viscosity in the reaction mixture is added dropwise ethanol.

After the addition of all of the phosphorus pentoxide and ethyl alcohol, the temperature was raised to 65°C and maintained at this temperature for two hours to complete the reaction of dissociation. The pH of the reaction product of approximately 304 m is KOH/g

Then the reaction mixture is transferred into a secondary reactor described above. To reduce the pH value to approximately 50, just need the same selected number of servings to 12 mol of cyclic simple ether. This broadcast may be a combination of ethylene oxide and propylene oxide in any molar ratio. Preferred is the reaction temperature is in the range from 55°C. to 65°C.

It should be noted that simultaneously with the acid number is reduced and the viscosity.

The following table shows some examples of transformations in the secondary reactor, and the method further curing of the final product with the formation of transparent fire-resistant films or intumescent paints and flexible coatings.

The final acid number505050
A crosslinking agentHAMA 2ERL 4206Ammonium complex Zn
Number7%10%15%
The conditions of curing Room temperature,10 minutes140°C, 15 minVarious
Film propertiesTransparent, solid, swellingShiny, transparent, plasticSolid, translucent
The phosphorus content in the film14,5%14,5%15%

HAMA 2 is a commercially available polyfunctional aziridine, the company's product Flevo Chemie. ERL 4206 is a cycloaliphatic bifunctional epoxide, supplied by Union Carbide. The ammonia complex of zinc contains 7.2% of zinc oxide, 8,7% ammonia solution and 12.7% of ammonium carbonate in demineralized water,

The composition obtained in accordance with example 3

Using the above apparatus. In the hopper for pentoxide phosphorus load several portions 4,5 gram-mole of phosphorus pentoxide. Charged to the reactor the same number of servings in 8 gram-moles of tetrahydrofuran and 0.5 gram-mole of ethanol. Through a separate funnel chamber connected with the reactor, download the same number of servings in 6 gram-moles of ethanol. The contents of the vessel are heated to 35°C. Include stirring.

Begin the process of adding phosphorus pentoxide. Set minimum speed stirrers, necessary for fast absorption powder phosphorus pentoxide, falling on the surface of the reaction mixture. The proportional controller should discontinue addition, if the temperature of the reaction mixture reaches a maximum value of 37°C, and start the flow of coolant in the jacket of the reaction vessel. When the temperature falls to the minimum allowable value of 33°With the addition of phosphorus pentoxide should be resumed automatically by the controller. With the passage of the reaction mixture are added dropwise additional amount of ethanol in the approximate molar proportions corresponding to the number of phosphorus pentoxide.

After the addition of all of the phosphorus pentoxide and ethanol the temperature was raised to 65°C and maintained at this temperature for two hours to complete the reaction of dissociation. The reaction product is transferred to the secondary reactor described above and then treated with the same amount of servings in 8 moles of gaseous ethylene oxide and/or propylene oxide, as described above. The pH of the obtained neutral oligomers enriched in phosphorus and containing functional hydroxyl groups, should be less than 7 mg KOH/g

Sod the neigh of phosphorus in the specified material is at 16.1%. There is no need to sew the isocyanate groups polyols. If the product is subjected to the stitching methylcholantrene, in the absence of another polyol, a phosphorus content in the product is at 12.9%. The obtained film is not only flammable but also swelling.

If the oligomer is modified by adding the appropriate regulator foaming, such as NIAX 264 (supplied by OSI), and about 1% water, using colordistance (TDI or MDI oligomer forms a dense, elastic, flexible foam, suitable for the manufacture of non-flammable upholstery material, which under the action of a strong flame allocates only a small amount of smoke.

Even the song in which such embodiments of the invention, as the oligomers are present only in concentrations of 30 parts per thousand of the number of polyols, still have adequate flame-retardant properties, approximately corresponding to the level required for modified flame resistant foams in accordance with the standards of the UK, but in contrast, can be either flexible or rigid, depending on the number of hydroxyl groups in the polyol.

If the above precursor reacts with the number of ethylene oxide sufficient to reduce the acid number from the value of 50 mg KOH/g to m is it 7 mg KOH/g, the branched oligomer can be used for the manufacture of fire-retardant paints and varnishes. This oligomer is soluble in most ketones and, therefore, can be mixed with other film-forming polyols, such as Voeg Desmophen 800, or can be used without additives. It can be sewn calculated stoichiometric amount of diphenylmethanediisocyanate (DHS), isophorondiisocyanate or trimethylhexamethylenediamine, and the catalyst may be any system, commonly used in the art. Enriched with phosphorus polymers PRP - polyols of the Form 4 can be processed in the same way as any other polyols used in traditional technology of polyurethanes, subject to the restrictions imposed by their compatibility.

The composition obtained in accordance with example 3

The form can be used as a fire retardant for low-melting thermoplastics without the need for crosslinking hydroxyl functional groups. The oligomer was obtained as described above. It was added with a speed of 15 wt.% to pellets of polystyrene. The resulting mass was gently heated to obtain a rubbery mass. It was cooled and subjected to granulation by grinding with a mortar and pestle. Then mass was subjected to hot pressing to obtain flat sheets. the I et, compared to non-modified polystyrene sheets these sheets was a clear brown color, they showed a significant fire-retardant properties.

Next will be described embodiments of the present invention relating to the preparation of polymeric material in the form of a salt, in which to prepare polymeric salt of ester of phosphoric acid along with melamine apply neutralizing agents-based mixed amines. If the functional amino group is suspended in an aliphatic chain, you can achieve maximum neutralizing efficiency from the viewpoint of molecular weight. Thus, the most effective neutralizing agent is polyethylenimine. It can be represented by the following General formula:

However, it also has secondary and tertiary amines. Monomeric link has a molecular mass of 43 one functional amino group, which is much less than in any other applicable structure. The product prepared by the polymerization of ethylenimine. The product is commercially available in various forms under the trade name Lubristol. The most convenient commercially available form is Lubristol P, which represents a 50% aqueous solution of polyethylenimine supplied by BASF.

Polyethylenimine mo is et to be used as the sole precipitant for oligomeric partial esters of phosphoric acid; you get soft gels, tend to absorb water due to solvation. However, when using mixed neutralizing agents consisting of melamine and polyethylenimine, get a number of insoluble salts, the phosphorus content of which depends on the ratio of melamine to polyethylenimine in the mixture used for the neutralization of the acid functional groups. The smaller melamine is used to neutralize partial esters of phosphoric acid, the higher the resulting phosphorus content and the lower the activation temperature.

The following example shows a typical method of preparation of the polymeric salt. In this example, partial ester of phosphoric acid obtained by the method described in UK patent application 0310650.7, by the reaction of 2 moles of phosphorus pentoxide with 3 moles of 1,4-butanediol. Acid number of the oligomer is 600 mg/g KOH, and it represents a Form 1 is enriched in phosphorus polymers (PRP F1).

In a vessel with stirring download cold water.

Add powdered melamine in an amount sufficient to obtain a 5% solution.

Heated with stirring until then, until the temperature of the contents of the vessel will not reach values in the range from 85°to 98°Smellin is not soluble in hot water, but when heated the cold mixture forms a 5% solution.

Add in paramesh is the so called partial ester of phosphoric acid and stirred.

Add with stirring polyethylenimine and stirred.

Continue to heat and stir. Polymer salt begins to precipitate after about 5 minutes.

Continue to heat for about four hours.

Leave to cool and settle overnight.

Drained by decantation of the liquid above the sediment.

Again fill the container with water and stir polymer salt to the formation of the suspension.

Again heated for about four hours.

Leave the polymer salt is deposited.

Remove the liquid above the sediment.

Again fill the tank and leave the polymer salt is deposited, remove the liquid above the sediment, getting wet concentrate. Repeat washing.

Wet concentrate at this stage it is already possible to use.

Next obtained at this stage the product (i.e. wet concentrate) referred to as the "polymer suspension".

To obtain polymer powder slurry may be dried on the filter and then milled into powder; alternatively the slurry may be spray dried. In all cases, the final drying should occur at 130°C to remove water.

The following table presents the composition to obtain different grades of polymer salt of incomplete complex ester of phosphoric acid.

Composers the AI are specified in order to increase the ratio of melamine to polyethylenimine. Dimension indicated in the mass parts.

ExamplePRP F1MelamineWaterLubrisol PThe output of solidsP%
1100,027,0540,073,722,112,8
2100,0to 33.8675,060,118,912,8
3100,040,5810,064,5of 17.012,2
4100,047,3945,059,315,411,9
5100,054,01080,014,1the 11.6
6100,060,81215,050,713,011,3
7100,067,51350,046,112,211,0

As can be seen, the higher the concentration of melamine, the more sludge is produced which must be disposed.

Form 1 is enriched in phosphorus polymers (PRP F1) can be replaced by partial complex ester of phosphoric acid prepared in the same molar ratio, but using as the alcohol 1,3-propane diol; in this case, the figures in the examples 1-7 for partial esters of phosphoric acid should be reduced from 100 to 95,3 mass parts.

Any other polymeric amine or polyamine with a number of functional amino groups in level greater than or equal to 2, can be included in the composition with appropriate refinements concentrations of amine in the composition. Such additional materials alter the values of hardness and, thus, facilitate the grinding of dry salts. However, the most EF the objective to neutralize orthophosphate from polymeric amines should recognize Lubrisol P. Furthermore, the addition of polyamines with a lower content of amino groups greatly increases the additional number of carbon atoms in the salt, which reduces the phosphorus content and increases smoke emission in case of fire. It was found that the most effective polyamino reducing the solubility of these salts is melamine.

These salts can also be prepared by direct neutralization of the components at elevated temperature. For this purpose use a zigzag blade mixer or three-bladed stirrer, or any other mixer, which can mix thick paste. Apparatus for cooking must withstand temperatures in the range from 130°C to 140°C, and, in addition, its design should allow to quickly heat the mixture of the reactants.

Example 8

The method is best seen by example. Use any of the songs mentioned in examples 1-7, or any other suitable combination of incomplete complex phosphate ester carbonization polyols, melamine and polyfunctional amine; polyfunctional amine and melamine loaded into the mixer and raise the temperature to about 100°C. the Blend of neutralizing amines carefully stir to distribute the melamine in the mixture.

Then to the hot mixture, which should be covered to avoid R is sbrazhivanija components, but still communicated with the atmosphere, is slowly added partial ester of phosphoric acid and carbonization polyol (RRE). It releases a significant amount of heat and steam, and the viscosity of the reaction mixture increases.

After addition of the total number of re temperature raise up to 130-140°C and maintained for 15 minutes to complete the reaction.

The mixture is then either poured from the mixer, dried and crushed, or the mixture can be left to cool down to a temperature below 100°C., and then diluted with water with formation of a suspension of polymer particles of salt, similar suspension polymer salt obtained in the above-described wet method. The size of the particles obtained in this way polymer salt is very small, and the suspension is very viscous.

Example 9

Flame-retardant thermoplastics can be produced by introducing the dried polymer salt in the fallopian mixture of thermoplastic used for extrusion or molding. With the introduction of approximately 30 mass parts of the polymer salt in the original polymer, such as polypropylene, extrudable or moldable from it products become fireproof and successfully tested for suitability in aircraft construction, as described, for example, in FAR 25, Appendix G, and tests for class B1 according to DIN 4102. The introduction of more low con is entrace, approximately 6 mass parts, allows you to pass fire endurance test in less severe conditions.

Alternatively, the same result can be obtained by coating granules of masterbatches in suspension polymer salt. This allows you to exclude the operation of drying and grinding the polymer salt. Granules are poured into a wet slurry of polymer salt which adheres to the surface of thermoplastic. Then the granules can be dried in a tumble dryer and used for extrusion or injection molding in the usual ways. The polymeric salt may be introduced into the process of extrusion or casting in the form in which it is received, and distributed within the product, which leads to the already described results.

It was shown that the polymer salt is effective in the introduction of it in most of polypropylene, polyethylene and acrylic polymers. Thus, it would be logical to assume that, given the limitations imposed only by the temperatures of the processing of thermoplastics, polymer salt can be used effectively in most thermoset, moldable and extrudable materials.

Example 10

Reinforced thermoplastic composites, such as Twintex (manufactured by the company St. Gobin, USA), or other reinforced fiberglass or fiber composers who am, produced in the form of fabrics, can be made flame-retardant properties by pulling the finished fabric or yarn through the suspension polymer salt. Polymer salt does not form a suspension in water. Therefore, roller, guide the yarn or fabric to pass through the suspension should be at the bottom of the tank for the coating of the suspension. Polymer salt not only adheres to the polyolefin, but also gets stuck between the fibers. Then the fabric calendarbut to remove excess water, and the polymer salt is allowed to flow by gravity back into the reservoir for the suspension. Next, the fabric is dried in a drying Cabinet with circulating air at a temperature between 105°C and 150°C. the Fabric then can be sealed in the usual way, getting a fire-resistant composite fire-resistant characteristics which depend on the mass of the polymer salt deposited on unshaped fabric.

If thus treated yarn for the manufacture of cloth, then it is also possible to weave into the fabric of which then formed a flame-retardant thermoplastic composites.

Example 11

Similarly flame-retardant properties can be given a woven or non-woven fabrics when pulling these tissues through the suspension polymer salt, followed by drying and calendering. Polypropylene fleece fabric treated in this way, dealing 40 wt.% salt on the fabric weight, and received fleece fabric extruded on the surface of the polypropylene; this tissue showed significant resistance when making high speed propane torch.

Example 12

The dry powdered polymer salt was introduced in the usual composition of an acrylic sealant, in which the flame retardant substances traditionally used 25% of three-hydrate of aluminum based on the weight of the composition. The resistance that is comparable to the resistance obtained in the traditional way, was created using the 8% concentration powdery polymer salt; at the same time increased the acceptability of the sealing composition. It is assumed that similar behavior will be observed in adhesive compositions that traditional media cannot fireproofing.

Example 13

To receive intumescent coating polymer salt may be introduced into the latex composition. The following simple compositions have good bloating. However, experts in the art should understand that the height of the foaming/opplevelse layer depends on the viscosity of the melt resin carrier. As expected, in example 12D was obtained the lowest foamed layer. Since the polymer salt is yellow, its coloring ability is low and can be easily tamaskar the van titanium dioxide in the form of rutile, as shown in example 12B. In all the examples, except example 12G, the compositions include a much smaller volume concentration of pigment than traditional intumescent composition, which makes them, in contrast to conventional compositions, water-based, easy to use and manufacture.

-
Example14A14V14C14D1414F14G
Revacryl 34489-----89
Pliolite LS 1-125----
Haloflex 202--100----
Silikophen P65W--125---
Emultex 523----100--
Araldite PY 340-2-----a 38.5
Araldite HY 2992----11,5-
Polymeric Sol50505050505060
Titanium dioxide - rutile-5---9,0
Processed mineral fiber------0,5
2-Butoxyethanol--05---

Revacryl (Revacryl) 344 (manufactured by the company Harco, UK) and Pliolite (Pliolite) LS 1 (manufactured by the company Eliochem, USA) are SamAccountName styrene-acrylic emulsion; Haloflex (Haloplex) 202 (manufactured by the company Zeneca, UK) is a vinyl chloride-vinylidenechloride emulsion. Silikophen (Cilician) P65W (manufactured by Thomas Goldshmidt, Germany) is a phenyl/methyl-siloxane emulsion. Emultex (Emulex) 523 (manufactured by the company Harco) is a VeoVa emulsion, traditionally used for the manufacture of intumescent coatings water-based. Araldite® (Araldit) PY 340-2 is a dispersible in water liquid epoxy resin, a Araldite HY 2992 is a typed is the hardener. If necessary, as colesterolo solvent using 2-butoxyethanol.

When applied to soft wood all of these songs from 14A to 14F give the surface spread of flame, which corresponds to less than 12 in accordance with BS 475, part 6. Composition 14G designed to protect structural steel. When tested on a small test bench, designed to assess the protective compositions for structural steel, this composition forms a carbonized layer and has an insulation characteristic of the traditional songs.

Since all the components of the traditional foaming compositions slightly soluble in water, none of these songs may not be open for a long time without a coating. Since the polymer salt is insoluble, it is logical to assume that all data composition resistant to external influences.

Polymer salt you can also enter in the composition to obtain a surface coating based on polyurethane, epoxy and alkyd resins simple adulteration powder salt to commercially available compositions, receiving depending on the input concentration or intumescent or fire resistant composition. Similarly, the product can be easily introduced in the polyester and epoxy compositions. the product can also be used to improve the flame retardant properties of the phenol-aldehyde resins, although there is a very weak swelling.

1. A method of obtaining a flame-retardant polymeric material comprising the first reaction, in which the polymeric material precursor containing ester of phosphoric acid, and a second reaction in which the polymer material of the precursor to receive fire-resistant polymer material, while the first reaction involves reacting a first reagent containing anhydrous phosphorus pentoxide, with a second reagent, wherein the second reagent selected from the group consisting of (a) a diol and (b) a mixture of cyclic simple ether and alcohol, and the diol is selected from one or more substances, which represents a 1,3-propandiol and 1,4-butanediol, and cyclic simple ether selected from one or more substances that represents tetrahydrofuran, and tetrahydropyran, the polymeric material precursor, derived from the diol group (a)has a structure represented by a formula

where R is alkylene having 3 or 4 carbon atoms.

2. The method according to claim 1, wherein the polymeric material precursor includes a partial ester of phosphoric acid.

3. The method according to claim 1 or 2, wherein the alcohol comprises an initiator that initiates the reaction of the first reagent with simple ether and/or alcohol includes an agent of an open circuit in the polymeric material is Yale predecessor.

4. The method according to claim 3, in which the alcohol comprises monohydroxy alcohol and/or polyol containing 4 carbon atoms or less.

5. The method according to claim 4, in which the polyol comprises diol.

6. The method according to claim 1, in which the carbon chain alcohol containing four or less carbon atoms.

7. The method according to claim 1, wherein the alcohol comprises one or more substances selected from methanol, ethanol, isopropanol, n-propanol, n-butanol, Isobutanol.

8. The method according to claim 1, wherein the alcohol comprises one or more substances selected from pentaerythritol, glycerol, trimethylolpropane, ethanediol, 1,2-propane diol, 1,3-propane diol, 1,4-butanediol and glucose.

9. The method according to claim 1, in which the diol is a reaction vessel, and the first reagent added to the reaction vessel by means of submission.

10. The method according to claim 1, in which a simple ester is a reaction vessel, which serves the first reagent and alcohol.

11. The method according to claim 10, in which the first reagent contained in a holding element and fed into the reactor using the rescue funds, which include pipeline.

12. The method according to claim 11, in which the tubing set screw mechanism for feeding a first reagent into the reaction vessel.

13. The method according to item 12, in which the boot end funds in the free space of the reaction vessel, and the retaining element and the boot means p is given an inert gas to prevent reaction between the first and second reagents inside the loading means.

14. The method according to claim 10, in which alcohol is served in the reaction vessel by means of a drip feed.

15. The method according to 14, in which the reaction vessel is an optional second reactant.

16. The method according to claim 9, in which, in the case of alcohol, the first reagent and alcohol is served in the reaction vessel until such time as the temperature reaches the set value, and when reaching a certain temperature, the flow of the first reagent and alcohol stop or reduce.

17. The method according to clause 16, in which the reaction vessel contains cooling means for cooling the reactants and by reducing the temperature of the reactants below a specified setpoint cooling means can be turned off and the flow of the first reagent and, if necessary, the alcohol can be resumed.

18. The method according to clause 16, in which the preset temperature is from 25 to 65°C.

19. The method according to p, in which the preset temperature is from 33 to 37°C., preferably, essentially, is 35°C.

20. The method according to p, in which the desired temperature can be from 43 to 47°C, preferably, essentially, is 45°C.

21. The method according to clause 16, in which, after adding all the ingredients of the reaction mixture is heated to a temperature of from 55 to 75°C., more preferably, essentially, part of 55°C or, essentially, part 75°C.

2. The method according to claim 1, wherein in the second reaction of the polymer material of the precursor obtained in the first reaction between the first reagent and simple ether and alcohol, is introduced into reaction with the third reagent.

23. The method according to item 22, in which the third reagent comprises cyclic simple ether, such as ethylene oxide, propylene oxide and/or glycidol.

24. The method according to claim 1, wherein the polymeric material, the precursor is obtained from the first reagent and diol, and the reagents are mixed in stoichiometric proportions.

25. The method according to claim 1, wherein the polymeric material, the precursor is obtained from the first reagent and simple ether and alcohol, and the first reagent and simple ether are in the molar ratio of the first reagent: a simple broadcast from 1:1 to 1.5:1, preferably between 1,1:1 and 1.2:1.

26. The method according to item 22, in which the reaction product of the first reagent and simple ether and alcohol is introduced into reaction with a third reagent, the first reagent and simple ether are in the molar ratio of the first reagent: a simple broadcast from 1:1 to 2:1, preferably between 1,6:1 and 1.85:1.

27. The method according to item 22, in which the second reaction between the specified product and the third reagent occurs at a temperature of from 30 to 60°C., preferably from 40 to 50°C.

28. The method according to item 22, in which the second reaction is performed in the second reaction vessel, which includes a vessel equipped isol is zational shirt and includes means for mixing.

29. The method according to p, in which the second reaction vessel is the product of the reaction of the first reagent with simple ether and alcohol, and to download the third reagent is provided startup funds.

30. The method according to claim 1, where the method involves the reaction of ester of phosphoric acid with the amine and flame-retardant polymeric material is a salt.

31. The method according to item 30, which involves the reaction of an amine and a complex ester of phosphoric acid with an additional reagent, and the additional reagent includes Amin, and each includes organic amine amine.

32. The method according to p, in which each amine includes polyamine and/or a polymer containing functional amino group.

33. The method according to p, in which the polyamine comprises melamine.

34. The method according to p, in which the polymer containing functional amino group includes polyethylenimine.

35. The method according to item 30, in which the ester of phosphoric acid is introduced into reaction with melamine and polyethylenimine.

36. The method according to item 30, in which the reaction is carried out at temperatures up to 100°C., preferably from 85 to 98°C.

37. The method according to item 30, in which the reaction is carried out at a temperature of from 90 to 150°C., preferably essentially at 135°C.

38. The method according to item 30, in which the ester of phosphoric acid includes orthophosphate.

39. The method according to item 30, in which polim the RNA material in salt form may be suspended and/or dissolved in water, providing a pH of from 4 to 8.

40. Fire-retardant composition comprising a polymeric material in the form of a salt obtained by the method according to any of p-39.

41. Fire retardant enriched with phosphorus polymer obtained by the method according to any one of claims 1 to 39.

42. The polymer according to paragraph 41, which includes more than 4 wt.% of phosphorus.

43. The polymer according to paragraph 41, which includes more than 9 wt.% of phosphorus.

44. The polymer according to paragraph 41, in which the polyol comprises about 40 wt.% primary hydroxyl groups.

45. Water-insoluble intumescent polymeric Sol obtained by the method according to any of p-39.

46. Intumescent polymeric salt according to item 45, in which the ester of phosphoric acid is a reaction product of phosphorus pentoxide with 1,4-butanediol and/or 1,3-propane diol.

47. The material comprising the product according to any one of p-46.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention refers to fire retardant based on mixed hydroxyethylated tetramethylphosphonylpentaerithrite and methylphosphonic acid ethers and applied in aircraft industry as additive to polymer honeycombs and composite materials thus decreasing combustibility thereof. Offered fire retardant is characterised by production method and physical and chemical properties. Method of offered fire retardant production interaction of dimethylphosphonate and methylphosphonic acid dichloranhydride with pentaerithrite. Prepared mixture is trated with ethylene oxide. Stages of production method can include application of water or hydrochloric acid solution. All components of reaction mixture are taken in specified molar ratio at certain temperature conditions. Produced fire retardant is liquid of dynamic viscosity 270.0-280.0 centipoise at 75°C. Phosphorus mass fraction is 15.8-16.2%. Volatile mass fraction is 1.2-2.0%. Alcohol hydroxyl OH-group content is 10.8-11.4 %. Acid value is 1.0-2.0 mg KOH per for 1 g.

EFFECT: production of new effective additive to polymer honeycombs and composite materials thus decreasing combustibility thereof.

1 cl, 3 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention refers to fire retardant based on hydroxyethylated diethyleneglycol and methylphosphonic acid ethers and applied as additive to polymer honeycombs and composite materials thus decreasing combustibility thereof. Offered fire retardant is characterised by production method and physical and chemical properties. Method of fire retardant production includes interaction of methylphosphonic acid dichloranhydride with diethyleneglycol. Besides water, hydrochloric acid and dimethylphosphonate can be appliedfor process. Then produced mixture is treated with ethylene oxide. Reagents are used in specified molar ratio at certain temperature conditions. Produced fire retardant is moderately viscous liquid of dynamic viscosity 600.0-630 centipoise at 25°C, phosphorus mass fraction 16.8-17.5 %, volatile mass fraction 1.2-1.3 %.

EFFECT: production of new effective additive to polymer honeycombs and composite materials thus decreasing combustibility thereof.

1 cl, 3 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention refers to fire retardants based on pentaerythrite and methylphosphoric acid esters including that oxypropylated which can be used as the additive in composite polymeric materials for combustibility decrease. Offered fire retardants are characterised by production methods and physical and chemical properties. Fire retardants production methods include interaction of methylphosphoric acid dichloranhydride and pentaerythrite in certain molar ratio and certain temperature conditions. And for fire retardant production dimethylmethylphosphonate can be used. Resulted from interaction of methylphosphoric acid dichloranhydride and pentaerythrite, fire retardant is viscous water- and alcohol-soluble liquid at 20÷25°C being semicrystalline substance with phosphorus content 14.1÷14.36%, alcohol OH-group content 13.6-14.0 %, acid OH-group content 2.5-3.5 % and pentaerythrite 1.15-1.3 %. Once produced fire retardant is processed with propylene oxide at certain temperature conditions, it is possible to produce fire retardant representing viscous substance with phosphorus content 10.0÷10.3%, alcohol OH-group content 10÷12%, volatile content 1.5-2.0 % and KOH acid value 0.1-0.4 mg per 1 g of product.

EFFECT: production of new effective polymer-honeycomb additives and combustibility decreasing composite materials.

2 cl, 4 ex, 1 tbl

FIELD: construction engineering.

SUBSTANCE: invention relates to bio- and fire protection of the objects and is designed to prevent origination and development of biological damages, as well as to up fire resistance of construction objects and structures. A method is described to determine the optimum content of substance components and the substance for biological protection of construction objects, as well as for fire and biological protection of wood materials, the said substance containing component C1, i.e. ether acids of phosphorous acids, component C2, i.e. readily coking carbohydrate components, component C3, i.e. active gas developing agent, component C4, i.e. homogenising and interbonding component, wherein the content (percent by weight) of component C1, ether acids of phosphorous acids, and that of component C2, readily coking carbohydrate components are interrelated by the expression 0,053≤(α1C12C2)/C1≤2,l, where α1 is an experimental factor selected depending upon resistance against biological damages of the object processed surface in the range of 0,051≤α1≤l,3, α2 is an experimental factor selected depending upon the object processed surface fire resistance in the range of 0,012≤α2≤1,1, and the content of component C1, i.e. ether acids of phosphorous acids, that of component C2, i.e. readily coking carbohydrate component and that of component C3, i.e. active gas developing agent are interrelated by the expression 0,62≤(α1C12C2+βC3)/C1≤6,l, where β is an experimental factor selected depending upon the temperature of decomposition of the active gas developing agent in the range of 0,715≤β≤2,2. Here, the content of component C1, i.e. ether acids of phosphorous acids, that of component C2 readily coking carbohydrate component, that of component C3, i.e. active gas developing agent and that of component C4, i.e. homogenizing and interbonding components taken together, do not exceed 100 percent by weight, and are selected from the expression l,7≤(α1C12C2+βC3+C4)/(C1+C2)≤12, where γ is an experimental factor selected depending upon the degree of the preset homogeneity of the substance in the range of 0,93≤γ≤1,08. here, the substance as the component C1, i.e. ether acids of phosphorous acids, contains dimethyl-phosphite, as the component C2, i.e. readily coking carbohydrate component it contains starch and/or lignine, as the component C3, i.e. active gas developing agent it contains dicarboxylic acid amides, as the component C4, i.e. homogenizing and interbonding component it contains water.

EFFECT: proposed substance with the optimum content of selected components improves fire and biological protection in compliance with this invention.

3 cl, 3 ex, 1 tbl

FIELD: fire-resistant materials.

SUBSTANCE: porous substrate, in particular polymer substrate, is impregnated with fire-resistant agent, namely organophosphorus compound having hydrophilic or hydrophobic nature to be compatible with surface of porous carrier. Impregnation is effected according to dry impregnation technique.

EFFECT: considerably improved fire resistance of materials without harmful effect on properties of material at temperatures above 200°C.

30 cl, 2 tbl, 4 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to methods for synthesis of antipyrenes used in fireproofing wood materials. Method for synthesis of antipyrenes is carried out by mixing two components one of that - amidophosphate is synthesized by interaction of carbamidoformaldehyde concentrate comprising, wt.-%: carbamide, 21-25; formaldehyde, 54-60, and water, the balance, with ammonia water taken in equimolar ratio with respect to formaldehyde and ammonia, at heating in weakly alkaline medium, in the presence of aminoalcohol chosen from the group comprising monoethanolamine, diethanolamine, triethanolamine, amine modifying agent AM-1 adding in common with ammonia water in the amount 0.01-0.3 wt.-% as measured for carbamidoformaldehyde concentrate followed by addition of 1-10 wt.-% of carbamide as measured for 100 wt.-% of carbamidoformaldehyde concentrate, cooling and neutralization of the reaction mixture with ortho-phosphoric acid to pH 6.0-8.0, and the second component - an aqueous dispersion of acrylic or vinyl acetate polymers. Invention provides optimization conditions for synthesis of antipyrenes with simultaneous retention of their high effectiveness after contact of water with wood.

EFFECT: improved method of synthesis.

1 tbl, 6 ex

FIELD: fire-retardant ornamental textile materials, fillers for fire retardant composites.

SUBSTANCE: claimed method includes burn retardant into polyester fiber. As burn retardant 5-7 % dimethyl phosphonate aqueous solution is used. Additionally material is treated with CO2-laser irradiation with power of 350 W, density of 5.3 W/cm, for 25-30 s up to dimethyl phosphonate content on fiber of 12-15 mass %. Fibers are characterized with oxygen index of 31.5-33 %, and fiber durability is narrow increased.

EFFECT: new flame-retardant materials.

1 tbl, 11 ex

FIELD: polymer materials.

SUBSTANCE: invention provides a method for manufacturing polyvinyl alcohol-based modified films with elevated fire resistance by means treatment with phosphorus-containing compounds. In particular, 5-15% aqueous solution of methyl phosphite borate is used and films are treated during 1-2 min and then dried at ambient temperature. Thus obtained polymers are characterized by good film-forming properties, exhibit self-extinction capability, and show water absorption at a level of 1.14%. Films can be used in various industry and national economy fields.

EFFECT: improved performance characteristics of films.

1 tbl, 3 ex

FIELD: textile industry.

SUBSTANCE: invention relates to technology of manufacturing flame retarded textile materials, which may be used as filler when manufacturing flame retarded composites and decorative and finishing textile materials. Method of invention comprises applying burning retardant, namely Antipyrene T-2 (methylphosphonamide ammonium salt) onto polycaproamide or polyethylene terephthalate fiber, retardant being used in the form of 5-7% aqueous solution. Fiber is the additionally exposed for 25-30 sec to 350 W CO2-laser emission. Treated fiber contains 22-25% Antipyrene T-2 and is characterized by oxygen index: 35% (polycaproamide) and 42.5% (polyester fiber). Strength of fibers is slightly increased.

EFFECT: substantially increased fire resistance of textiles.

1 tbl, 32 ex

FIELD: methods of production of antipyrines for fireproof treatment of wood materials.

SUBSTANCE: proposed method includes interaction of carbamide formaldehyde concentrate of the following composition, mass-%: carbamide, 21-25; formaldehyde, 54-60; the remainder being water with ammonia water taken at equimolar ratio by formaldehyde and ammonia at heating in weak-alkaline medium in presence of aminoalcohol selected from group containing mono-ethanol amine, di-ethanol amine, tri-ethanol amine and amine modifying agent AM-1 added together with ammonia water in the amount of 0.01-0.3 mass-% in terms of carbamide formaldehyde concentrate followed by introduction of carbamide in the amount of 1-10 mass-% per 100 mass-% of carbamide formaldehyde concentrate; then, reaction mixture is cooled and neutralized with ortho-phosphoric acid to pH= 6.0-8.0.

EFFECT: optimization of synthesis process of antipyrines at retained fire resistance efficiency.

1 tbl, 2 ex

The invention relates to the production of self-extinguishing sealing compounds based on epoxy resins and can be used for impregnation of electrical goods, in particular for casting high-voltage devices, such as transformers, ignition coils

The invention relates to the production of polyorganosiloxane with integral alkoxygroup and to the application of this polyorganosiloxane as a component of CGT-1-alkoxycarbonyl (CGT means "vulcanization at room temperature")

The invention relates to the production of polymer compositions based on epoxy resins used for corrosion protection of metals and construction materials, and in particular to mastic-based resin FEED-8

The invention relates to compositions based on polycarbonate, structural materials on the basis of which possess high mechanical strength, chemical resistance and resistance to weathering

The invention relates to the production of polymeric materials technical and special purpose
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