RU2795580C2 - Modified diene-containing (co)polymer, method of its production and application as a fire retardant - Google Patents

Abstract

FIELD: organic chemistry.

SUBSTANCE: modified diene-containing (co)polymers, in particular a modified butadiene-styrene copolymer. Invention can be used as a flame retardant for polymer compositions based on expandable polystyrene. Modified diene-containing (co)polymer containing in its structure halogen atoms, at least one epoxy group, at least one hydroxyl group and at least an amino group, having a temperature of 5% weight loss of at least 180°C, a weight average molecular weight of at least 1500 g/mol and a halogen content of at least 35% by weight, based on the weight of the total (co)polymer, is described. The invention also relates to a method for producing a modified diene-containing (co)polymer and use as a flame retardant for polystyrene, including expandable polystyrene.

EFFECT: increased heat resistance of modified diene-containing (co)polymers, which consists in increasing the temperature of 5% weight loss, which is at least 180°C, while the (co)polymers obtained according to the present invention are characterized by a molecular weight of at least 1500 g/mol and a halogen content of at least 35% by weight, based on the weight of the entire (co)polymer, and also do not affect the polymerization process and formation of polystyrene granules.

54 cl, 2 dwg, 2 tbl, 5 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, in products based on expandable polystyrene, to give them flame retardant properties [Stockholm Convention on Persistent Organic Pollutants, UNEP/POPS/POPRC.6/10, 15.10. 2010]. In such polymer compositions, various low molecular weight brominated compounds, for example, hexabromocyclododecane (HBCD), are usually used as flame retardants (flame retardants). However, the results of many studies have shown the ability of HBCD to bioaccumulate, high toxicity and resistance to environmental factors [Stockholm Convention on Persistent Organic Pollutants, UNEP/POPS/POPRC.6/10, 15.10.2010, paragraph 4]. 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 [Stockholm Convention on Persistent Organic Pollutants, UNEP/POPS/POPRC.6/10, 10/15/2010, paragraph 74], processing temperatures are often very high, resulting in a 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 of 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 low 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 of products obtained from it. .

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 its low thermal stability, which manifests itself at high processing temperatures of expandable polystyrene, as well as the absence of functional groups capable of absorbing HBr released at high temperatures.

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.

Closest to the developed flame retardant (flame retardant) and the method of its production is brominated and epoxidized styrene-butadiene copolymer according to patent RU2530021 (prototype), which is used as a flame retardant (flame retardant) for expandable polystyrene.

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

epoxidizing the starting styrene-butadiene copolymer with a molecular weight of at least 700 g/mol such that at least a portion of the non-conjugated carbon-carbon double bonds undergo epoxidation;

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 above invention is characterized by a molecular weight of at least 1500 g/mol, a bromine content of at least 35 wt.% and a temperature of five percent (5%) weight loss of at least 180 ^about 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 a low compatibility of such a flame retardant (flame retardant) with polystyrene.

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 not affect the polymerization process and the formation of polystyrene granules and, at the same time, will provide excellent fire-retardant properties of polystyrene, including expandable polystyrene.

Figures illustrating the present invention

To explain the technical solutions that reveal the essence of the present invention, Figure 1 and Figure 2 are presented.

Figure 1 is a block diagram showing the sequence of stages for obtaining a modified diene-containing (co)polymer in accordance with the present invention.

The Figure 2 shows the nuclear magnetic resonance spectrum on hydrogen nuclei ( ¹ H NMR spectrum) obtained modified diene-containing (co)polymer containing epoxy groups, hydroxyl groups, amino groups and halogen atoms.

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 technical result of the present invention is to increase the heat resistance of the modified diene-containing (co)polymers, in particular, to increase the temperature of the 5% weight loss, which is at least 180 ^° C, while the (co)polymers obtained according to the present invention are characterized by a molecular weight at least 1500 g/mol and a halogen content of at least 35 wt. % based on the weight of the entire (co)polymer, and also do not affect the polymerization process and the formation of polystyrene granules.

The specified technical result is achieved by obtaining a modified diene-containing (co)polymer, including epoxy groups, hydroxyl groups, amino groups, and halogen atoms, which is obtained by epoxidation of the initial diene-containing (co)polymer and further carrying out successive stages of interaction with an aminating agent and a halogenating agent .

The inventors of the present invention have surprisingly found that a modified diene-containing (co)polymer comprising epoxy groups, hydroxyl groups, amino groups, as well as halogen atoms is heat-resistant, and also does not affect the polymerization process and the formation of polystyrene granules.

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

Detailed description of the invention

In accordance with the present invention, the modified diene-containing (co)polymer contains in its structure halogen atoms, at least one epoxy group, at least one hydroxyl group and at least one amino group, and has a temperature of 5% weight loss, according to at least 180 ^° C., a weight average molecular weight of at least 1500 g/mol and a halogen content of at least 35% by weight, based on the weight of the total (co)polymer.

The modified diene-containing (co)polymer obtained according to the invention is a heat-resistant modified diene-containing (co)polymer, which is characterized by a weight average molecular weight of at least 1500 g/mol, preferably from 2000 to 280000 g/mol, more preferably from 10000 to 150000 g/mol , most preferably from 60,000 to 100,000 g/mol, and the presence of a plurality of non-conjugated carbon-carbon double bonds, where at least two (but less than all non-conjugated carbon-carbon double bonds) double bonds are modified, 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, at least one epoxidized non-conjugated carbon-carbon double bond , at least one hydroxyhalogenated non-conjugated carbon-carbon double bond, and at least one hydroxyaminated non-conjugated carbon-carbon double bond.

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

The obtained heat-resistant modified diene-containing (co)polymer contains at least one epoxy group, while the content of epoxy groups in the obtained modified diene-containing (co)polymer is from 0.01 to 5 wt.%, preferably from 0.03 to 3 wt.% , more preferably from 0.5 to 1 wt.% based on the weight of the total (co)polymer.

The obtained heat-resistant modified diene-containing (co)polymer contains at least one hydroxyl group, while the content of hydroxyl groups in the obtained modified diene-containing (co)polymer is from 0.01 to 0.5 wt.%, preferably from 0.02 to 0, 1 wt.%, more preferably from 0.03 to 0.08 wt.%, based on the weight of the total (co)polymer.

The heat-resistant modified diene-containing (co)polymer obtained according to the invention contains at least one amino group, while the content of amino groups in the obtained modified diene-containing (co)polymer is from 0.01 to 5 wt.%, preferably from 0.05 to 3 wt.% , more preferably from 1 to 2 wt.% based on the weight of the total (co)polymer.

The presence of three types of functional groups in addition to halogen atoms in the modified diene-containing (co)polymer allows solving several problems, namely, amino groups at elevated temperatures are converted into nitrogen-containing compounds, which effectively prevent the combustion process by releasing nitrogen oxides during combustion, which displace oxygen at the surface of the burning material , which is a combustion control mechanism. Epoxy groups function as scavengers for HBr, which, as mentioned above, can be released during the processing of polymers and polymer compositions containing a flame retardant (flame retardant) at elevated temperatures. In turn, the hydroxyl groups impart a polar and hydrophilic character to the (co)polymer.

As a result, when a flame retardant (flame retardant) is introduced into the process of styrene suspension polymerization, a stable suspension is formed, the styrene polymerization process proceeds without deviations due to the complex effect of four types of functional groups, namely the epoxy group, hydroxyl group, amino group and halogen atoms, simultaneously present in modified diene-containing (co)polymer. This leads to a better distribution of the flame retardant (flame retardant) in the suspension during the suspension polymerization of styrene, which makes it possible to obtain a granulometric composition of polystyrene that meets the requirements of consumers.

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 of the general formula (1):

(1)

(1)

where R ₁ -R ₃ are the same or different, and can be hydrogen or a hydrocarbon group with the number of carbon atoms from 1 to 6, for example, an alkyl group, Hal - is a halogen, which is selected from chlorine, bromine or iodine; k, m, l, h, p may be the same or different and preferably 1<k<37, 1<m<19, 2<(l+p)<3660, 1<h<15, more preferably 6<k <12, 3<m<6, 610<(l+p)<1220, 2<h<10, most preferably 7<k<10, 4<m<5, 730<(l+p)<980, 3 <h<5, n is the number of polymer chain units, which is 50<n<450, preferably 100<n<350, more preferably 140<n<250.

As initial diene-containing (co)polymers, polymers and copolymers of conjugated dienes can be used.

In the context of the present invention, an organic solvent is one that is liquid and inert under the conditions for producing a modified diene-containing (co)polymer.

In another implementation, the present invention relates to a method for producing a modified diene-containing (co)polymer, which includes the following steps:

the stage of dissolution, which carry out (optionally) preliminary grinding of the original diene-containing (co)polymer, and its subsequent dissolution in a solvent;

an epoxidation step in which an epoxidizing agent is added to the solvent solution of the initial diene-containing (co)polymer obtained in step a);

a neutralization and separation step in which an aqueous solution of a neutralizing agent is added to the reaction mass obtained in step b), and the aqueous and organic layers are separated;

an amination step in which an aminating agent and optionally an organotin catalyst are added to the organic layer obtained in step c);

a neutralization and separation step in which an aqueous solution of a neutralizing agent is added to the reaction mass obtained in step d), and the aqueous and organic layers are separated;

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

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

a separation step in which the modified diene-containing (co)polymer is precipitated or degassed from the organic layer obtained in step g);

the stage of filtration and subsequent drying of the isolated modified diene-containing (co)polymer.

Stage a) dissolution

At this stage, optionally, preliminary grinding of the original diene-containing (co)polymer is carried out, followed by its dissolution in an organic solvent with stirring.

Grinding, if necessary, of the original diene-containing (co)polymer is carried out by any methods known from the prior art, for example, using crushers (in particular, knife, hammer, rotary crushers), mills (for example, jet or screw), and other methods known to the skilled person.

The original diene-containing (co)polymer may be polymers and copolymers of conjugated dienes.

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 their mixtures. Preferably, 1,3-butadiene or isoprene or a mixture thereof 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, or mixtures thereof. Preferably, styrene or α-methylstyrene or mixtures thereof are used.

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

Preferably, as the diene-containing (co)polymer, (co)polymers such as butadiene, butadiene-styrene and butadiene-styrene-isoprene can be used, 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) , styrene-butadiene 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 polybutadiene part of the (co)polymer.

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, organic 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 organic solvents are those which are liquid under the conditions of modification of the original diene-containing (co)polymer, and which are inert under the conditions of stage b) epoxidation of the original diene-containing (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 organic solvent and 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 time of the dissolution process is not more than 60 minutes, in particular not more than 50 minutes, including not more than 40 minutes, in particular not more than 30 minutes, in particular not more than 25 minutes, in particular not more than 20 minutes, in in particular, not more than 15 minutes, in particular, not more than 13 minutes, in particular, not more than 11 minutes, in particular, not more than 9 minutes, in particular, not more than 7 minutes, in one embodiment, not 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 an organic solvent.

Step b) epoxidation

In step b) of epoxidation, an epoxidizing agent is added to the original 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, as an epoxidizing agent, pure substances containing active oxygen, as well as solutions of such substances, or mixtures thereof, in organic solvents with an epoxidizing agent content of from 10 to 50 wt.%, preferably from 15 to 30 wt. %, more preferably from 20 to 25 wt.%.

Suitable epoxidizing agents according to the present invention are peracids, for example, performic acid, peracetic acid, metachloroperbenzoic acid, and peroxides, for example hydrogen peroxide, or mixtures thereof, including in the presence of catalysts, for example, derivatives of molybdenum or tungsten, but not limited to them.

The epoxidizing agent is dissolved in an organic solvent or a mixture of organic solvents, preferably having a purity of 99% or more, which is an ether, for example, tetrahydrofuran, halogenated saturated aliphatic hydrocarbons, for example, chloroform, dibromomethane, dichloromethane, 1,2-dichloroethane, cycloaliphatic hydrocarbons, eg cyclohexane, aromatic hydrocarbons, eg toluene, halogenated aromatic hydrocarbons, eg 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 to epoxidize no more than 6 mole % non-aromatic double bonds, preferably no more than 2.5 mole % non-aromatic double bonds, more preferably no more than 0.5 mole % 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 -20 ^° C. to 100 ^° C., preferably -10 ^° C. to 50 ^° C., more preferably 0 ^° C. 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, and the like.

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.

Stage d) amination

In step d) amination, an aminating agent and optionally an organotin catalyst are added to the organic layer obtained in step c) containing the partially epoxidized diene-containing (co)polymer.

Suitable aminating agents include, but are not limited to, primary amines such as monoethanolamine, methylamine, secondary amines such as diethylamine, dimethylamine, tertiary amines such as trimethylamine, triethylamine, as well as pyridine, ammonia, phenylenediamines, hexamethylenediamine, aniline. Preferably, secondary amines, namely diethylamine, dimethylamine, are used as the aminating agent.

Suitable organotin catalysts include, but are not limited to, dibutyltin dilaurate, dioctyltin di(2-ethylhexanoate), dioctyltin dithioglycolate, dioctyltin dilaurate, dioctyltin oxide, dibutyltin diacetate, monobutyltin oxide, dioctyltin stantansan.

The molar ratio of epoxidized diene-containing (co)polymer:aminating agent:organotin catalyst is 1:0.01:0.08 to 1:1:8, more preferably 1:0.05:0.4 to 1:0.5 :4, most preferably from 1:0.09:0.75 to 1:0.11:0.85.

The aminating agent is used in an amount sufficient to aminate no more than 99 mole % epoxidized units, preferably no more than 50 mole % epoxidized units, more preferably no more than 30 mole % epoxidized units.

Preferably, during the amination step, the aminating agent or its solution 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.

The amination 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 amination step is carried out at -20 ^° C. to 100 ^° C., preferably -10 ^° C. to 50 ^° C., more preferably 0 ^° C. to 20 ^° C., and atmospheric pressure.

The duration of the amination step can be any sufficient to achieve the desired degree of amination of the initial diene-containing (co)polymer described above. Preferably, the duration of the amination step is at least 30 minutes, at least 60 minutes, at least 180 minutes, at least 240 minutes, at least 300 minutes, at least 360 minutes, at least 420 minutes.

The reaction mass obtained after stage d) of the amination contains a partially epoxidized and aminated diene-containing (co)polymer.

Step e) neutralization and separation

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

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

The molar ratio of neutralizing agent to added aminating agent is usually 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°C to 50°C, preferably 20°C to 40°C, more preferably 25°C 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 and aminated 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) halogenation

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

Chlorine, bromine or iodine is used as the halogen in the halogenating agent, preferably bromine is used as the halogen.

Thus, elemental bromine (Br ₂ ) is preferably used as a halogenating agent as such, and also in the form of a solution in an organic 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. tetraethylphosphonium 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 and/or allyl carbon atoms, which , in turn, affects the heat resistance of the resulting modified diene-containing (co)polymer.

As the aliphatic alcohol, alcohols with a carbon content of from 1 to 6 are used, for example, selected from the group consisting of methanol, ethanol, propanol, iso-propanol, butanol, iso-butanol, pentanol, or hexanol, but are not limited to them. Preferably, the aliphatic alcohol is propanol, butanol, iso-butanol, pentanol, more preferably butanol, iso-butanol and pentanol, or mixtures thereof.

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 and the aliphatic alcohol, if used, to the organic layer obtained in step e) can be any. Preferably, an aliphatic alcohol is first added to the organic layer containing the partially epoxidized and aminated diene-containing (co)polymer, followed by the addition of a halogenating agent. In this case, 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 organic solvent.

The addition of elemental bromine is preferably carried out in the form of its solution in an organic solvent by dosing the solution into the reaction mass at a rate of 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 a solution of elemental bromine (Br ₂ ) to the solution obtained in step e) can lead to crosslinking of the (co)polymer, 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 an organic 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 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 and aminated diene-containing (co)polymer obtained in step e) is carried out without access to light, for example, by carrying out the modification process in dark glass vessels, by wrapping the reactor in foil, or by carrying out the process in metal reactors, in order to reduce the probability of the reactions of non-selective photocatalytic halogenation occurring.

The halogenation step is carried out at a temperature of 0 ^° C. to 50 ^° C., preferably 20 ^° C. to 45 ^° C., more preferably 30 ^° C. 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 duration of the halogenation step can be any length sufficient to achieve the desired degree of halogenation of the acyloxyhalogenated diene-containing (co)polymer described above. Preferably, the duration of the partial halogenation 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 at stage f) contains the target product - a modified diene-containing (co)polymer containing acyloxyhalogenated diene units and halogen atoms.

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

Step g) neutralization and separation

This stage includes neutralization of the reaction mass obtained in stage f) 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 a neutralizing agent, water bases known from the prior art are used, but are not limited to, for example, sodium hydroxide, sodium thiosulfate, sodium bisulfite, sodium carbonate.

The molar ratio of neutralizing agent to added halogenating 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 ^° C. to 50° C., preferably 20 ^° C. to 40° C., more preferably 25 ^° C. 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 h) isolation

If the method for producing a modified diene-containing (co)polymer is implemented in accordance with one of the embodiments of the present invention through the stage of precipitation of the obtained modified diene-containing (co)polymer, then in order to isolate the modified diene-containing (co)polymer obtained in step f) to that obtained in step g) an alcohol-precipitant is added to the organic layer containing the modified diene-containing (co)polymer. The weight ratio of alcohol-non-solvent:modified diene-containing (co)polymer ranges 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, iso-propanol, butanol, iso-butanol. Preferably, methanol and ethanol are used as the precipitating alcohol.

If the method for producing a modified diene-containing (co)polymer is carried out in accordance with one of the embodiments of the present invention through the stage of degassing the obtained modified diene-containing (co)polymer, then at the stage h) isolation, water is added to the organic layer obtained at stage g), followed by distillation water-solvent mixtures at elevated temperature and reduced pressure in order to isolate the target modified diene-containing (co)polymer and remove water and/or its vapors, solvent and/or its vapors from it.

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

The amount of added water in relation to the organic solvent is from 1:1 to 10:1, preferably from 1:1 to 5:1, more preferably from 2:1 to 4:1.

According to ^the present invention, the temperature of the water when added to the system is at most 30 ^° C, preferably at most 25 ^° C, more preferably at most 20 ^° C. evaporation of the solvent, which, in turn, can lead to a change in the physico-mechanical characteristics of the resulting modified diene-containing (co)polymer.

The degassing is carried out in any suitable equipment known from the prior art, in particular in apparatuses that provide good mixing, heat exchange and maintenance of reduced pressure. Examples of such apparatuses include, but are not limited to, continuous or batchwise agitators provided with a jacket.

The temperature of the degassing step is 20°C to 150°C, preferably 50°C to 100°C, most preferably 80°C to 95°C.

The pressure in the degassing step is kept below 800 mbar, preferably below 300 mbar, more preferably below 100 mbar.

Preferably the duration of the degassing step is at least 30 minutes, more preferably at least 60 minutes, most preferably at least 120 minutes.

Stage i) filtration and drying

At stage i) filtration and drying to purify the modified diene-containing (co)polymer from solvent residues and precipitating alcohol, filtration is carried out using any apparatus known from the prior art, for example, using filters equipped with porous filter septa, suction filters and other filters known from the prior art.

Filtration of the modified diene-containing (co)polymer is carried out at a temperature of from 20 ^about C 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 (for example, distillation of the solvent under reduced pressure, drying in a vacuum oven), as well as using drying reagents that remove moisture due to adsorption, hydrate formation or chemical reaction with water and solvents.

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

The invention is illustrated in more detail by Figure 1, which shows a block diagram for obtaining a modified diene-containing (co)polymer, where 101 is the dissolution unit of the original diene-containing (co)polymer, 102 is the epoxidation unit of the original diene-containing (co)polymer, 103 is the neutralization and separation unit , 104 - amination block, 105 - neutralization and separation block, 106 - halogenation block, 107 - neutralization and separation block, 108 - extraction block, 109 - filtration block, 110 - drying block.

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 an organic 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 amination unit 104 , which is also supplied with an aminating agent (10) and an organotin catalyst (11) if used, resulting in a reaction mass (12 ) containing a partially epoxidized aminated diene-containing (co)polymer. After that, the resulting reaction mass (12), containing a partially epoxidized aminated diene-containing (co)polymer, enters the neutralization and separation unit 105 , into which a neutralizing agent (13) is supplied, followed by water (14) for washing the neutralized reaction mass, after whereby the separation of the organic layer (16) containing the epoxidized aminated diene-containing (co)polymer and the aqueous layer (15) is carried out. Then, the organic layer (16) containing the epoxidized aminated diene-containing (co)polymer is sent to the halogenation unit 106 , which is also supplied with a halogenating agent (17) and aliphatic alcohol (18), resulting in a reaction mass containing a modified diene-containing (co) ) a polymer that includes epoxy groups, hydroxyl groups, amino groups and halogen atoms. After that, the resulting reaction mass (19), containing a modified diene-containing (co)polymer, enters the neutralization and separation unit 107 , into which a neutralizing agent (20) is supplied, followed by water (21) for washing the neutralized reaction mass, after which separating the organic layer (23) containing the modified diene-containing (co)polymer and the aqueous layer (22). Then, the organic layer (23) containing the modified diene-containing (co)polymer enters the recovery unit 108' . Next, the isolated modified diene-containing (co)polymer (24) is sequentially fed to the filtration unit 109 and (25) to the drying unit 110 in order to obtain the final product - the modified diene-containing (co)polymer (26). 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 scheme shown in Figure 1 is an exemplary embodiment of the present invention and does 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, the flame retardants must be compatible with the polymer or polymer composition.

In accordance with the present invention, the modified diene-containing (co)polymer is introduced into the polymer or polymer composition at the stage of obtaining. So, for example, 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 and other components, followed by the stage of foaming the resulting polystyrene (as disclosed, for example, in US5086078).

In yet another embodiment, the present invention relates to an expandable polystyrene containing as a flame retardant (flame retardant) the specified modified diene-containing (co)polymer. 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, per 100 wt.h. polymer, otherwise the effectiveness of improving the fire-resistant characteristics of the resulting polymer or polymer composition, in particular expandable polystyrene or a composition based on it, is reduced.

In addition, in another embodiment of the present invention, polymer compositions are claimed, for example, based on expandable polystyrene containing a modified diene-containing (co)polymer 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, but not limited to antistatic agents, stabilizers, dyes, lubricants, fillers, anti-agglomerators.

According to the present invention, expandable polystyrene compositions can be used to produce a wide range of products, such as building thermal and acoustic insulation, in particular, thermal and acoustic insulation boards, fixed formwork, automotive components, floating products, as well as in as a raw material for polystyrene blocks required 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 heat resistance, namely, the temperature of 5% weight loss of at least 180 ^° C, measured by thermogravimetric analysis, does not affect the polymerization process and the formation of polymer granules, in particular, polystyrene, which is confirmed by the granulometric composition of the resulting polystyrene. In addition, the flame retardant (flame retardant) produced in accordance with the present invention imparts flame retardant properties to expandable polystyrene, which makes it possible to classify 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 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 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.

EXAMPLES OF CARRYING OUT 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 is measured by studying the thermal behavior of the (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°С to 600°С, heating rate 10°С/min.

Nuclear magnetic resonance (NMR) method

The microstructure of the polymer chain of samples of the modified diene-containing (co)polymer is 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 is dissolved in 0.6 ml of deuterated chloroform. Number of scans on ¹ H-32 cores.

Gel Permeation Chromatography (GPC)

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

Analysis conditions: eluent - tetrahydrofuran; dissolution and measurement temperature 40°C, eluent flow rate 1.0 ml/min; column PLgel Mixed-C (2-3 pcs). The calculation is carried out according to 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 is determined on a HAVER EML digital plus particle sieving apparatus. For sieving, a set of sieves with a mesh diameter of 2.0 is used; 1.6; 1.0; 0.70; 0.40; 0.20 mm. Sieving time 15 minutes. The mass of the powder on the sieves is determined by the gravimetric method.

Fire test

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

Sample preparation: Cut 40 mm from the molded part and discard. Then 5 samples are cut out with dimensions (190±1)×(90±0.5)×(20.0±0.5) mm so that there is no technological film formed during the formation of the block, cracks, chips and shells. The lower face of the sample is cut smoothly, has sharp edges, and forms 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:

Prepare and bring the device to the operating mode. Turn off the ventilation in the chamber. The air velocity is measured with a hot-wire anemometer in the exhaust pipe of the test chamber. The required value is between 0.5 and 0.8 m/s.

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

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

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

Under the sample at the bottom of the test chamber in a wire box is placed in 2 layers of filter paper.

Testing:

The firing chamber is closed. From the side, a burner with a flame turned at an angle of 45 ^° is brought to the center of the free end (edge) of the sample, after which the stopwatch is turned on. The sample is exposed to the flame for 15 seconds, after which the burner is withdrawn and the combustion of the sample is observed. In this case, the time is measured from the beginning of exposure to the flame until the moment when the top of the flame of the burning sample reaches the measuring mark of 150 mm, if before that the flame did not go out by itself. The tests are interrupted after 20 s (from the beginning of the flame treatment of the sample) and the maximum height of the flame and dripping (falling off of burning fragments) are 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 (according to the invention) . Obtaining a modified butadiene-styrene copolymer containing 0.05 wt.% hydroxyaminated butadiene units

The solution of the original styrene-butadiene (co)polymer (4 g in 40 g of dichloromethane) with stirring is cooled to a temperature of 0-5°C. 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) is dosed to the cooled copolymer solution. The temperature of the cooling bath is maintained at 0-5°C. After adding the entire volume of acid, the reaction mass is stirred at a given temperature for another 30 minutes, then for 1 hour at a temperature of 25 ^about C and for 1 hour at 50°C. After the end of epoxidation, the residues of m-chloroperbenzoic acid are neutralized with a sodium hydroxide solution, and the reaction mass is washed with a threefold volumetric excess of water, followed by separation of the aqueous and organic layers.

Next, the organic layer containing the partially epoxidized styrene-butadiene copolymer is loaded into the flask. Start stirring and set the bath temperature to 35°C. A solution of 0.4 g of diethylamine in 1 g of dichloromethane is dosed into the flask over 1 minute, after 15 minutes the organic catalyst solution (3.16 g of dibutyltin dilaurate and 10 g of dichloromethane) is added, the temperature is raised to 38° C. and stirred for 6 hours. Then the reaction mass is washed with a threefold volumetric excess of water, followed by separation of the aqueous and organic layers.

Next, the organic layer containing the partially epoxidized and aminated butadiene-styrene copolymer is charged into a dark glass flask, stirring is started and the bath temperature is set to 35°C. 12 g of butanol, 2 g of water are added, a solution of bromine in dichloromethane is dosed (7.5 g of bromine per 7.5 ml of dichloromethane) over 5-20 minutes. After adding all the bromine solution in dichloromethane, stirring is continued for 30 minutes, then 10% sodium thiosulfate solution is added and bromine is neutralized for 60 minutes. After that, the inorganic layer is drained off, and the organic layer containing the modified styrene-butadiene copolymer is washed with a three-volume excess of distilled water. Then, the modified styrene-butadiene copolymer containing epoxy groups, hydroxyl groups, amino groups, and bromine atoms is precipitated in a fivefold excess of alcohol, separated, and dried by distilling off 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.

The ¹ H NMR spectrum of the resulting modified styrene-butadiene copolymer is shown in FIG. 2.

¹ H NMR spectrum (CDCl ₃ , δ, ppm): 6.3-7.2 (styrene); 5.2-5.7 (1,4-butadiene); 4.9 -5.05 (1,2-butadiene); 4.05-4.2 (amino groups); 2.8-3.0 (epoxy groups).

Example 2 (comparative). Obtaining a hydroxy-brominated copolymer (according to RU2530021)

The solution of the original butadiene-styrene copolymer (20 g in 200 g of dichloromethane) with stirring is cooled to a temperature of 0-5°C. A solution of 0.083 g of 77% m-chloroperbenzoic acid in dichloromethane (1 mol of acid per 1 mol of epoxidized diene units) is dosed to the cooled copolymer solution. The temperature of the cooling bath is maintained at 0-5°C. After adding the entire volume of acid, the reaction mass is stirred at a given temperature for another 30 minutes, then for 1 hour at a temperature of 25°C and for 1 hour at 50°C. After the end of epoxidation, the residues of m-chloroperbenzoic acid are neutralized with a sodium hydroxide solution, and the reaction mass is washed with a threefold volumetric excess of water, followed by separation of the aqueous and organic layers.

Next, the organic layer containing the epoxidized styrene-butadiene copolymer is placed in a dark glass flask, to which 60 g of butanol and 5 g of water are also added, and a solution of bromine in dichloromethane (39.4 g of bromine per 50 ml of dichloromethane) is dosed over 10-20 min. After adding all the bromine solution in dichloromethane, stirring is continued for 30 minutes, then 10% sodium thiosulfate solution is added and bromine is neutralized for 60 minutes. After that, the inorganic layer is drained, and the organic layer is washed with a three-volume excess of distilled water. Then the resulting hydroxybrominated butadiene-styrene copolymer is precipitated in a fivefold excess of alcohol, separated and dried by distilling off 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 2 are shown in Table. 1.

Example 3 (comparative). Obtaining epoxy-brominated copolymer (according to RU2530021)

The solution of the original butadiene-styrene copolymer (10 g in 100 g of dichloromethane) with stirring is cooled to 0-5°C. A solution of 1.32 g of 77% m-chloroperbenzoic acid in dichloromethane (1 mol of peroxide per 1 mol of epoxidized diene units) is dosed to the cooled copolymer solution. The temperature of the cooling bath is maintained at 0-5°C. After adding the entire volume of acid, the reaction mass is stirred at a given temperature for another 30 minutes, then for 1 hour at 25°C and for 1 hour at 50°C. After the end of epoxidation, the residues of m-chloroperbenzoic acid are neutralized with a sodium hydroxide solution, and the reaction mass is washed with a threefold volumetric excess of water, followed by separation of the aqueous and organic layers. Further, water and solvent are distilled off from the epoxidized butadiene-styrene copolymer at 91°C and 9 kPa, followed by drying in a vacuum oven at 91°C and 1 kPa.

Next, the organic layer containing the epoxidized butadiene-styrene copolymer is placed in a dark glass flask, to which a solution of tetrabutylammonium in dichloromethane (36.13 g of tetrabutylammonium per 20 ml of dichloromethane) is also added and a solution of bromine in dichloromethane (17.9 g of bromine) is dosed per 20 ml of dichloromethane) for 10-20 minutes. After adding all the bromine solution in dichloromethane, stirring is continued for 30 minutes, then 10% sodium thiosulfate solution is added and bromine is neutralized for 60 minutes. After that, the inorganic layer is drained, and the organic layer containing the epoxy-brominated styrene-butadiene copolymer is washed with a three times volume excess of distilled water. Then, the resulting modified styrene-butadiene copolymer containing epoxy groups and bromine atoms is precipitated in a fivefold excess of alcohol, separated and dried by distilling off 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 3 are shown in Table. 1.

Example 4 . Obtaining hydroxy-epoxy-brominated copolymer

A solution of the starting styrene-butadiene copolymer in dichloromethane (10 g of copolymer per 150 g of dichloromethane) is added to a 250 ml dark glass flask. Next, 30 g of butanol, 7.6 g of water are added to the flask, after which a solution of 17.74 g of bromine in 20 ml of dichloromethane is dosed. The modification reaction is carried out for 30-40 minutes. After the reaction is complete, sodium hydroxide (NaOH) solution is added to the flask and neutralization is carried out for 1 hour. Then the reaction mass containing the modified styrene-butadiene copolymer is washed with a threefold volume excess of water.

Further, the resulting modified styrene-butadiene copolymer is filtered off, followed by its precipitation in isopropanol, after which it is dried by distilling off the solvent at a temperature of 30-95°C and a pressure of 3 kPa, followed by additional drying in a vacuum oven at 70 ^o C and 0, 5 kPa.

Characteristics of the modified styrene-butadiene copolymer obtained according to Example 4 are presented in Table. 1.

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

Example No. Degree of amination,% Weight average molecular weight, g/mol Temperature 5% weight loss, °C Styrene content,
wt% The content of 1,2-butadiene units, wt.% The content of 1,4-butadiene units, wt.% Bromine content, wt.% The content of OH groups, wt.% The content of epoxy groups, wt.% Example 1 0.05 95 000 236 20.99 - - 78.72 0.08 0.21 Example 2
(compar.) absent 92 500 190 20.2 - - 79.8 0.15 - Example 3
(compar.) absent 238 000 215 20.53 0.53 1.33 73.6 - 4.01 Example 4 absent 109 500 220 20.69 - - 77.23 1.56 0.53

Example 5 Production of expandable polystyrene

In a flask, 87 parts of water, 0.43 parts of a polymerization stabilizer (a mixture of sodium pyrophosphate and magnesium sulfate) are mixed at a temperature of 25 ^° C. To this mixture is 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) based on a modified styrene-butadiene copolymer obtained in accordance with examples 1-4, and 0.21 parts of a synergist flame retardant (flame retardant) - dicumyl peroxide. The mixture is stirred for 2 hours at a temperature up to 85°C, then heated to 115°C for 4.5 hours. 70 minutes after the temperature in the flask reached 80°C, a 10% aqueous solution of polyvinylpyrrolidone was introduced into the reaction mixture. After an additional 100-120 minutes, a polystyrene foaming step is carried out, in which a solution of 0.10 parts of a chain transfer agent in 4.7 parts of a foaming agent (n-heptane) is added to the reaction mass. After reaching 115° C., the flask is maintained at a constant temperature for 3 hours, after which the mixture is cooled to a temperature of 25 ^° C. for 3 hours.

Next, the granulometric composition of the polystyrene obtained before the foaming stage is determined. 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) in accordance with TU 2214-019-53505711-2010

Example 5 Flame retardant used (according to example) Sieve No. Example 1 Example 2 Example 3 Example 4 2.00 0.10 0.06 8.55 0.08 1.60 2.21 1.15 5.61 1.85 1.00 50.15 40.75 49.39 62.27 0.70 40.84 47.48 29.2 27.59 0.40 5.32 9.11 6.3 6.51 0.2 1.33 1.26 - 2.54 bottom 0.05 0.19 0.95 0.16

From the data given in Table. 1 it can be seen that the copolymer having in its structure amino groups together with epoxy groups, hydroxyl groups and bromine atoms (Example 1) has better thermal stability (236 ° C) compared to copolymers containing only epoxy and / or hydroxide groups in its structure and bromine atoms (Example 2-4).

From the data given in Table. Table 2 shows that when the copolymer according to Example 1 is introduced into polystyrene, a stable suspension is formed, and polystyrene granules of the required sizes are obtained that fully meet the requirements of TU 2214-019-53505711-2010 (Table 2), the yield of target fractions is 93.2%.

Claims (63)

1. A modified diene-containing (co)polymer containing in its structure halogen atoms, at least one epoxy group, at least one hydroxyl group and at least an amino group, having a 5% weight loss temperature of at least 180° C, a weight average molecular weight of at least 1500 g/mol and a halogen content of at least 35% by weight, based on the weight of the total (co)polymer. 2. The modified diene-containing (co)polymer according to claim 1, which has a 5% weight loss temperature of at least 200°C, preferably at least 220°C. 3. The modified diene-containing (co)polymer according to claim 1, which has a weight average molecular weight of 2,000 to 280,000 g/mol, preferably 10,000 to 150,000 g/mol, more preferably 60,000 to 100,000 g/mol. 4. The modified diene-containing (co)polymer according to claim 1, in which the content of halogen atoms is at least 60 wt.%, more preferably at least 75 wt.%, based on the weight of the entire (co)polymer. 5. The modified diene-containing (co)polymer according to claim 1, wherein the content of epoxy groups is from 0.01 to 5% by weight, based on the weight of the entire (co)polymer. 6. The modified diene-containing (co)polymer according to claim 5, in which the content of epoxy groups is preferably from 0.03 to 3 wt.% based on the weight of the entire (co)polymer. 7. The modified diene-containing (co)polymer according to claim 5, in which the content of epoxy groups is more preferably from 0.5 to 1 wt.% based on the weight of the entire (co)polymer. 8. The modified diene-containing (co)polymer according to claim 1, in which the content of hydroxyl groups is from 0.01 to 0.5 wt.% based on the weight of the entire (co)polymer. 9. The modified diene-containing (co)polymer according to claim 8, in which the content of hydroxyl groups is preferably from 0.02 to 0.1 wt.% based on the weight of the entire (co)polymer. 10. The modified diene-containing (co)polymer according to claim 8, in which the content of hydroxyl groups is more preferably from 0.03 to 0.08 wt.% based on the weight of the entire (co)polymer. 11. Modified diene-containing (co)polymer according to claim 1, in which the content of amino groups is from 0.01 to 5 wt.% based on the weight of the entire (co)polymer. 12. The modified diene-containing (co)polymer according to claim 11, in which the content of amino groups is preferably from 0.05 to 3 wt.% based on the weight of the entire (co)polymer. 13. The modified diene-containing (co)polymer according to claim 11, in which the content of amino groups is more preferably from 1 to 2 wt.% based on the weight of the entire (co)polymer. 14. Modified diene-containing (co)polymer according to any one of paragraphs. 1-13, where the (co)polymer is a modified butadiene polymer, butadiene-styrene, butadiene-styrene-isoprene copolymer. 15. The modified diene-containing (co)polymer according to claim 14, wherein the (co)polymer is a modified styrene-butadiene copolymer. 16. The method of obtaining a modified diene-containing (co)polymer according to any one of paragraphs. 1-15, which includes the following steps: a dissolution step comprising dissolving the initial diene-containing (co)polymer in a solvent; an epoxidation step comprising adding an epoxidizing agent to the solvent solution obtained in step a) of the original diene-containing (co)polymer; 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; an amination step comprising adding an aminating agent to the organic layer obtained in step c) containing a partially epoxidized diene-containing (co)polymer, the aminating agent being used in an amount sufficient to aminate not more than 99 mole % of the epoxidized units; a neutralization and separation step comprising adding an aqueous solution of a neutralizing reagent to the reaction mass obtained in step d) and separating the aqueous and organic layers; a halogenation step comprising adding a halogenating agent, water and optionally an aliphatic alcohol to the organic layer obtained in step e); a neutralization and separation step comprising adding an aqueous solution of a neutralizing agent to the reaction mass obtained in step f) and separating the aqueous and organic layers; a separation step comprising precipitating or degassing the modified diene-containing (co)polymer from the organic layer obtained in step g); the stage of filtration and subsequent drying of the isolated modified diene-containing (co)polymer. 17. The method according to p. 16, characterized in that pure substances containing active oxygen, or mixtures thereof, are used as an epoxidizing agent in stage b) of epoxidation, solutions of such substances with an epoxidizing agent content of 10 to 50% wt.%, preferably from 15 to 30% wt.%, more preferably from 20 to 25% wt.%, or mixtures thereof. 18. The method according to claim 17, characterized in that performic acid, peracetic acid, metachloroperbenzoic acid, hydrogen peroxide, or mixtures thereof are used as the epoxidizing agent. 19. The method according to p. 16, 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. 20. The method according to claim 16, characterized in that primary amines such as monoethanolamine, methylamine, secondary amines such as diethylamine, dimethylamine, tertiary amines such as trimethylamine, triethylamine, as well as pyridine, ammonia, phenylenediamines, hexamethylenediamine, aniline. 21. The method according to claim 20, characterized in that secondary amines such as diethylamine, dimethylamine are preferably used as the aminating agent. 22. Process according to claim 16, characterized in that an organotin catalyst is used in step d) of the amination. 23. The method according to claim 22, characterized in that dibutyltin dilaurate, dioctyltin di(2-ethylhexanoate), dioctyltin dithioglycolate, dioctyltin dilaurate, dioctyltin oxide, dibutyltin diacetate, monobutyltin oxide, dioctyltin stantansan are used as an organotin catalyst. 24. The method according to p. 16, characterized in that the molar ratio of epoxidized diene-containing (co)polymer : aminating agent : organotin catalyst is from 1:0.01:0.08 to 1:1:8. 25. The method according to claim 24, characterized in that the molar ratio of epoxidized diene-containing (co)polymer : aminating agent : organotin catalyst is more preferably from 1:0.05:0.4 to 1:0.5:4. 26. The method according to claim 24, characterized in that the molar ratio of epoxidized diene-containing (co)polymer : aminating agent : organotin catalyst is most preferably from 1:0.09:0.75 to 1:0.11:0.85. 27. The method according to p. 16, characterized in that the aminating agent is used in an amount sufficient to aminate not more than 99 mol.% epoxidized units, preferably not more than 50 mol.% epoxidized units, more preferably not more than 30 mol.% epoxidized units . 28. The method according to p. 16, characterized in that the initial diene-containing (co)polymer is a polymers and copolymers of a conjugated diene. 29. The method according to p. 28, characterized in that the conjugated diene is a conjugated diene selected from the group containing 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. 30. The method of claim 28, wherein the conjugated diene is preferably 1,3-butadiene or isoprene. 31. The method according to p. 28, characterized in that vinylaromatic compounds selected from the group containing styrene, α-methylstyrene, ortho-, meta- and para-methylstyrene, 3-vinyltoluene are used as comonomers in the initial diene-containing (co)polymer , ethylvinylbenzene, 4-cyclohexylstyrene, para-tert-butylstyrene, methoxystyrenes, vinylmesitylene, divinylbenzene, 1-vinylnaphthalene, 2,4,6-trimethylstyrene, or mixtures thereof. 32. The method according to p. 28, characterized in that styrene or α-methylstyrene is preferably used as the comonomer in the initial diene-containing (co)polymer. 33. The method according to p. 16, characterized in that the initial diene-containing (co)polymer is a butadiene, butadiene-styrene, butadiene-styrene-isoprene copolymer. 34. The method according to p. 33, characterized in that the initial diene-containing (co)polymer is preferably a butadiene-styrene copolymer. 35. The method according to p. 16, 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. 36. The method according to p. 16, 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. 37. The method according to p. 16, 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 (co)polymer. 38. The method according to any one of paragraphs. 16-37, characterized in that the original diene-containing (co)polymer is pre-crushed. 39. The method according to p. 16, characterized in that at stage f) halogenation, chlorine, bromine, iodine are used as halogen in the halogenating agent. 40. Process according to claim 39, characterized in that bromine is preferably used as the halogen in the halogenation agent in step f) of the halogenation. 41. The method according to p. 16, 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. 42. The method according to p. 41, characterized in that elemental bromine and quaternary ammonium bromides or quaternary phosphonium bromides are preferably used simultaneously as a halogenating agent. 43. The method according to p. 41, 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. 44. The method according to p. 41, characterized in that tetramethylphosphonium bromide, tetraethylphosphonium bromide, tetrapropylammonium bromide, tetra-n-butyl-ammonium tribromide, or mixtures thereof are used as quaternary phosphonium bromide. 45. The method according to p. 16, characterized in that stage f) halogenation is carried out in the presence of an aliphatic alcohol. 46. The method according to p. 45, 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 1:2:3 to 1:4:3, most preferably 1:2.5:3 to 1:3:3. 47. The method according to p. 42, characterized in that the molar ratio of elemental bromine : bromine atoms in the quaternary ammonium bromide or quaternary phosphonium bromide in the halogenating agent is from 1:1 to 1:4, more preferably from 1:2 to 1:3 , most preferably from 1:1 to 1:1.5. 48. The method according to p. 45, characterized in that methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol are used as aliphatic alcohol in stage f) of halogenation. 49. The use of a modified diene-containing (co)polymer according to any one of paragraphs. 1-15 as a flame retardant (flame retardant). 50. Use according to claim 49, characterized in that the modified diene-containing (co)polymer is used as a flame retardant (flame retardant) in expandable polystyrene. 51. Expandable polystyrene containing a modified diene-containing (co)polymer according to any one of paragraphs. 1-15 as a flame retardant (flame retardant). 52. Expandable polystyrene according to claim 51, wherein the content of the modified diene-containing (co)polymer is at least 0.5 parts by weight, preferably at least 0.7 parts by weight, more preferably at least 1 part by weight. 53. Flame retardant polymer composition based on expandable polystyrene, including a modified diene-containing (co)polymer according to any one of paragraphs. 1-15 as a flame retardant (fire retardant) and additives that provide a set of technological, physical, mechanical and operational characteristics. 54. Fire-retardant polymer composition according to claim 53, in which antistatic agents, stabilizers, dyes, lubricants, fillers, anti-agglomerators are used as additives.

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