RU2794096C2 - Modified diene-containing (co)polymer, method of its production and application as a fire retardant - Google Patents

Abstract

FIELD: polymers.

SUBSTANCE: present invention relates to a group of inventions: a modified diene-containing (co)polymer, variants of methods for producing a modified diene-containing (co)polymer, the use of a modified diene-containing (co)polymer, expandable polystyrene and a polymer composition based on expandable polystyrene. The modified diene-containing (co)polymer contains halogen atoms and hydroxyhalogenated diene units in its structure, has a temperature of 5% weight loss, which is at least 180°C, a weight-average molecular weight of at least 1500 g/mol, a halogen content of at least 35% by weight based on the weight of the total (co)polymer and a content of hydroxyhalogenated diene units in an amount of from 0.05 to 1.9% by weight calculated based on the weight of the entire (co)polymer. The method for obtaining a modified diene-containing (co)polymer includes: the stage of dissolving the original diene-containing (co)polymer in a hydrocarbon solvent; an epoxidation step including the addition of an epoxidizing agent, or a modification step by adding components of the modifying system; a neutralization and separation step comprising adding an aqueous solution of a neutralizing agent and separating the aqueous and organic layers; an halogenation step including adding a halogenating agent, water to the organic layer, or an absence of this step; a neutralization and separation step comprising adding an aqueous solution of a neutralizing agent to the reaction mass and separating the aqueous and organic layers; a precipitation step comprising precipitating the modified diene-containing (co)polymer by adding an excess alcohol-precipitant to the organic layer; a separation step comprising filtration and subsequent drying of the precipitated modified diene-containing (co)polymer. This modified diene-containing (co)polymer is used as a flame retardant. Expandable polystyrene containing a modified diene-containing (co)polymer is used as a flame retardant. A polymer composition based on expandable polystyrene, including a modified diene-containing (co)polymer, is used in the field of construction as a flame retardant and may include additives that provide a set of technological, physical, mechanical and operational characteristics.

EFFECT: development of a flame retardant based on a diene-containing (co)polymer, which will be heat-resistant, will meet environmental requirements, and will also show good compatibility and provide excellent fire-retardant properties to polystyrene, including expandable polystyrene.

105 cl, 5 dwg, 2 tbl, 8 ex

Description

The field of technology to which the invention belongs

The invention relates to the field of modified diene-containing (co)polymers, in particular, a modified butadiene-styrene copolymer, which can be used as a flame retardant (flame retardant) for polymer compositions based on expandable polystyrene. In particular, the invention relates to a modified diene-containing (co)polymer, a method for its preparation and use as a flame retardant (flame retardant) for polystyrene, including expandable polystyrene.

State of the art

Flame retardants (flame retardants) are widely used in products made from various polymers and polymer compositions, for example, products based on expandable polystyrene, to impart flame retardant properties to them. In such polymer compositions, various low molecular weight brominated compounds, for example, hexabromocyclododecane (HBCD), are usually used as flame retardants (flame retardants). However, many studies have shown HBCD to be bioaccumulative, highly toxic and environmentally resistant. This led to the restriction of the use of HBCD as a flame retardant (flame retardant) in order to reduce environmental risks.

For some polymer compositions, such as those based on expandable polystyrene, processing temperatures are often very high, as a result of which the flame retardant (flame retardant) may decompose during the processing of the polymer composition. In this case, there is a loss of flame retardant properties of the polymer compositions and the formation of decomposition products, such as HBr. Therefore, it is important that the flame retardant (flame retardant) be thermally stable at the temperatures of processing of polymeric materials, and also meet the requirements of non-toxicity and environmental friendliness.

As an alternative to HBCD, flame retardants (flame retardants) that are more environmentally friendly than HBCD and are based on diene-containing (co)polymers, in particular styrene-butadiene copolymers, are known from the prior art.

Examples of such flame retardants (flame retardants) are brominated styrene-butadiene copolymers disclosed, for example, in application WO2008021417 and patent RU2414479.

Thus, patent RU2414479 proposes a heat-resistant brominated butadiene-styrene copolymer, which can be used as a flame retardant (flame retardant) in foamed and non-foamed polymeric materials. Said brominated styrene-butadiene copolymer is characterized by a level of non-brominated non-aromatic double bonds less than or equal to 15% based on the level of non-aromatic double bonds in the copolymer before bromination, as determined by ¹ H NMR spectroscopy, and a temperature of 5% weight loss , equal to at least 200 ^about C as determined by the method of thermogravimetric analysis (TGA).

Also, the invention according to patent RU2414479 proposes a method for producing the above-mentioned heat-resistant brominated copolymer, which includes:

obtaining a homogeneous reaction solution of the copolymer, brominating agent, in particular tetraalkylammonium tribromide, and solvent;

keeping the reaction solution under the reaction conditions for a period of time sufficient to brominate at least 85% of the non-aromatic double bonds contained in the copolymer;

recovering the brominated copolymer by passing the filtrate through silica gel or a bed of ion exchange resin;

washing the filtrate with an aqueous solution of sodium hydrosulfite to neutralize the unreacted brominating agent;

recovery of the brominated copolymer by precipitation in methanol.

In addition, the invention according to patent RU2414479 proposes a polymer mixture containing the specified heat-resistant brominated butadiene-styrene copolymer, as well as a molded product containing the specified polymer mixture.

The disadvantage of this flame retardant (flame retardant) is its lower thermal stability, which manifests itself at high processing temperatures of expandable polystyrene, as well as the limited compatibility of highly brominated butadiene-styrene copolymers, which can cause difficulties in obtaining a homogeneous structure of foamed polystyrene at large thicknesses obtained from it. products.

In addition, from the prior art (patent RU2530021) it is known to use a brominated and epoxidized butadiene-styrene copolymer as a flame retardant (flame retardant) for expandable polystyrene.

According to the specified invention, the flame retardant (flame retardant) is obtained by a method including:

epoxidizing the starting styrene-butadiene copolymer with a molecular weight of at least 700 such that at least a portion of the non-conjugated carbon-carbon double bonds are epoxidized;

brominating at least a portion of the remaining non-conjugated carbon-carbon double bonds by contacting the epoxidized styrene-butadiene copolymer in step a) with quaternary ammonium tribromide to form a brominated and epoxidized styrene-butadiene copolymer.

The flame retardant (fire retardant) obtained in accordance with the invention is characterized by a molecular weight of at least 1500, a bromine content of at least 35 wt.% and a five percent (5%) weight loss temperature of at least 180 ^° C.

However, despite the fact that the specified flame retardant (flame retardant) contains epoxy groups capable of absorbing HBr released at high processing temperatures of polymer compositions based on expandable polystyrene, there is an effect of such a flame retardant (flame retardant) on the polymerization process and the yield of polystyrene granules, which confirmed by the comparative experiments below.

Also one example of polymeric flame retardants (flame retardants) for expandable polystyrene are hydroxybrominated butadiene-styrene copolymers, disclosed, for example, in the application WO2016123263.

The flame retardant (flame retardant) proposed in the application WO2016123263 is obtained by reacting a styrene-butadiene copolymer with quaternary ammonium tribromide to brominate from 50 to 98% of the butadiene repeat units in the initial copolymer to obtain a partially brominated copolymer, followed by the interaction of a partial brominated copolymer with an N-haloimide, for example, N-chlorosuccinimide, N-bromosuccinimide, in the presence of water and a water-miscible solvent to halohydrate a portion of the butadiene repeating units to form a hydroxybrominated butadiene-styrene copolymer. The resulting hydroxybrominated styrene-butadiene copolymer contains 2 to 50% by weight of butadiene units that are hydroxybrominated and 50 to 98% by weight of butadiene units that are brominated and has a 5% weight loss temperature of at least 250 ^o C.

The disadvantage of this flame retardant (flame retardant) is the high content of hydroxyl groups, which leads to a significant increase in the polarity of the flame retardant (flame retardant) molecule, which, in turn, leads to a deterioration in the stability of the system during the process of obtaining polystyrene, thereby worsening the granulometric composition of polystyrene , which is confirmed by the experiments below.

In addition, the disadvantages of the method of obtaining a flame retardant (flame retardant) proposed in this invention are the duration of the stage for obtaining a hydroxybrominated butadiene-styrene copolymer, the duration of the stage of its isolation from the reaction mass, and the need to use expensive reagents, in particular, N-haloimide.

Thus, flame retardants (flame retardants) known from the prior art based on diene-containing (co)polymers and methods for their preparation are not effective enough, and also require large economic and time costs.

In this regard, one of the promising areas is the development of a flame retardant (flame retardant) based on a diene-containing (co)polymer, which will be heat-resistant, will meet environmental requirements, and will also show good compatibility and provide excellent fire-retardant properties to polystyrene, including expandable polystyrene. polystyrene.

The essence of the invention

The objective of the present invention is to develop a modified diene-containing (co)polymer that can be used as a flame retardant (flame retardant) for expandable polystyrene, as well as to develop a method for its production.

The resulting modified diene-containing (co)polymers are characterized by high thermal stability, namely the temperature of 5% weight loss, which is at least 180 ^about C, are characterized by a molecular weight of at least 1500 g/mol and a halogen content of at least 35 wt.% based on the weight of the entire (co)polymer, which does not affect the polymerization process and the formation of polystyrene granules, and also exhibits high compatibility with polystyrene.

Additional technical resultis the provision of the flame retardant (flame retardant) proposed in the present invention with fire retardant properties expandable polystyrene, which make it possible to attribute expandable polystyrene, which contains the flame retardant (flame retardant) proposed in accordance with the present invention, to moderately flammable materials with flammability class B2 (in accordance with clause 7, article 13 of the "Technical Regulations on Fire Safety Requirements" (Federal Law of 07/22/2008 N 123-FZ, as amended on 07/29/2017)).

This technical problem is solved and the achievement of the technical result is ensured by a modified diene-containing (co)polymer, including hydroxyhalogenated diene units in an amount of from 0.05 to 5 wt.%, as well as halogen atoms in an amount of at least 35 wt.% based on the weight of the entire (co)polymer.

In addition, the present inventors have found that said modified diene-containing (co)polymer can be obtained by using a mixture of halogen and water as the modifying system in the presence of an aliphatic alcohol. The modifying system makes it possible to introduce hydroxyl groups and halogen atoms into the structure of the initial (co)polymer.

The present inventors have found that a modified diene-containing (co)polymer comprising a relatively small amount of hydroxyhalogenated diene units (units that include a halogen atom and a hydroxyl group), namely from 0.05 to 5 wt.%, and also including halogen atoms in an amount of at least 35 wt.% based on the weight of the total (co)polymer, is heat-resistant, does not affect the polymerization process and the formation of polystyrene granules, exhibits good compatibility with polystyrene, and also provides high fire-retardant properties to expandable polystyrene.

Presumably, it is the low content of hydroxyhalogenated diene units that makes it possible to achieve a balance of hydrophilic and hydrophobic properties in the molecule of the modified diene-containing (co)polymer, thereby ensuring the stability of the entire system in the process of obtaining polystyrene, while not affecting the formation of polystyrene granules, and also providing high fire retardant properties. properties of expandable polystyrene.

The present invention makes it possible to obtain a modified diene-containing (co)polymer containing hydroxyhalogenated diene units, as well as halogen atoms, which can be used as a flame retardant (flame retardant) in various polymer compositions, for example, based on polystyrene, including expandable polystyrene.

Description of figures

To explain the technical solutions that reveal the essence of the present invention are presented in Fig. 1, Fig. 2, fig. 3, fig. 4 and FIG. 5.

On FIG. 1 is a flowchart showing the sequence of steps for obtaining a modified diene-containing (co)polymer according to the present invention through an epoxidation step.

On FIG. 2 is a flowchart showing the sequence of steps for preparing a modified diene-containing (co)polymer in accordance with the present invention using a modifying system.

On FIG. Figure 3 shows the spectrum of nuclear magnetic resonance on hydrogen nuclei ( ¹ H NMR spectrum) of the obtained butadiene-styrene copolymer containing hydroxyl groups and bromine atoms.

On FIG. 4 shows the distribution of bromine in samples of polystyrene containing a modified diene-containing (co)polymer obtained in accordance with the present invention, obtained by X-ray fluorescence analysis (XRFA).

On FIG. 5 shows the distribution of the modified diene-containing (co)polymer obtained in accordance with the present invention in polystyrene, obtained by scanning electron microscopy (SEM).

Detailed description of the invention

The following is a description of various aspects of the implementation of the present invention.

According to the present invention, the modified diene-containing (co)polymer obtained is a heat-resistant modified diene-containing (co)polymer which has a weight average molecular weight of at least 1500 g/mol, preferably 2000 to 280,000 g/mol, more preferably 10,000 to 150,000 g/mol, most preferably from 60,000 to 100,000 g/mol, as well as a plurality of non-conjugated carbon-carbon double bonds, with at least one (but less than all non-conjugated carbon-carbon double bonds) undergoing modification, and the modified diene (co) the polymer contains at least 35 wt.%, preferably at least 60 wt.%, more preferably at least 75 wt.% halogen based on the weight of the entire (co)polymer, and at least one hydroxyhalogenated non-conjugated carbon-carbon double connection.

The term "heat resistance" in the present invention means the temperature of five percent (5%) weight loss of the modified diene-containing (co)polymer, determined by the method of thermogravimetric analysis (TGA), described below.

The resulting heat-resistant modified diene-containing (co)polymer contains hydroxyhalogenated diene units in an amount of from 0.05 to 5 wt.%, preferably from 0.1 to 3 wt.%, more preferably from 0.15 to 2 wt.% based on weight the total (co)polymer.

The presence of hydroxyhalogenated diene units in an amount of from 0.05 to 5 wt.%, as well as halogen atoms in an amount of at least 35 wt.%, based on the weight of the entire (co)polymer in the modified diene-containing (co)polymer, makes it possible to obtain polystyrene granules with the necessary physical and mechanical characteristics, to increase the compatibility of the (co)polymeric flame retardant (flame retardant) with polystyrene, and also to provide high fire retardant properties to expandable polystyrene.

Accordingly, the temperature of the 5% weight loss of the modified diene-containing (co)polymer is at least 180 ^° C, preferably at least 200 ^° C, more preferably at least 220 ^° C.

An example of a modified diene-containing (co)polymer obtained in accordance with the present invention is, but is not limited to, a modified diene-containing (co)polymer with the general formula (1):

(1)

(1)

where R ₁ -R ₃ - are the same or different and may represent hydrogen or a hydrocarbon group with the number of carbon atoms from 1 to 6, for example, an alkyl group, Hal - represents a halogen; m, l, p - may be the same or different and is preferably 1<m<37, 2<(l+p)<3680, more preferably 6<m<12, 610<(l+p)<1225, most preferably 7<m<10, 735<(l+p)<985, n is the number of polymer chain units, which is preferably 50<n<450, more preferably 100<n<350, most preferably 140<n<250.

In accordance with the present invention, the modified diene-containing (co)polymer can be obtained by any of the methods known from the prior art, which allow introducing hydroxyl groups and halogen atoms into the structure of the original diene-containing (co)polymer.

In this case, the original diene-containing (co)polymer, from which the modified diene-containing (co)polymer is obtained, can be polymers and copolymers of a conjugated diene.

Suitable conjugated dienes are conjugated dienes with 4 to 12 carbon atoms, for example 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2-ethyl-1,3-butadiene, 2,3- di(C1-C5 alkyl)-1,3-butadienes such as 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1, 3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene, phenyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 2-methyl-pentadiene, 4-methyl-pentadiene, or mixtures thereof, etc. Preferably, 1,3-butadiene or isoprene is used.

Suitable comonomers in the original diene-containing (co)polymer are vinylaromatic compounds such as styrene, α-methylstyrene, ortho-, meta- and para-methylstyrene, 3-vinyltoluene, ethylvinylbenzene, 4-cyclohexylstyrene, p-tert-butylstyrene, methoxystyrenes, vinylmesitylene , divinylbenzene, 1-vinylnaphthalene, 2,4,6-trimethylstyrene, etc., or mixtures thereof. Preferably, styrene or α-methylstyrene is used.

Suitable conjugated diene polymers and copolymers contain at least 30% by weight, preferably at least 50% by weight, more preferably 70% by weight of polymerized conjugated diene units.

Preferably, such (co)polymers as butadiene, butadiene-styrene and butadiene-styrene-isoprene can be used as the initial diene-containing (co)polymer, most preferably butadiene-styrene copolymer, which can be di- and triblock copolymers of butadiene and styrene .

Examples of commercially available diene-containing (co)polymers include, but are not limited to, butadiene polymers with the trade name SKD-ND (BR-1243 Nd Grade B (LP)), SKD-ND (BR-1243 Nd Grade B), SKD-ND BB (BR-1243 ND HV), block copolymers of butadiene and styrene with the trade name DST R 30-00, SBS L 30-01A, SBS R 30-00A, DST L 30-01, DST L 30-01 (SR), butadiene - styrene copolymer obtained by solution polymerization with the trade name DSSK-2560-M27 (grade AA), DSSK-2560-M27 BB (grade A), DSSK-4040-M27 (grade A) produced by PJSC SIBUR-Holding.

Suitable starting diene-containing (co)polymers have a weight average molecular weight of at least 700 g/mol, preferably 1000 to 400,000 g/mol, more preferably 2000 to 300,000 g/mol, more preferably 5000 to 200,000 g/mol, more preferably from 20,000 to 120,000 g/mol, most preferably from 20,000 to 50,000 g/mol, with a polydispersity coefficient from 0.8 to 3, more preferably from 1 to 1.8, most preferably from 1.1 to 1.5, with the amount 1,2 units equal to at least 10 to 100 wt.%, preferably at least 50 to 99 wt.%, more preferably 60 to 80 wt.% on the polydiene part of the (co)polymer.

According to the present invention, the modified diene-containing (co)polymer can be obtained by a method which includes the following steps:

a dissolution step: dissolving in a hydrocarbon solvent, optionally pre-crushed, the original diene-containing (co)polymer;

an epoxidation step: adding an epoxidizing agent to the solution of the original diene-containing (co)polymer obtained in step a) in a hydrocarbon solvent;

a neutralization and separation step: adding an aqueous solution of a neutralizing reagent to the reaction mass obtained in step b) and separating the aqueous and organic layers;

a halogenation step: adding a halogenating agent, water, and optionally an aliphatic alcohol to the organic layer obtained in step c);

a neutralization and separation step: adding an aqueous solution of a neutralizing agent to the reaction mass obtained in step d) and separating the aqueous and organic layers;

precipitation step: precipitation of the modified diene-containing (co)polymer by adding an excess alcohol-precipitant to the organic layer obtained in step (e);

isolation step: filtration and subsequent drying of the precipitated modified diene-containing (co)polymer.

Stage a) dissolution

At this stage, the original diene-containing (co)polymer, optionally pre-crushed, is dissolved in a hydrocarbon solvent with stirring.

Grinding, if necessary, of the initial diene-containing (co)polymer is carried out by any methods known from the prior art, for example, using crushers (knife, hammer, rotary), mills (jet, screw), etc.

When dissolving the original diene-containing (co)polymer, mixing can be carried out by any method known from the prior art, for example, using an apparatus with a stirrer, a static mixer, at a temperature of from 10 to 50 ^° C, preferably from 15 to 40 ^° C, more preferably from 20 to 30 ^o C.

Suitable solvents include, but are not limited to, hydrocarbon solvents, preferably having a purity of 99% or more, and representing ethers, for example, tetrahydrofuran, halogenated saturated aliphatic hydrocarbons, for example, carbon tetrachloride, chloroform, dibromomethane, dichloromethane, 1,2- dichloroethane, cycloaliphatic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene, halogenated aromatic hydrocarbons such as bromobenzene, chlorobenzene and dichlorobenzene. Preferred hydrocarbon solvents are those which are liquid under the conditions of modification of the original diene-containing (co)polymer, and which do not undesirably react with the modifying system or the original (co)polymer. Preferably, tetrahydrofuran, chloroform, dichloromethane, dichloroethane, cyclohexane, toluene are used as the solvent, most preferably tetrahydrofuran, chloroform, dichloromethane is used.

The weight ratio of the hydrocarbon solvent to the original diene-containing (co)polymer is from 5:1 to 30:1, preferably from 8:1 to 20:1, more preferably from 10:1 to 15:1.

The dissolution process time is no more than 60 minutes, no more than 50 minutes, no more than 40 minutes, no more than 30 minutes, no more than 25 minutes, no more than 20 minutes, no more than 15 minutes, no more than 13 minutes, no more than 11 minutes, no more than 9 minutes, no more than 7 minutes, no more than 5 minutes.

The mass obtained as a result of the dissolution step described above is a solution of the original diene-containing (co)polymer in a hydrocarbon solvent.

Step b) Epoxidation

In step b) of epoxidation, an epoxidizing agent is added to the initial diene-containing (co)polymer solution obtained in step a), resulting in the oxidation of non-conjugated carbon-carbon double bonds to form epoxy groups.

In accordance with the present invention, pure substances containing active oxygen are used as an epoxidizing agent, as well as solutions of such substances in hydrocarbon solvents with an epoxidizing agent content of from 10 to 50 wt.%, preferably from 15 to 30 wt.%, more preferably from 20 up to 25 wt.%

Suitable epoxidizing agents include, but are not limited to, peracids, such as performic acid, peracetic acid, metachloroperbenzoic acid, and peroxides, such as hydrogen peroxide, or mixtures thereof, including in the presence of catalysts, such as molybdenum or tungsten derivatives.

The epoxidizing agent may be dissolved in a hydrocarbon solvent or a mixture thereof, preferably 99% or more pure, which is an ether such as tetrahydrofuran, halogenated saturated aliphatic hydrocarbons such as chloroform, dibromomethane, dichloromethane, 1,2-dichloroethane, cycloaliphatic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene, halogenated aromatic hydrocarbons such as bromobenzene, chlorobenzene and dichlorobenzene. Preferably, the epoxidizing agent is added as a solution thereof in the same solvent used in step a) to dissolve the original diene-containing (co)polymer.

The epoxidizing agent is used in an amount sufficient for epoxidation of not more than 6 mol%. non-aromatic double bonds, preferably not more than 2.5 mol%. non-aromatic double bonds, more preferably not more than 0.5 mol%. non-aromatic double bonds.

Preferably, the epoxidizing agent or solution thereof is dosed at a rate of 0.80 to 50 ml/min, preferably 1 to 10 ml/min, more preferably 1.5 to 5 ml/min during the epoxidation step. A very high dosing rate leads to crosslinking of the polymer in the reaction mass, and a low dosing rate leads to a significant increase in the synthesis time.

The epoxidation step is carried out in any batch or continuous equipment known from the prior art. Suitable equipment includes, but is not limited to, a continuous stirred reactor, a batch stirred reactor, a stirred autoclave.

The epoxidation step is carried out at a temperature of (-20) to 100 ^° C, preferably (-10) to 50 ^° C, more preferably 0 to 20 ^° C, and atmospheric pressure.

The time of the epoxidation step can be any time sufficient to achieve the desired degree of epoxidation of the initial diene-containing (co)polymer described above. Preferably the time of the epoxidation step is at least 15 minutes, at least 20 minutes, at least 25 minutes, at least 30 minutes, at least 45 minutes, at least 60 minutes, at least 120 minutes.

The reaction mass obtained after step b) of epoxidation contains a partially epoxidized diene-containing (co)polymer.

Step c) neutralization and separation

This stage includes the neutralization of the reaction mass obtained in stage b) containing the partially epoxidized diene-containing (co)polymer by adding a neutralizing agent solution, followed by washing the neutralized reaction mass with water and separating the aqueous layer and the organic layer containing the partially epoxidized diene-containing (co)polymer.

As the neutralizing agent, aqueous basic solutions known from the prior art are used, but are not limited to, for example, sodium hydroxide, sodium thiosulfate, sodium bisulfite, sodium carbonate, etc.

The molar ratio of neutralizing agent to added epoxidizing agent is generally 1:1 to 3:1, preferably 1:1 to 2:1, more preferably 1:1.

Preferably, the neutralization process is carried out at a temperature of 15 to 50°C, preferably 20 to 40°C, more preferably 25 to 30°C, and atmospheric pressure.

Washing with water is carried out using at least one, preferably at least two, more preferably at least three times excess of water relative to the volume of the reaction mass subjected to neutralization, resulting in separation of the reaction mass into two layers: an organic layer containing partially an epoxidized diene-containing (co)polymer, and an aqueous layer.

The separation of the organic and aqueous layers is carried out using any method known from the prior art, for example, using a separating funnel, separator, sump.

Step d) halogenation

In step d) halogenation, a halogenating agent, water and optionally an aliphatic alcohol are added to the organic layer obtained in step c) containing the partially epoxidized diene-containing (co)polymer.

As the halogen in the halogenating agent, chlorine, bromine or iodine is used in the form of elemental compounds as such, as well as in the form of solutions in a hydrocarbon solvent.

Preferably, elemental bromine (Br ₂ ) is used as a halogenating agent as such, and also in the form of a solution in a hydrocarbon solvent with a bromine content of not more than 70 wt.%, more preferably not more than 60 wt.%, most preferably not more than 50 wt.%. Also suitable halogenating agents are, but are not limited to, quaternary ammonium bromides, e.g. bromide, tetrapropylammonium bromide, tetra-n-butyl-ammonium tribromide, or mixtures thereof.

Preferably, elemental bromine (Br ₂ ) and quaternary ammonium bromides or quaternary phosphonium bromides are used simultaneously as the halogenating agent. At the same time, elemental bromine reacts with epoxy groups in the presence of water, which leads to the opening of epoxy rings and the formation of hydroxybrominated diene units, and the use of quaternary ammonium bromide or quaternary phosphonium bromide makes it possible to avoid significant substitution of hydrogen for bromine at tertiary or allyl carbon atoms, which, in in turn, affects the heat resistance of the resulting modified diene-containing (co)polymer.

In the context of the present invention, water is, but is not limited to, distilled, deionized, demineralized, osmotic, bidistilled water, and is used in an equimolar amount relative to the amount of epoxy groups.

As aliphatic alcohol, alcohols with a content of carbon atoms from 1 to 6 are used, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, but are not limited to them. Preferably, propanol, butanol, isobutanol, pentanol are used as the aliphatic alcohol, more preferably butanol, isobutanol and pentanol are used.

The molar ratio of the original diene-containing (co)polymer:halogenating agent:aliphatic alcohol is from 1:1.5:3 to 1:5:3, more preferably 1:2:3 to 1:4:3, most preferably from 1:2 ,5:3 to 1:3:3. Wherein, in the case of combined use of elemental bromine and quaternary ammonium bromide or quaternary phosphonium bromide as a halogenating agent, the molar ratio of elemental bromine:bromine atoms in quaternary ammonium bromide or quaternary phosphonium bromide is from 1:1 to 1:4, more preferably from 1:2 to 1:3, most preferably 1:1 to 1:1.5.

The order of adding the halogenating agent, water and aliphatic alcohol to the partially epoxidized diene-containing (co)polymer obtained in step c) can be any. Preferably, an aliphatic alcohol is first added to the partially epoxidized diene-containing (co)polymer obtained in step c), followed by the addition of water and a halogenating agent. At the same time, when quaternary ammonium bromide or quaternary phosphonium bromide and elemental bromine are used together as a halogenating agent, the entire volume of quaternary ammonium bromide or quaternary phosphonium bromide is added to the reaction mass at once in the form of its solution in an aliphatic hydrocarbon solvent.

The addition of elemental bromine is preferably carried out in the form of its solution in an aliphatic hydrocarbon solvent by dosing the solution into the reaction mass at a rate of from 0.80 to 50 ml/min, preferably from 1 to 10 ml/min, more preferably from 1.5 to 5 ml/ min. A very high dosing rate leads to local overheating of the reaction mass, an increase in its viscosity, which in turn can lead to the production of a modified diene-containing (co)polymer with a low (less than 35 wt.%) content of halogen atoms.

Also, adding the entire volume of a solution of elemental bromine (Br ₂ ) to the partially epoxidized diene-containing (co)polymer obtained in step c) can lead to its crosslinking, to local overheating of the reaction mass, an increase in the viscosity of the reaction mass, which can also lead to the production of a modified diene-containing ( co)polymer with a low (less than 35 wt.%) content of halogen atoms.

The halogenating agent may be dissolved in a hydrocarbon solvent or a mixture thereof, preferably having a purity of 99% or more, and which is an ether, for example, tetrahydrofuran, halogenated saturated aliphatic hydrocarbons, for example, chloroform, dibromomethane, dichloromethane, 1,2-dichloroethane, cycloaliphatic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene, halogenated aromatic hydrocarbons such as bromobenzene, chlorobenzene and dichlorobenzene. Preferably, the halogenating agent is added as a solution thereof in the same solvent used in step a) to dissolve the original diene-containing (co)polymer.

The halogenation step is carried out in any batch or continuous equipment known from the prior art. Suitable equipment includes, but is not limited to, continuous stirred reactor, batch stirred reactor, stirred autoclave, which are designed to handle highly corrosive media.

Preferably, the halogenation step of the partially epoxidized diene-containing (co)polymer obtained in step c) is carried out without access to visible radiation, for example, by carrying out the halogenation process in tinted glass vessels, by wrapping the reactor in foil, or by carrying out the process in metal reactors, in order to reduce the likelihood reactions of non-selective photocatalytic halogenation.

The halogenation step is carried out at a temperature of 0 to 50 ^° C, preferably 20 to 45 ^° C, more preferably 30 to 40 ^° C, and atmospheric pressure.

The stirring speed of the reaction mass after addition of the halogenating agent is 50 to 600 rpm, preferably 100 to 500 rpm, more preferably 200 to 300 rpm.

The time of the halogenation step may be any time sufficient to achieve the desired degree of halogenation of the partially epoxidized diene-containing (co)polymer described above. Preferably, the halogenation time is at least 15 minutes, at least 20 minutes, at least 25 minutes, at least 30 minutes, at least 45 minutes, at least 60 minutes, at least 120 minutes.

The reaction mass obtained after step d) of halogenation contains the target product, a modified diene-containing (co)polymer containing hydroxyl groups and halogen atoms.

Step e) neutralization and separation

This stage includes neutralization of the reaction mass obtained in stage d) containing a modified diene-containing (co)polymer by adding a neutralizing agent solution, followed by washing the neutralized reaction mass with water and separating the aqueous layer and the organic layer containing the modified diene-containing (co)polymer.

As the neutralizing agent, aqueous basic solutions known from the prior art are used, but are not limited to, for example, sodium hydroxide, sodium thiosulfate, sodium bisulfite, sodium carbonate, etc.

The molar ratio of neutralizing agent to added halogen is generally 1:1 to 3:1, preferably 1:1 to 2:1, more preferably 1:1.

Preferably, the neutralization process is carried out at a temperature of 15 to 50°C, preferably 20 to 40°C, more preferably 25 to 30°C, and atmospheric pressure.

Washing with water is carried out using at least one, preferably at least two, more preferably at least three times excess of water relative to the volume of the reaction mass subjected to neutralization, resulting in separation of the reaction mass into two layers: an organic layer containing a modified a diene-containing (co)polymer, and an aqueous layer.

The separation of the organic and aqueous layers is carried out using any method known from the prior art, for example, using a separating funnel, separator, sump.

Step f) Deposition

To precipitate the modified diene-containing (co)polymer obtained in step e), to the organic layer obtained in step e), containing the modified diene-containing (co)polymer, a precipitant alcohol is added in a mass ratio of precipitant alcohol:modified (co)polymer from 10 to 1 , preferably 15 to 5, more preferably 5 to 4.

Suitable precipitant alcohols include, but are not limited to, aliphatic alcohols of 1 to 4 carbon atoms. Examples of such alcohols include, but are not limited to, methanol, ethanol, propanol, isopropanol, butanol, isobutanol. Preferably, methanol and ethanol are used as the precipitating alcohol.

Step g) isolation

At stage g) isolation to purify the modified diene-containing (co)polymer from solvent residues and precipitant alcohol, filtration is carried out in any apparatus known from the prior art, for example, in filters equipped with porous filter septa, suction filters, etc.

Filtration of the modified diene-containing (co)polymer is carried out at a temperature of from 20 to 40°C inclusive.

In order to remove water and/or its vapors, solvent and/or its vapors from the resulting modified diene-containing (co)polymer, the said (co)polymer is dried. The drying process of the modified diene-containing (co)polymer can be carried out by physical methods commonly used for separating and purifying organic substances (distillation of the solvent under reduced pressure, drying in a vacuum oven, etc.), as well as using drying reagents that remove moisture due to adsorption, hydrate formation or chemical reaction with water and solvents.

Preferably, the drying is carried out at a temperature of 50 to 105° C. and a pressure of 1 to 20 kPa.

In accordance with another embodiment of the present invention, the modified diene-containing (co)polymer can be obtained by a method that includes the following steps:

a dissolution step: dissolving in a hydrocarbon solvent, optionally pre-crushed, the original diene-containing (co)polymer;

modification step: adding the components of the modifying system to the solution of the original diene-containing (co)polymer obtained in step a) in a hydrocarbon solvent;

a neutralization and separation step: adding an aqueous solution of a neutralizing agent to the reaction mass obtained in step b) and separating the aqueous and organic layers;

a precipitation step: precipitating the modified diene-containing (co)polymer by adding an excess alcohol precipitant to the organic layer;

isolation step: filtration and subsequent drying of the precipitated modified diene-containing (co)polymer,

wherein the method is characterized in that in stage b) of the modification, a mixture of halogen and water is used as the modifying system in the ratio halogen:water from 1:0.01 to 1:1, preferably from 1:0.7 to 1:0.5 , more preferably from 1:0.25 to 1:0.7 based on the total number of double bonds.

Stage a) dissolution

At this stage, the original diene-containing (co)polymer, optionally pre-crushed, is dissolved in a hydrocarbon solvent with stirring.

Grinding, if necessary, of the initial diene-containing (co)polymer is carried out by any methods known from the prior art, for example, using crushers (knife, hammer, rotary), mills (jet, screw), etc.

When dissolving the original diene-containing (co)polymer, mixing can be carried out by any method known from the prior art, for example, using an apparatus with a stirrer, a static mixer, at a temperature of from 10 to 50 ^° C, preferably from 15 to 40 ^° C, more preferably from 20 to 30 ^o C.

Suitable solvents include, but are not limited to, hydrocarbon solvents, preferably having a purity of 99% or more, and representing ethers, for example, tetrahydrofuran, halogenated saturated aliphatic hydrocarbons, for example, carbon tetrachloride, chloroform, dibromomethane, dichloromethane, 1,2- dichloroethane, cycloaliphatic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene, halogenated aromatic hydrocarbons such as bromobenzene, chlorobenzene and dichlorobenzene. Preferred hydrocarbon solvents are those which are liquid under the conditions of modification of the original diene-containing (co)polymer, and which do not undesirably react with the modifying system or the original (co)polymer. Preferably, tetrahydrofuran, chloroform, dichloromethane, dichloroethane, cyclohexane, toluene are used as the solvent, most preferably tetrahydrofuran, chloroform, dichloromethane is used.

The weight ratio of the hydrocarbon solvent to the original diene-containing (co)polymer is from 5:1 to 30:1, preferably from 8:1 to 20:1, more preferably from 10:1 to 15:1.

The dissolution process time is no more than 60 minutes, no more than 50 minutes, no more than 40 minutes, no more than 30 minutes, no more than 25 minutes, no more than 20 minutes, no more than 15 minutes, no more than 13 minutes, no more than 11 minutes, no more than 9 minutes, no more than 7 minutes, no more than 5 minutes.

The mass obtained as a result of the dissolution step described above is a solution of the original diene-containing (co)polymer in a hydrocarbon solvent.

Stage b) modification

At stage b) modification, the components of the modifying system are added to the solution of the initial diene-containing (co)polymer obtained at stage a).

In accordance with the present invention, halogen and water are jointly used as a modifying system in the presence of an aliphatic alcohol in a mass ratio of halogen:water from 1:0.01 to 1:1, preferably from 1:0.7 to 1:0.5, more preferably 1:0.25 to 1:0.7 based on the total number of double bonds.

The halogen used is chlorine, bromine or iodine in the form of elemental compounds as such, as well as in the form of solutions in a hydrocarbon solvent.

Preferably, elemental bromine (Br ₂ ) is used as the halogen as such, and also in the form of a solution in a hydrocarbon solvent with a bromine content of not more than 70 wt.%, more preferably not more than 60 wt.%, most preferably not more than 50 wt.%

In the context of the present invention, water is, but is not limited to, distilled, deionized, demineralized, osmotic, bidistilled water.

As aliphatic alcohol, alcohols with a content of carbon atoms from 1 to 6 are used, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, but are not limited to them. Preferably, propanol, butanol, isobutanol, pentanol are used as the aliphatic alcohol, more preferably butanol, isobutanol and pentanol are used.

The ratio of initial diene-containing (co)polymer: modifying system: aliphatic alcohol is from 1:1.5:3 to 1:5:3, more preferably 1:2:3 to 1:4:3, most preferably from 1:2, 5:3 to 1:3:3.

The order of adding the components of the modifying system and aliphatic alcohol to the solution of the initial diene-containing (co)polymer can be any. Preferably, an aliphatic alcohol is first added to the initial diene-containing (co)polymer solution, followed by the addition of water and a halogen or a solution thereof, or vice versa.

The addition of the halogen is preferably carried out in the form of its solution in an aliphatic hydrocarbon solvent by dosing the solution into the reaction mass. The halogen may be dissolved in a hydrocarbon solvent or a mixture thereof, preferably 99% or more pure, and which is an ether such as tetrahydrofuran, halogenated saturated aliphatic hydrocarbons such as chloroform, dibromomethane, dichloromethane, 1,2-dichloroethane, cycloaliphatic hydrocarbons , for example, cyclohexane, aromatic hydrocarbons, for example, toluene, halogenated aromatic hydrocarbons, for example, bromobenzene, chlorobenzene and dichlorobenzene. Preferably, the halogen is dosed in the form of its solution in the same solvent that was used in step a) to dissolve the initial diene-containing (co)polymer.

It is also possible to dose the halogen into the reaction mass in the form of a solution in a hydrocarbon solvent, as indicated above, after preliminary mixing of such a solution with water.

The dosing rate of the halogen solution or the mixture of halogen solution and water is 0.80 to 50 ml/min, preferably 1 to 10 ml/min, more preferably 1.5 to 5 ml/min. A very high dosing rate leads to local overheating of the reaction mass, an increase in its viscosity, which in turn can lead to the production of a modified diene-containing (co)polymer with a low (less than 35 wt.%) content of halogen atoms.

Also, adding the entire volume of the halogen solution to the solution of the original diene-containing (co)polymer can lead to its crosslinking, to local overheating of the reaction mass, an increase in the viscosity of the reaction mass, which can also lead to the production of a modified diene-containing (co)polymer with a low (less than 35 wt. %) content of halogen atoms.

The modification step is carried out in any batch or continuous equipment known from the prior art. Suitable equipment includes, but is not limited to, continuous stirred reactor, batch stirred reactor, stirred autoclave, which are designed to handle highly corrosive media.

Preferably, the step of modifying the original diene-containing (co)polymer is carried out without access to visible radiation, for example, by carrying out the modification process in darkened glass vessels, by wrapping the reactor in foil, or by carrying out the process in metal reactors, in order to reduce the likelihood of non-selective photocatalytic halogenation reactions.

The modification step is carried out at a temperature of 0 to 50 ^° C, preferably 20 to 45 ^° C, more preferably 30 to 40 ^° C, and atmospheric pressure.

The stirring speed of the reaction mass after adding the modifying system is from 50 to 600 rpm, preferably from 100 to 500 rpm, more preferably from 200 to 300 rpm.

The time of the modification step may be any convenient time sufficient to achieve the desired degree of modification of the initial diene-containing (co)polymer described above. Preferably, the modification time is at least 15 minutes, at least 20 minutes, at least 25 minutes, at least 30 minutes, at least 45 minutes, at least 60 minutes, at least 120 minutes.

The mass obtained after stage b) of modification contains the target product, a modified diene-containing (co)polymer.

Step c) neutralization and separation

This stage includes the neutralization of the reaction mass obtained in stage b) containing the modified diene-containing (co)polymer by adding a neutralizing agent solution, followed by washing the neutralized reaction mass with water and separating the aqueous layer and the organic layer containing the modified diene-containing (co)polymer.

As a neutralizing agent, non-alkaline aqueous solutions known from the prior art are used, but are not limited to, for example, sodium thiosulfate, sodium bisulfite, sodium carbonate, etc.

The molar ratio of neutralizing agent to added halogen is generally 1:1 to 3:1, preferably 1:1 to 2:1, more preferably 1:1.

Preferably, the neutralization process is carried out at a temperature of 15 to 50°C, preferably 20 to 40°C, more preferably 25 to 30°C, and atmospheric pressure.

Washing with water is carried out using at least one, preferably at least two, more preferably at least three times excess of water relative to the volume of the reaction mass subjected to neutralization, resulting in separation of the reaction mass into two layers: an organic layer containing a modified a diene-containing (co)polymer, and an aqueous layer.

The separation of the organic and aqueous layers is carried out using any method known from the prior art, for example, using a separating funnel, separator, sump.

Stage d) precipitation

To precipitate the modified diene-containing (co)polymer obtained in step b), a precipitating alcohol is added to the organic layer obtained in step c), containing the modified diene-containing (co)polymer. The weight ratio of alcohol-precipitant:modified diene-containing (co)polymer is in the range from 15:1 to 1:1, preferably from 10:1 to 3:1, more preferably from 5:1 to 4:1.

Suitable precipitant alcohols include, but are not limited to, aliphatic alcohols of 1 to 4 carbon atoms. Examples of such alcohols include, but are not limited to, methanol, ethanol, propanol, isopropanol, butanol, isobutanol. Preferably, methanol and ethanol are used as the precipitating alcohol.

Step e) isolation

At stage e) isolation to purify the modified diene-containing (co)polymer from solvent residues and precipitant alcohol, filtration is carried out using any apparatus known from the prior art, for example, using filters equipped with porous filtering baffles, suction filters, etc.

Filtration of the modified diene-containing (co)polymer is carried out at a temperature of from 20 to 40°C inclusive.

In order to remove water and/or its vapors, solvent and/or its vapors from the resulting modified diene-containing (co)polymer, the said (co)polymer is dried. The drying process of the modified diene-containing (co)polymer can be carried out by physical methods commonly used for separating and purifying organic substances (distillation of the solvent under reduced pressure, drying in a vacuum oven, etc.), as well as using drying reagents that remove moisture due to adsorption, hydrate formation or chemical reaction with water and solvents.

Preferably, the drying is carried out at a temperature of 50 to 105° C. and a pressure of 1 to 20 kPa.

The invention is explained in more detail in FIG. 1 , which shows a flowchart for obtaining a modified diene-containing (co)polymer through the epoxidation stage, where 101 is the block for dissolving the original diene-containing (co)polymer, 102 is the epoxidation block for the original diene-containing (co)polymer, 103 is the block for neutralization and separation, 104 - halogenation unit, 105 - neutralization and separation unit, 106 - precipitation unit, 107 - filtration unit, 108 - drying unit.

According to the presented method, if necessary, the crushed original diene-containing (co)polymer (1) is sent to the dissolution unit 101 , where it is mixed with a hydrocarbon solvent (2) to obtain a solution of the original diene-containing (co)polymer (3). Next, said solution of (co)polymer (3) enters the epoxidation unit 102 , which is also supplied with an epoxidizing agent (4). After that, the partially epoxidized diene-containing (co)polymer (5) obtained in block 102 is sent to the neutralization and separation unit 103 , into which a neutralizing agent (6) is supplied, followed by water (7) to wash the neutralized reaction mass, after which the separation of the organic a layer (9) containing a partially epoxidized diene-containing (co)polymer, and an aqueous layer (8). Then the organic layer (9) containing the partially epoxidized diene-containing (co)polymer enters the halogenation unit 104 , which is also supplied with water (10), aliphatic alcohol (11) and halogenating agent (12), resulting in a reaction mass, containing a modified diene-containing (co)polymer, which includes hydroxyl groups and halogen atoms. After that, the resulting reaction mass (13), containing a modified diene-containing (co)polymer, enters the neutralization and separation unit 105 , into which a neutralizing agent (14) is supplied, followed by water (15) for washing the neutralized reaction mass, after which separating the organic layer (17) containing the modified diene-containing (co)polymer and the aqueous layer (16). Then, the organic layer (17) containing the modified diene-containing (co)polymer enters the precipitation unit 106 , which is also supplied with an alcohol-precipitant (18) to precipitate the modified diene-containing (co)polymer. Next, the precipitated modified diene-containing (co)polymer (19) is sequentially fed to the filtration unit 107 and (20) to the drying unit 108 in order to obtain the final product - the modified diene-containing (co)polymer (21). Also, the method for producing a modified diene-containing (co)polymer may include a hydrocarbon solvent regeneration unit with its subsequent recycling to the initial diene-containing (co)polymer dissolution unit 101 (not shown in Fig. 1).

The invention is also explained in more detail in FIG. 2 , which shows a flowchart for obtaining a modified diene-containing (co)polymer using a modifying system, where 201 is a block for dissolving the original diene-containing (co)polymer, 202 is a block for modifying the original diene-containing (co)polymer, 203 is a block for neutralization and separation, 204 - settling unit, 205 - filtration unit, 206 - drying unit.

According to the presented method, if necessary, the crushed original diene-containing (co)polymer (1) is sent to the dissolution unit 201 where it is mixed with a hydrocarbon solvent (2) to obtain a solution of the original diene-containing (co)polymer (3). Next, the specified solution of (co)polymer (3) enters the modification unit 202 , which also serves modifying system (4) and aliphatic alcohol (5). After that, the modified diene-containing (co)polymer (6) obtained in block 202 is sent to the neutralization and separation unit 203 , into which a neutralizing agent (7) is supplied, followed by water (8) for washing the neutralized reaction mass, after which the separation of the organic layer is carried out (10) containing a modified diene-containing (co)polymer, and an aqueous layer (9). Then, the organic layer (10) containing the modified diene-containing (co)polymer enters the deposition unit 204 , which is also supplied with an alcohol-precipitant (11) to precipitate the modified diene-containing (co)polymer. Next, the precipitated modified diene-containing (co)polymer (12) is sequentially fed to the filtration unit 205 and (13) to the drying unit 206 in order to obtain the final product - the modified diene-containing (co)polymer (14). Also, the method for producing a modified diene-containing (co)polymer may include a block for regenerating a hydrocarbon solvent with its subsequent recycling to a block 201 for dissolving the original diene-containing (co)polymer (not shown in Fig. 2).

Shown in FIG. 1 and FIG. 2 diagrams are examples of the present invention and do not limit it.

The modified diene-containing (co)polymers obtained in accordance with the present invention can be used as flame retardants (flame retardants) in various polymers and polymer compositions, for example, based on expandable polystyrene, to impart flame retardant properties to them. In this case, flame retardants (flame retardants) must be compatible with the polymer or polymer composition.

In accordance with the present invention, a modified diene-containing (co)polymer is introduced into expandable polystyrene at the stage of its production by a method including the production of polystyrene by polymerization of styrene in the presence of a polymerization initiator, a polymerization stabilizer, etc., followed by the stage of foaming the resulting polystyrene (see patent US5086078, for example).

The content of the modified diene-containing (co)polymer used as a flame retardant (flame retardant) should not be less than 0.5 parts by weight, preferably not less than 0.7 wt. hours, more preferably not less than 1 wt. hours, otherwise the effectiveness of improving the fire-resistant characteristics of the resulting expandable polystyrene is reduced.

In addition, compositions based on expandable polystyrene, according to the present invention, may also include the following conventional additives to achieve the required set of technological, physical, mechanical and operational characteristics, for example: antistatic agents, stabilizers, dyes, lubricants, fillers, anti-agglomerators, etc. .

In accordance with the present invention, expandable polystyrene compositions can be used for the production of a wide range of products, such as building heat and sound insulation, in particular heat and sound insulation boards, fixed formwork, components for cars, floating products, and also as raw materials for polystyrene foam blocks used in the construction of roads and bridges, packaging of household appliances.

The modified diene-containing (co)polymer obtained according to the present invention can be used as a flame retardant (flame retardant) in expandable polystyrene, because. characterized by high thermal stability, namely, the temperature of 5% weight loss of at least 180 ^° C, measured by thermogravimetric analysis, does not affect the polymerization process and the process of formation of polystyrene granules, which is confirmed by the granulometric composition of the resulting polystyrene, and also exhibits high compatibility with polystyrene. In addition, the flame retardant (flame retardant) obtained in accordance with the present invention imparts fire retardant properties to the expandable polystyrene, which makes it possible to classify the expandable polystyrene, which contains the flame retardant (flame retardant) proposed in accordance with the present invention, as moderately flammable materials with a flammability class B2 (in accordance with Clause 7, Article 13 of the Technical Regulations on Fire Safety Requirements (Federal Law No. 123-FZ of July 22, 2008, as amended on July 29, 2017)).

The present invention is more specifically described in the following examples. These examples are provided only to illustrate the present invention and do not limit it.

Implementation of the invention

Methods for studying the modified (co)polymer

Thermogravimetric analysis (TGA)

In order to determine the thermal stability of the obtained modified diene-containing (co)polymer, the temperature of 5% weight loss was measured by studying the thermal behavior of (co)polymer samples by the method of simultaneous thermal analysis (STA) (combined methods of differential scanning calorimetry (DSC) and thermogravimetry (TG) ) in accordance with ISO11358 using the STA 449 Jupiter NETZSCH.

Experimental conditions: inert atmosphere (argon) in the temperature range from 30°C to 600°C, heating rate - 10°C/min.

Nuclear magnetic resonance (NMR) method

The microstructure of the polymer chain of samples of the modified diene-containing (co)polymer was determined by ¹ H NMR spectroscopy using a Bruker Avance III instrument (400 MHz). To prepare a solution for research, a sample weighing 30 mg was dissolved in 0.6 ml of deuterated chloroform. The number of scans on ¹ H cores is 32.

Gel Permeation Chromatography (GPC)

The molecular weight characteristics of samples of the original diene-containing (co)polymer and modified diene-containing (co)polymer were determined by low-temperature GPC in accordance with ISO16014-3 on an Agilent 1200 liquid chromatograph, a refractometric detector.

Analysis conditions: eluent - tetrahydrofuran; temperature of dissolution and measurement - 40°C, eluent flow rate 1.0 ml/min; column PLgel Mixed-C (2-3 pcs). The calculation was carried out by relative calibration according to polystyrene standards (EasiVial PS-H 4ml, Agilent Technologies) using Mark-Houwink constants for (co)polymer K=0.000374, α=0.699.

Granulometric composition of polystyrene

The granulometric composition of the polystyrene powder was determined on a HAVER EML digital plus particle sieving apparatus. For sieving, a set of sieves with a mesh diameter of 2.0 was used; 1.6; 1.0; 0.70; 0.40; 0.20 mm. Sieving time - 15 minutes. The mass of the powder on the sieves was determined by the gravimetric method.

Pressing polystyrene samples

The samples were pressed on a Collin hydraulic press with a force of 300 kN. The sample was preliminarily kept in an oven at a temperature of 50°C. The pressing of the samples was carried out for 18 minutes, with gradual heating to 190°C for 5 minutes, a pressure of 50 bar; kept the sample under pressure of 50 bar 190°C for 3 minutes. Subsequently, the sample was cooled to 40° C. under a pressure of 50 bar for 10 minutes.

X-ray fluorescence analysis

The distribution of the modified diene-containing (co)polymers in polystyrene was determined by measuring the intensity of the distribution of bromine atoms in the layer of the polystyrene sample.

The study was carried out on a SHIMADZU XRF-1800 wave-dispersive X-ray fluorescence spectrometer with a mapping function. A preliminarily prepared compressed polystyrene sample in the form of a plate 1 mm thick was placed in a special holder for local analysis with a mask diameter of 30 mm. Measurement parameters: pitch 0.5 mm, X-ray tube voltage and current (Rh-anode) 40kV, 95mA, angle 29.97 ^° . The intensity of bromine was measured at each point, and histograms of the distribution of bromine in the samples were modeled from the data obtained.

Scanning electron microscopy (SEM)

The compatibility of the modified diene-containing (co)polymer containing hydroxyl groups and bromine atoms obtained in accordance with the present invention with polystyrene was determined by measuring the distribution intensity of bromine atoms in the layer of the polystyrene sample.

The study is carried out using an FEI Quanta 3D scanning electron microscope at an accelerating voltage of 30 kV and a DualBSD (backscatter detector) in low vacuum.

Fire test

Determination of the fire resistance of samples of expanded polystyrene containing a flame retardant (flame retardant) was carried out in accordance with TU 2214-019-53505711-2010.

Sample preparation: 40 mm was cut from the molded part and discarded. Then, 5 samples were cut out with dimensions (190±1)×(90±0.5)×(20.0±0.5) mm so that there was no technological film formed during the formation of the block, cracks, chips and shells. The lower face of the sample should be cut smoothly with sharp edges and form right angles with the side faces.

The method is based on determining the height of the flame of a burning sample, within 20 s after the removal of the fire source.

Test preparation:

The device was prepared and put into operation. The ventilation in the chamber was turned off. The air velocity was measured with a hot-wire anemometer in the exhaust pipe of the test chamber. The required value is from 0.5 to 0.8 m/s.

Before testing, the samples were conditioned for at least 14 days at a temperature of (23±5)ᵒС and relative air humidity (50±20)% to constant weight.

Next, a mark was applied to the sample at a distance of 150 mm from the lower edge on the front and back sides. Then the samples were hung in the firing chamber vertically in the mount with the measuring mark up, and the lower edge was placed in the same plane with the mark of the tripod holder. Then the holder with the sample was moved vertically so that the nozzle-stabilizer for exposure to the flame touched the lower edge of the sample.

After that, the burner was lit and the flame was adjusted using a template held on the side so that the height of the flame with a yellow glow was (20 ± 1) mm. Before each flame exposure to the sample, the height of the flame was checked.

Filter paper was placed in 2 layers under the sample at the bottom of the test chamber in a wire box.

Testing:

The firing chamber was closed. From the side, a burner with a flame turned at an angle of 45 ^° was brought to the center of the free end (edge) of the sample, after which the stopwatch was turned on. The sample was exposed to the flame for 15 seconds, after which the burner was withdrawn and the combustion of the sample was observed. In this case, the time was measured from the beginning of exposure to the flame until the moment when the top of the flame of the burning sample reached the measured mark of 150 mm, if before that the flame did not go out by itself. The tests were interrupted after 20 s (from the beginning of the sample treatment with a flame) and the maximum flame height and dripping (falling off of burning fragments) were evaluated.

The test is considered completed if, for each of the 5 tested samples, the top of the flame of the burning sample does not go beyond the measuring mark before the expiration of the 20th second, and when burning drops fall (burning fragments fall off), they burn on filter paper for no more than 2 s, and also do not ignite the filter paper.

Example 1 . Obtaining a modified butadiene-styrene copolymer containing 0.05 wt.% hydroxybrominated butadiene units

The solution of the original styrene-butadiene (co)polymer (20 g in 200 g of dichloromethane) was cooled with stirring to a temperature of 0-5°C. To the cooled solution of the (co)polymer was dosed 0.4 g of a 10 wt.% solution of m-chloroperbenzoic acid in dichloromethane (1 mol of acid per 1 mol of epoxidized diene units). The temperature of the cooling bath was maintained at 0-5°C. After adding the entire volume of acid, the reaction mass was stirred at a given temperature for another 30 min, then for 1 h at a temperature of 25°C and for 1 h at 50°C. After the end of epoxidation, the residues of m-chloroperbenzoic acid were neutralized with a sodium hydroxide solution, and the reaction mass was washed with a threefold volume excess of water, followed by separation of the aqueous and organic layers.

Next, the organic layer was placed in a dark glass flask, 60 g of butanol and 5 g of water were added, a solution of bromine in dichloromethane (39.4 g of bromine per 50 ml of dichloromethane) was dosed over 10–20 min. After adding all the bromine solution in dichloromethane, stirring was continued for 30 min, then 10% sodium thiosulfate solution was added and bromine was neutralized for 60 min. After that, the inorganic layer was decanted, and the organic layer was washed with a three-volume excess of distilled water. Then, the modified styrene-butadiene (co)polymer containing hydroxyl groups and bromine atoms was precipitated in a fivefold excess of alcohol, separated, and dried by distillation of the solvent at 91 ^° C and 10 kPa, followed by additional drying in a vacuum oven at 70 ^° C and 0.5 kPa.

Characteristics of the product obtained according to Example 1 are shown in Table. 1.

Example 2 . Obtaining a modified butadiene-styrene copolymer containing 0.15 wt.% hydroxybrominated butadiene units

Carried out as in Example 1, except that 1.08 g of a 10% by weight solution of m-chloroperbenzoic acid in dichloromethane was added.

Characteristics of the product obtained according to Example 2 are shown in Table. 1.

The ¹ H NMR spectrum of the resulting modified styrene-butadiene copolymer is shown in FIG. 3.

^1H NMR spectrum (CDCl3, δ, ppm): 6.6-7.1 (styrene); 5.6 (1,4-butadiene); 5.1 (1,2-butadiene); 3.8-4.2 (brominated butadienes); 3.6 (hydroxyl groups).

Example 3. Obtaining a modified styrene-butadiene copolymer containing 1.25 wt.% hydroxybrominated butadiene units

Carried out according to Example 1, except that at the stage of epoxidation, 9 g of a 10 wt.% solution of m-chloroperbenzoic acid in dichloromethane was added to the reaction mass.

Characteristics of the product obtained according to Example 3 are shown in Table. 1.

Example 4. Obtaining a modified styrene-butadiene copolymer containing 1.9 wt.% hydroxybrominated butadiene units

It was carried out according to Example 1, except that at the stage of epoxidation, 13.7 g of a 10 wt.% solution of m-chloroperbenzoic acid in dichloromethane was added to the reaction mass.

Characteristics of the product obtained according to Example 4 are shown in Table. 1.

Example 5 Preparation of a Modified Styrene-Butadiene Copolymer Containing 5.5 Wt% Hydroxybrominated Butadiene Units (Comparative)

Carried out according to Example 1, except that at the stage of epoxidation, 35.99 g of a 10 wt.% solution of m-chloroperbenzoic acid in dichloromethane was added to the reaction mass.

Characteristics of the product obtained according to Example 5 are shown in Table. 1.

It is worth noting that in the process of pressing polystyrene plates in order to determine the compatibility of the compatibility of the flame retardant (flame retardant) proposed in accordance with the present invention with polystyrene using XPLA and SEM methods at a pressure of 50 bar, a short-term pressure change was observed for samples of polystyrene containing a flame retardant according to Example 3 to 58 bar due to the low density of the resulting polystyrene pellets, which led to the sticking of the polystyrene pellets, which in turn made it impossible to carry out fire tests on the expanded polystyrene.

Example 6 Preparation of a Brominated Styrene Butadiene Copolymer

A solution of the starting styrene-butadiene copolymer in dichloromethane (10 g of copolymer per 150 g of dichloromethane) was added to a dark glass flask with a volume of 250 ml. Next, 30 g of butanol was added to the flask, after which a solution of 19.66 g of bromine in 20 ml of dichloromethane was dosed. The bromination reaction was carried out for 30–40 min. After completion of the reaction, sodium hydroxide (NaOH) solution was added to the flask and neutralization was carried out for 1 hour. Then the reaction mass containing the brominated butadiene-styrene copolymer was washed with a three-fold volume excess of water.

Next, the obtained brominated styrene-butadiene copolymer was filtered, followed by its precipitation in isopropanol, after which it was dried by distilling off the solvent at a temperature of 30-95 ^° C and 3 kPa, followed by additional drying in a vacuum oven at 70 ^° C and 0.5 kPa .

Characteristics of the brominated styrene-butadiene copolymer obtained according to Example 6 are presented in Table. 1.

Example 7 Preparation of Modified Styrene Butadiene Copolymer Containing 0.15 Wt % Hydroxybrominated Butadiene Units Using a Modifying System

A solution of the starting styrene-butadiene copolymer in dichloromethane (10 g of (co)polymer per 150 g of dichloromethane) was added to a dark glass flask with a volume of 250 ml. Next, 30 g of butanol, 10 g of water were added to the flask, after which a solution of 19.7 g of bromine in 20 ml of dichloromethane was dosed. The modification reaction was carried out for 30-40 min. After completion of the reaction, a 20% sodium metabisulfite solution was added to the flask and neutralization was carried out for 1 hour. Then the reaction mass containing the modified diene-containing copolymer was washed with a three-fold volume excess of water.

Further, the resulting modified diene-containing copolymer was filtered off, followed by its precipitation in isopropanol, after which it was dried by distilling off the solvent at a temperature of 30-95 ^° C and 3 kPa, followed by additional drying in a vacuum oven at 70 ^° C and 0.5 kPa.

Characteristics of the product obtained according to Example 7 are shown in Table. 1.

Table 1. Comparative table of experimental results for the preparation of modified diene-containing (co)polymers

Example No. Degree of hydroxybromination, % Weight average molecular weight, g/mol Temperature 5% weight loss, °C Styrene content,
wt% Bromine content, wt.% Content of OH-groups, wt.% Example 1 0.05 95 000 209 21.2 78.72 0.08 Example 2 0.15 92 500 212 20.2 79.80 0.15 Example 3 1.25 91 000 210 20.64 78.73 0.62 Example 4 1.90 91 000 211 20.3 78.40 1.3 Example 5 5.00 90 000 210 19.59 78.80 1.60 Example 6 absent 310 000 190 20.79 79.21 - Example 7 0.15 92 700 212 19.8 80.03 0.17

Example 8. Obtaining expandable polystyrene

87 parts of water and 0.43 parts of a polymerization stabilizer (a mixture of sodium pyrophosphate and magnesium sulfate) were mixed in a flask at a temperature of 25 ^° C. To this mixture was added with stirring a mixture of 100 parts of styrene, 0.46 parts of a mixture of polymerization initiators (benzoyl peroxide and tert -butylperbenzoate), 0.62 parts of a flame retardant (flame retardant) obtained in accordance with examples 1-5 , and 0.21 parts of a flame retardant initiator (flame retardant) (dicumyl peroxide). The mixture was stirred for 2 hours at up to 85°C, then heated to 115°C for 4.5 hours. 70 min after the temperature in the flask reached 80°C, a 10% aqueous solution of polyvinylpyrrolidone was added to the reaction mixture. After an additional 100-120 minutes, a solution of 0.10 parts of a chain transfer agent in 4.7 parts of a blowing agent (n-heptane) was added to the reaction mass - the step of foaming the polystyrene. After reaching 115° C., the flask was kept at a constant temperature for 3 hours, after which the mixture was cooled to a temperature of 25 ^° C. for 3 hours.

Further, the determination of the particle size distribution of the polystyrene obtained before the foaming stage was carried out. The results of determining the particle size distribution are given in Table. 2.

Table 2. Granulometric composition of polystyrene containing a flame retardant (flame retardant)

Granule size, mm Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 2.00 1.70 0.06 0.80 0.29 20.02 1.30 1.60 4.01 1.15 3.70 1.17 12.09 2.51 1.00 29.57 40.75 18.20 30.22 24.79 21.57 0.70 53.92 47.48 64.20 54.89 28.98 47.52 0.40 15.8 9.11 12.66 10.62 11.05 25.30 0.2 0.20 1.26 0.44 0.81 0.36 - bottom 1.80 0.19 0 0 0 1.80 Sum of fractions
(1.60+1.00+0.70)
according to TU 2214-019-53505711-2010 87.50 89.38 86.10 84.28 65.86 71.60

The particle size distribution according to TU 2214-019-53505711-2010 should have a total yield of fractions (1.60+1.00+0.70) (target fractions) of more than 85%.

Comparison of the particle size distribution of polystyrene samples containing flame retardants (flame retardants) according to Examples 1-4 (Table 2) shows that the introduction of hydroxyl groups into the (co)polymer structure in a small amount (from 0.05 to 1.90 wt. % of hydroxybrominated diene units) does not adversely affect the stability of the suspension in the synthesis of polystyrene, and also does not worsen its particle size distribution. At the same time, an increase in the content of hydroxybrominated diene units in the structure of the flame retardant (flame retardant) (Example 5) to 5.5 wt.% leads to a decrease in the yield of target polystyrene fractions due to the high polarity of the flame retardant (flame retardant) molecule, resulting in a shift in particle size distribution towards larger fractions. In this case, there is a tendency for such granules to stick together.

In order to assess the compatibility of the flame retardant (flame retardant) obtained in accordance with the present invention with polystyrene, polystyrene plates are studied by XRF and SEM methods according to the methods described above.

On FIG. Figure 4 shows the distribution of bromine in samples of polystyrene containing a flame retardant (flame retardant): (a) HBCD, (b) brominated styrene-butadiene copolymer, (c) modified styrene-butadiene copolymer containing 0.15 wt.% hydroxybrominated butadiene units, ( d) modified butadiene-styrene copolymer containing 5.5 wt.% hydroxybrominated butadiene units. Meanwhile, in FIG. 4, the brightest (red) regions correspond to the highest concentration of bromine atoms, and the brightest (yellow) regions correspond to the lowest concentration of bromine atoms, respectively.

From the data shown in Fig. Figure 4 shows that sample a) of polystyrene containing HBCD as a flame retardant (flame retardant) has a high uniform concentration of bromine throughout the entire volume under study. A polystyrene sample b) containing a brominated copolymer of butadiene and styrene as a flame retardant (flame retardant) has a smaller area of the dark (red) region, which indicates a low concentration of bromine in the sample.

It follows from the presented data that polystyrene containing a modified butadiene-styrene copolymer containing 0.15 wt.% hydroxybrominated butadiene units has a high concentration of bromine in its composition, and also has a distribution in polystyrene similar to the distribution of bromine in polystyrene containing HBCD. Therefore, said modified styrene-butadiene copolymer provides expandable polystyrene with fire retardant properties comparable to HBCD, which is also confirmed by the fire tests carried out, which made it possible to classify expandable polystyrene containing the flame retardant (flame retardant) proposed in accordance with the present invention as a moderately flammable material with a class flammability B2 (in accordance with clause 7, article 13 of the "Technical Regulations on Fire Safety Requirements" (Federal Law of July 22, 2008 N 123-FZ, as amended on July 29, 2017)).

The concentration of bromine in polystyrene containing a modified butadiene-styrene copolymer containing 5.5 wt.% hydroxybrominated butadiene units is lower than for polystyrene containing HBCD, and is similar to the distribution of bromine in polystyrene containing a brominated butadiene-styrene copolymer. This is explained by the fact that due to the high content of hydroxybrominated butadiene units in the flame retardant (flame retardant) molecule, the total amount of brominated butadiene units decreases, which, in turn, does not allow the specified modified styrene-butadiene copolymer to provide the required fire retardant properties to expandable polystyrene.

On FIG. 5 shows photographs of samples of polystyrene containing a flame retardant (flame retardant): (a) HBCD, (b) brominated styrene-butadiene copolymer, (c) modified styrene-butadiene copolymer containing 0.15 wt.% hydroxybrominated butadiene units, (d) modified butadiene-styrene copolymer containing 5.5 wt.% hydroxybrominated butadiene units, obtained by SEM.

From the data obtained, it can be seen that the resulting domains (light areas) containing bromine, due to the insufficiently uniform distribution of the flame retardant (flame retardant) sample in polystyrene, become the brightest on all samples, with the exception of sample (a) with HBCD, which is evenly distributed in polystyrene . It should be noted that for polystyrene samples containing a modified butadiene-styrene copolymer (with a content of hydroxybrominated butadiene units of 0.15 wt.% and 5.5 wt.%), the number of domains is small, which also indicates a more uniform distribution of the flame retardant (flame retardant) in polystyrene samples compared to a polystyrene sample containing brominated styrene-butadiene copolymer as a flame retardant (flame retardant).

Thus, the results of the experiments showed that the use of a modified styrene-butadiene copolymer containing hydroxyl groups and bromine atoms in its structure as a flame retardant (flame retardant) is evenly distributed in polystyrene, which also makes it possible to provide expandable polystyrene with fire retardant properties comparable to HBCD.

Claims (118)

1. Modified diene-containing (co)polymer containing in its structure halogen atoms and hydroxyhalogenated diene units, having a temperature of 5% weight loss, which is at least 180°C, a weight average molecular weight of at least 1500 g/mol, content halogen at least 35 wt.% based on the weight of the entire (co)polymer and the content of hydroxyhalogenated diene units in an amount of from 0.05 to 1.9 wt.% based on the weight of the entire (co)polymer. 2. Modified diene-containing (co)polymer according to claim 1, which contains hydroxyhalogenated diene units, preferably in an amount of from 0.05 to 1.75 wt.%. 3. The modified diene-containing (co)polymer according to claim 1, which contains hydroxyhalogenated diene units more preferably in an amount of from 0.1 to 1.75 wt.%. 4. The modified diene-containing (co)polymer according to claim 1, wherein the hydroxyhalogenated diene units are hydroxybrominated diene units. 5. Modified diene-containing (co)polymer according to claim 1, characterized by a temperature of 5% weight loss, preferably at least 200°C., more preferably at least 220°C. 6. The modified diene-containing (co)polymer according to claim 1, which has a weight average molecular weight of preferably 2,000 to 280,000 g/mol, more preferably 10,000 to 150,000 g/mol, most preferably 60,000 to 100,000 g/mol. 7. The modified diene-containing (co)polymer according to claim 1, in which the content of halogen atoms is preferably at least 60 wt.%, more preferably at least 75 wt.%. 8. Modified diene-containing (co)polymer according to any one of paragraphs. 1-7, where the (co)polymer is a modified butadiene, butadiene-styrene, butadiene-styrene-isoprene (co)polymer. 9. The modified diene-containing (co)polymer according to claim 8, wherein the (co)polymer is a modified styrene-butadiene copolymer. 10. The method of obtaining a modified diene-containing (co)polymer according to any one of paragraphs. 1-9, including the following steps: a) the step of dissolving the initial diene-containing (co)polymer in a hydrocarbon solvent; b) an epoxidation step comprising adding an epoxidizing agent to the solution of the original diene-containing (co)polymer obtained in step a) in a hydrocarbon solvent; c) a neutralization and separation step comprising adding an aqueous solution of a neutralizing reagent to the reaction mass obtained in step b) and separating the aqueous and organic layers; d) a halogenation step comprising adding a halogenating agent, water, to the organic layer obtained in step c); e) a neutralization and separation step comprising adding an aqueous solution of a neutralizing agent to the reaction mass obtained in step d) and separating the aqueous and organic layers; f) a precipitation step comprising precipitating the modified diene-containing (co)polymer by adding an excess alcohol precipitant to the organic layer obtained in step (e); g) a separation step comprising filtration and subsequent drying of the precipitated modified diene-containing (co)polymer. 11. The method according to p. 10, characterized in that the initial diene-containing (co)polymer is a polymers and copolymers of a conjugated diene. 12. The method according to p. 11, characterized in that the conjugated diene is a conjugated diene selected from the group: 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2-ethyl-1,3- butadiene, 2,3-di(C1-C5 alkyl)-1,3-butadienes such as 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl- 3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene, phenyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 2-methyl-pentadiene, 4-methyl-pentadiene, or mixtures thereof. 13. The process according to claim 12, wherein the conjugated diene is preferably 1,3-butadiene or isoprene. 14. The method according to p. 11, characterized in that as a comonomer in the original diene-containing (co)polymer, vinyl aromatic compounds selected from the group are used: styrene, α-methylstyrene, ortho-, meta- and para-methylstyrene, 3-vinyltoluene, ethylvinylbenzene, 4-cyclohexylstyrene, p-tert-butylstyrene, methoxystyrenes, vinylmesitylene, divinylbenzene, 1-vinylnaphthalene, 2,4,6-trimethylstyrene, or mixtures thereof. 15. The method according to p. 14, characterized in that styrene or α-methylstyrene is preferably used as the comonomer in the original diene-containing (co)polymer. 16. The method according to p. 10, characterized in that the original diene-containing (co)polymer is a butadiene, butadiene-styrene, butadiene-styrene-isoprene (co)polymer. 17. The method according to p. 16, characterized in that the initial diene-containing (co)polymer is preferably a butadiene-styrene copolymer. 18. The method according to p. 10, characterized in that the original diene-containing (co)polymer has a weight average molecular weight of at least 700 g/mol, preferably from 1000 to 400000 g/mol, more preferably from 2000 to 300000 g/mol, more preferably 5,000 to 200,000 g/mol, more preferably 20,000 to 120,000 g/mol, most preferably 20,000 to 50,000 g/mol. 19. The method according to p. 10, characterized in that the initial diene-containing (co)polymer has a polydispersity coefficient from 0.8 to 3, more preferably from 1 to 1.8, most preferably from 1.1 to 1.5. 20. The method according to p. 10, characterized in that the content of 1,2-units in the original diene-containing (co)polymer is from at least 10 to 100 wt.%, preferably from at least 50 to 99 wt.%, more preferably from 60 to 80 wt.% on the polydiene part of the (co)polymer. 21. The method according to claim 10, characterized in that hydrocarbon solvents are used as a solvent in the dissolution stage, which are ethers, such as tetrahydrofuran, halogenated saturated aliphatic hydrocarbons, such as carbon tetrachloride, chloroform, dibromomethane, dichloromethane, 1,2 -dichloroethane, cycloaliphatic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene, halogenated aromatic hydrocarbons such as bromobenzene, chlorobenzene and dichlorobenzene. 22. The method according to p. 21, characterized in that tetrahydrofuran, chloroform, dichloromethane, dichloroethane, cyclohexane, toluene are preferably used as a solvent in the dissolution step. 23. The method according to p. 22, characterized in that tetrahydrofuran, chloroform, dichloromethane is more preferably used as a solvent in the dissolution stage. 24. The method according to p. 10, characterized in that the dissolution in step a) is carried out at a temperature of from 10 to 50°C, preferably from 15 to 40°C, more preferably from 20 to 30°C. 25. The method according to p. 10, characterized in that the mass ratio of hydrocarbon solvent to the original diene-containing (co)polymer in stage a) dissolution is from 5:1 to 30:1, preferably from 8:1 to 20:1, more preferably from 10:1 to 15:1. 26. The method according to p. 10, characterized in that the time of the dissolution process is not more than 60 minutes, not more than 50 minutes, not more than 40 minutes, not more than 30 minutes, not more than 25 minutes, not more than 20 minutes, not more than 15 minutes , no more than 13 minutes, no more than 11 minutes, no more than 9 minutes, no more than 7 minutes, no more than 5 minutes. 27. The method according to any one of paragraphs. 10-26, characterized in that the original diene-containing (co)polymer is pre-crushed. 28. The method according to claim 10, characterized in that pure substances containing active oxygen or mixtures thereof are used as an epoxidizing agent in stage b) epoxidation, solutions of such substances with an epoxidizing agent content of 10 to 50 wt.%, preferably from 15 to 30% by weight, more preferably 20 to 25% by weight, or mixtures thereof. 29. The method according to claim 28, characterized in that performic acid, peracetic acid, metachloroperbenzoic acid, hydrogen peroxide, or mixtures thereof are used as the epoxidizing agent. 30. The method according to claim 10, characterized in that the epoxidizing agent is used in an amount sufficient to epoxidize no more than 6 mol.% non-aromatic double bonds, preferably no more than 2.5 mol.% non-aromatic double bonds, more preferably no more than 0 .5 mol.% non-aromatic double bonds. 31. The method according to claim 10, characterized in that the dosing of the epoxidizing agent is carried out at a rate of from 0.80 to 50 ml/min, preferably from 1 to 10 ml/min, more preferably from 1.5 to 5 ml/min. 32. The method according to p. 10, characterized in that stage b) epoxidation is carried out at a temperature of from -20 to 100°C, preferably from -10 to 50°C, more preferably from 0 to 20°C. 33. The method according to p. 10, characterized in that the time stage b) epoxidation is at least 15 minutes, at least 20 minutes, at least 25 minutes, at least 30 minutes, at least 45 minutes, at least at least 60 min, at least 120 min. 34. The method according to claim 10, characterized in that at stage c) neutralization and separation, aqueous solutions of sodium hydroxide, sodium thiosulfate, sodium bisulfite, sodium carbonate are used as a neutralizing agent. 35. The method according to p. 10, characterized in that in stage c) neutralization and separation, the molar ratio of the amount of neutralizing agent to the amount of added halogen is usually from 1:1 to 3:1, preferably from 1:1 to 2:1, more preferably 1:1. 36. The method according to p. 10, characterized in that in stage c) neutralization and separation, the neutralization process is carried out at a temperature of from 15 to 50°C, preferably from 20 to 40°C, more preferably from 25 to 30°C. 37. The method according to claim 10, characterized in that in stage d) halogenation, chlorine, bromine, iodine are used as halogen in the halogenating agent. 38. The method according to claim 37, characterized in that, in step d) of the halogenation, bromine is preferably used as the halogen in the halogenating agent. 39. The method according to p. 10, characterized in that the halogenating agent is bromine as such, a solution with a bromine content of not more than 70 wt.%, preferably not more than 60 wt.%, more preferably not more than 50 wt.%, quaternary bromides ammonium, quaternary phosphonium bromides or mixtures thereof. 40. The method according to claim 39, characterized in that elemental bromine and quaternary ammonium bromides or quaternary phosphonium bromides are preferably used simultaneously as the halogenating agent. 41. The method according to p. 39, characterized in that phenyltriethylammonium bromide, benzyltrimethylammonium bromide, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetra-n-butylammonium bromide or mixtures thereof are used as quaternary ammonium bromide. 42. The method according to claim 39, characterized in that tetramethylphosphonium bromide, tetraethylphosphonium bromide, tetrapropylammonium bromide, tetra-n-butyl-ammonium tribromide or mixtures thereof are used as quaternary phosphonium bromide. 43. The method according to p. 10, characterized in that stage d) halogenation is carried out in the presence of an aliphatic alcohol. 44. The method according to p. 43, characterized in that the molar ratio of the original diene-containing (co)polymer:halogenating agent:aliphatic alcohol is from 1:1.5:3 to 1:5:3, more preferably from 1:2:3 up to 1:4:3, most preferably from 1:2.5:3 to 1:3:3. 45. The method according to claim 10, characterized in that the molar ratio of elemental bromine: bromine atoms in quaternary ammonium bromide or quaternary phosphonium bromide is from 1:1 to 1:4, more preferably from 1:2 to 1:3, most preferably from 1:1 to 1:1.5. 46. The method according to p. 43, characterized in that methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol are used as aliphatic alcohol in stage d) of halogenation. 47. The method according to p. 10, characterized in that in stage d) halogenation, the rate of addition of bromine is from 0.80 to 50 ml/min, preferably from 1 to 10 ml/min, more preferably from 1.5 to 5 ml/ min. 48. The method according to p. 10, characterized in that stage d) halogenation is carried out at a temperature of from 0 to 50°C, preferably from 20 to 45°C, more preferably from 30 to 40°C. 49. The method according to p. 10, characterized in that in stage d) halogenation, the stirring speed of the reaction mass after adding the halogenating agent is from 50 to 600 rpm, preferably from 100 to 500 rpm, more preferably from 200 to 300 rpm /min 50. The method according to p. 10, characterized in that the time of stage d) halogenation is at least 15 minutes, at least 20 minutes, at least 25 minutes, at least 30 minutes, at least 45 minutes, according to at least 60 minutes, at least 120 minutes. 51. The method according to claim 10, characterized in that at stage e) neutralization and separation, aqueous solutions of sodium hydroxide, sodium thiosulfate, sodium bisulfite, sodium carbonate are used as a neutralizing agent. 52. The method according to p. 10, characterized in that in stage e) neutralization and separation, the molar ratio of the amount of neutralizing agent to the amount of added halogenating agent is usually from 1:1 to 3:1, preferably from 1:1 to 2:1, more preferably 1:1. 53. The method according to p. 10, characterized in that in stage e) neutralization and separation, the neutralization process is carried out at a temperature of from 15 to 50°C, preferably from 20 to 40°C, more preferably from 25 to 30°C. 54. The method according to claim 10, characterized in that at the stage of precipitation, methanol, ethanol, propanol, isopropanol, butanol, isobutanol are used as an alcohol-precipitant. 55. The method according to p. 10, characterized in that the mass ratio of alcohol-precipitant:modified (co)polymer is from 10 to 1, preferably from 15 to 5, more preferably from 5 to 4. 56. The method according to p. 10, characterized in that the filtration of the modified diene-containing (co)polymer is carried out using filters equipped with porous filter walls, suction filters. 57. The method according to p. 10, characterized in that the filtration of the modified diene-containing (co)polymer is carried out at a temperature of from 20 to 40°C. 58. The method according to p. 10, characterized in that the drying of the modified diene-containing (co)polymer is carried out at a temperature of from 50 to 105°C. 59. The method according to p. 10, characterized in that the drying of the modified diene-containing (co)polymer is carried out at a pressure of from 1 to 20 kPa. 60. The method of obtaining a modified diene-containing (co)polymer according to any one of paragraphs. 1-9, which includes the following steps: a) a dissolution step comprising dissolving the diene-containing (co)polymer in a hydrocarbon solvent; b) a modification step by adding the components of the modifying system to a solution of the initial diene-containing (co)polymer in a hydrocarbon solvent obtained in step a); c) a neutralization and separation step comprising adding an aqueous solution of a neutralizing agent to the reaction mass obtained in step b), followed by separation of the aqueous and organic layers; d) a step of precipitating the modified diene-containing (co)polymer by adding an excess alcohol-non-solvent; e) the step of isolating by filtration and subsequent drying of the precipitated modified diene-containing (co)polymer, characterized in that at stage b) of modification, a mixture of halogen and water is used as a modifying system in a ratio of halogen:water from 1:0.01 to 1:1 based on the total number of double bonds in the original diene-containing (co)polymer. 61. The method according to p. 60, characterized in that the ratio of halogen:water in the modifying system is preferably from 1:0.7 to 1:0.5. 62. The method according to p. 60, characterized in that the ratio of halogen:water in the modifying system is more preferably from 1:0.25 to 1:0.7. 63. The method according to p. 60, characterized in that chlorine, bromine, iodine are used as halogen in the modifying system. 64. The method according to p. 60, characterized in that bromine is preferably used as the halogen in the modifying system. 65. The method according to p. 60, characterized in that bromine in the modifying system is used in the form of bromine as such or in the form of a solution with a bromine content of not more than 70 wt.%, preferably not more than 60 wt.%, more preferably not more than 50 wt. .%. 66. The method according to p. 60, characterized in that the water in the modifying system is distilled, deionized, demineralized, osmotic or bidistilled water. 67. The method according to p. 60, characterized in that the initial diene-containing (co)polymer is a polymers and copolymers of a conjugated diene. 68. The method according to p. 60, characterized in that the conjugated diene is a conjugated diene selected from the group: 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2-ethyl-1,3- butadiene, 2,3-di(C1-C5 alkyl)-1,3-butadienes such as 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl- 3-ethyl-1,3-butadiene, 2-methyl-3-isopropyl-1,3-butadiene, phenyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 2-methyl-pentadiene, 4-methyl-pentadiene, or mixtures thereof. 69. The method according to p. 60, characterized in that the conjugated diene is preferably 1,3-butadiene or isoprene. 70. The method according to p. 60, characterized in that as a comonomer in the initial diene-containing (co)polymer, vinyl aromatic compounds selected from the group are used: styrene, α-methylstyrene, ortho-, meta- and para-methylstyrene, 3-vinyltoluene, ethylvinylbenzene, 4-cyclohexylstyrene, p-tert-butylstyrene, methoxystyrenes, vinylmesitylene, divinylbenzene, 1-vinylnaphthalene, 2,4,6-trimethylstyrene, or mixtures thereof. 71. The method according to p. 60, characterized in that styrene or α-methylstyrene is preferably used as the comonomer in the initial diene-containing (co)polymer. 72. The method according to p. 60, characterized in that the original diene-containing (co)polymer is a butadiene, butadiene-styrene, butadiene-styrene-isoprene (co)polymer. 73. The method according to p. 60, characterized in that the initial diene-containing (co)polymer is preferably a butadiene-styrene copolymer. 74. The method according to p. 60, characterized in that the original diene-containing (co)polymer has a weight average molecular weight of at least 700 g/mol, preferably from 1000 to 400000 g/mol, more preferably from 2000 to 300000 g/mol, more preferably 5,000 to 200,000 g/mol, more preferably 20,000 to 120,000 g/mol, most preferably 20,000 to 50,000 g/mol. 75. The method according to p. 60, characterized in that the initial diene-containing (co)polymer has a coefficient of polydispersity from 0.8 to 3, more preferably from 1 to 1.8, most preferably from 1.1 to 1.5. 76. The method according to p. 60, characterized in that the content of 1,2-units in the original diene-containing (co)polymer is from at least 10 to 100 wt.%, preferably from at least 50 to 99 wt.%, more preferably from 60 to 80 wt.% on the polybutadiene part of the rubber. 77. The method according to p. 60, characterized in that hydrocarbon solvents are used as a solvent in the dissolution stage, which are ethers, such as tetrahydrofuran, halogenated saturated aliphatic hydrocarbons, such as carbon tetrachloride, chloroform, dibromomethane, dichloromethane, 1,2 -dichloroethane, cycloaliphatic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene, halogenated aromatic hydrocarbons such as bromobenzene, chlorobenzene and dichlorobenzene. 78. The method according to p. 60, characterized in that tetrahydrofuran, chloroform, dichloromethane, dichloroethane, cyclohexane, toluene are preferably used as a solvent in the dissolution stage. 79. The method according to p. 60, characterized in that tetrahydrofuran, chloroform, dichloromethane is more preferably used as a solvent in the dissolution stage. 80. The method according to p. 60, characterized in that the dissolution in step a) is carried out at a temperature of from 10 to 50°C, preferably from 15 to 40°C, more preferably from 20 to 30°C. 81. The method according to p. 60, characterized in that the mass ratio of the hydrocarbon solvent to the initial diene-containing (co)polymer in the dissolution stage is from 5:1 to 30:1, preferably from 8:1 to 20:1, more preferably from 10 :1 to 15:1. 82. The method according to p. 60, characterized in that the time of the dissolution process is not more than 60 minutes, not more than 50 minutes, not more than 40 minutes, not more than 30 minutes, not more than 25 minutes, not more than 20 minutes, not more than 15 minutes , no more than 13 minutes, no more than 11 minutes, no more than 9 minutes, no more than 7 minutes, no more than 5 minutes. 83. The method according to any one of paragraphs. 60-82, characterized in that the original diene-containing (co)polymer is pre-crushed. 84. The method according to p. 60, characterized in that methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol are used as aliphatic alcohol at the modification stage. 85. The method according to claim 60, characterized in that propanol, butanol, isobutanol, pentanol are preferably used as aliphatic alcohol at the modification stage. 86. The method according to p. 60, characterized in that butanol, isobutanol, pentanol are more preferably used as aliphatic alcohol at the modification stage. 87. The method according to p. 60, characterized in that the ratio of the original diene-containing (co)polymer: modifying system: aliphatic alcohol is from 1: 1.5: 3 to 1: 5: 3, more preferably from 1: 2: 3 to 1:4:3, most preferably 1:2.5:3 to 1:3:3. 88. The method according to p. 60, characterized in that the modification is carried out at a temperature of from 0 to 50°C, preferably from 20 to 45°C, more preferably from 30 to 40°C. 89. The method according to p. 60, characterized in that at the stage of modification, the stirring speed of the reaction mass after adding the modifying system is from 50 to 600 rpm, preferably from 100 to 500 rpm, more preferably from 200 to 300 rpm . 90. The method according to p. 60, characterized in that the time of the modification step is at least 15 minutes, at least 20 minutes, at least 25 minutes, at least 30 minutes, at least 45 minutes, at least 60 min, at least 120 min. 91. The method according to p. 60, characterized in that at the neutralization stage, aqueous solutions of sodium thiosulfate, sodium bisulfite, sodium carbonate are used as a neutralizing agent. 92. The method according to p. 60, characterized in that the molar ratio of the amount of neutralizing agent to the amount of added halogen is usually from 1:1 to 3:1, preferably from 1:1 to 2:1, more preferably 1:1. 93. The method according to p. 60, characterized in that the neutralization process is carried out at a temperature of from 15 to 50°C, preferably from 20 to 40°C, more preferably from 25 to 30°C. 94. The method according to p. 60, characterized in that at the stage of precipitation, methanol, ethanol, propanol, isopropanol, butanol, isobutanol are used as an alcohol-precipitant. 95. The method according to p. 60, characterized in that the mass ratio of alcohol-non-solvent:modified (co)polymer is from 10 to 1, preferably from 15 to 5, more preferably from 5 to 4. 96. The method according to p. 60, characterized in that the filtration of the modified diene-containing (co)polymer is carried out using filters equipped with porous filter walls, suction filters. 97. The method according to p. 60, characterized in that the filtration of the modified diene-containing (co)polymer is carried out at a temperature of from 20 to 40°C. 98. The method according to p. 60, characterized in that the drying of the modified diene-containing (co)polymer is carried out at a temperature of from 50 to 105°C. 99. The method according to p. 60, characterized in that the drying of the modified diene-containing (co)polymer is carried out at a pressure of from 1 to 20 kPa. 100. The use of a modified diene-containing (co)polymer according to any one of paragraphs. 1-9 as a flame retardant (flame retardant). 101. Use according to claim 100, characterized in that the modified diene-containing (co)polymer is used as a flame retardant (flame retardant) in expandable polystyrene. 102. Expandable polystyrene containing a modified diene-containing (co)polymer according to any one of paragraphs. 1-9 as a flame retardant (flame retardant). 103. Expandable polystyrene according to claim 102, in which the content of the modified diene-containing (co)polymer is not less than 0.5 wt. hours, preferably not less than 0.7 wt. hours, more preferably not less than 1 wt. h. 104. Polymeric composition based on expandable polystyrene for use in the field of construction, including a modified diene-containing (co)polymer according to any one of paragraphs. 1-9 as a flame retardant (flame retardant) and additives that provide a set of technological, physical, mechanical and operational characteristics. 105. The polymer composition according to claim 104, where antistatic agents, stabilizers, dyes, lubricants, fillers, anti-agglomerators are used as additives.

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