RU2782606C2 - Modified diene-containing (co)polymer, its production method, and use as flame retardant - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to modified butadiene-styrene copolymer, which can be used as a flame retardant for polymer compositions based on foamed polystyrene. The present invention relates to a group of inventions: modified diene-containing (co)polymer, options of a method for the production of modified diene-containing (co)polymer, the use of modified diene-containing (co)polymer, foamed polystyrene, and a polymer composition based on foamed polystyrene for construction. Modified diene-containing (co)polymer contains halogen atoms and acyloxyhalogenated diene links, having a temperature of 5% weight loss of at least 180°C, average-mass molecular weight of at least 1500 g/mol, and halogen content of at least 35 wt.%. This modified diene-containing (co)polymer is used as a flame retardant. Foamed polystyrene contains modified diene-containing (co)polymer as a flame retardant. The polymer composition based on foamed polystyrene includes modified diene-containing (co)polymer as a flame retardant and additives providing a complex of technological, physical and mechanical, and operational characteristics.

EFFECT: development of a flame retardant based on diene-containing (co)polymer, which will be heat-resistant, will satisfy ecological requirements, as well as will not negatively affect a process of polymerization and formation of polystyrene granules, while it will show good compatibility and provide excellent fire-protection properties to polystyrene, including foamed polystyrene.

67 cl, 4 dwg, 5 tbl, 10 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.

From the prior art, presented by the application WO2008021417 and patent RU2414479, examples of such flame retardants (flame retardants) are known, such as, for example, brominated styrene-butadiene copolymers.

In particular, patent RU2414479 describes a heat-resistant brominated styrene-butadiene copolymer that 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°C, as determined by the method of thermogravimetric analysis (TGA).

Also, RU2414479 proposes a method for producing the above 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, RU2414479 proposes a polymer mixture containing said heat-resistant brominated styrene-butadiene copolymer, as well as a molded article containing said 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 styrene-butadiene copolymers, which can cause difficulties in obtaining a homogeneous structure of foamed polystyrene with large thicknesses of products obtained from it.

In addition, from 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 technical solution described in RU2530021, 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 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 RU2530021 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°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.

The closest to the developed flame retardant (flame retardant) and the method of its production is hydroxybrominated butadiene-styrene copolymer according to the application WO2016123263 (prototype), which is used as a flame retardant (flame retardant) for foaming polystyrene.

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°C.

The disadvantage of this flame retardant (flame retardant) is the high content of hydroxyl groups in the structure of the (co)polymer, 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, thus This leads to a deterioration in the granulometric composition of polystyrene.

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.

However, despite the fact that the state of the art has proposed a method for the preparation of brominated flame retardants (flame retardants) using, in particular, halosuccinimides, it is obvious that this method leads to the formation of relatively easy release of HBr when heated, hydroxybrominated units, which leads to decomposition of the flame retardant (flame retardant) and, as a result, the coloring of polystyrene compositions, including expandable 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, a promising direction is the development of a flame retardant (fire retardant) based on a diene-containing (co)polymer, which will be heat-resistant, meet environmental requirements, and will not adversely affect the polymerization process and the formation of polystyrene granules, and at the same time will show good compatibility and provide excellent fire retardant properties to polystyrene, including expandable polystyrene.

The essence of the invention

The objective of the present invention is to develop a modified diene-containing (co)polymer, which is 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 obtain a modified diene-containing (co)polymer characterized by high heat resistance, namely, a temperature of 5% weight loss of at least 180°C, 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.

The specified technical result is achieved by obtaining a modified diene-containing (co)polymer, including acyloxyhalogenated units (units that include halogen atoms and an acyloxy group) in an amount of from 0.01 to 10 wt.% based on the weight of the entire (co)polymer, as well as halogen atoms in an amount of at least 35 wt.% based on the weight of the entire (co)polymer.

The authors of the present invention have unexpectedly found that the specified modified diene-containing (co)polymer can be obtained by using as a modifying system a mixture of carboxylic acid and a halogenating agent to introduce acyloxyhalogenated groups into the structure of the (co)polymer, and an additional halogenating agent to introduce into the structure of a (co)polymer of an additional number of halogen atoms.

It has also been found by the present inventors that the modified diene-containing (co)polymer according to the present invention can be obtained by reacting hydroxyhalogenated diene-containing (co)polymers, such as those obtained according to WO2016123263, with the components of the acylating system.

In addition, the authors of the present invention have found that the modified diene-containing (co)polymer, including acyloxyhalogenated diene units, is heat-resistant, does not affect the polymerization process and the formation of polystyrene granules, exhibits good compatibility with polystyrene, and also provides high flame retardant properties to expandable polystyrene. .

Presumably, the presence of acyloxyhalogenated units 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 to foaming polystyrene .

The present invention makes it possible to obtain a modified diene-containing (co)polymer containing acyloxyhalogenated diene units, as well as halogen atoms, which is 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, Figures 1-4 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 through stage b) modification.

Figure 2 is a block diagram showing the sequence of stages for obtaining a modified diene-containing (co)polymer in accordance with the present invention through stage b) partial halogenation.

Figure 3 is a block diagram showing the sequence of stages for obtaining a modified diene-containing (co)polymer in accordance with the present invention from a hydroxyhalogenated diene-containing (co)polymer.

The Figure 4 shows the spectrum of nuclear magnetic resonance on hydrogen nuclei ( ¹ H NMR spectrum) of the obtained modified diene-containing (co)polymer containing acyloxyhalogenated diene units and halogen atoms.

Description of the invention

In accordance with the present invention, the claimed modified diene-containing (co)polymer 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 280,000 g/mol, more preferably from 10,000 to 150,000 g/mol, most preferably from 60,000 to 100,000 g/mol, in which a plurality of non-conjugated carbon-carbon double bonds, where at least two (but less than all non-conjugated carbon-carbon double bonds) are modified, and a 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 acyloxyhalogenated 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 heat-resistant modified diene-containing (co)polymer of the present invention contains acyloxyhalogenated diene units in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 1 to 3% by weight the total (co)polymer.

Said acyloxyhalogenated diene units are in particular acyloxybrominated diene units.

According to the invention, the temperature of the 5% weight loss of the modified diene-containing (co)polymer is at least 180°C, preferably at least 220°C, more preferably at least 230°C.

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

(1)

(one)

where R ₁ -R ₄ - 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, which is selected from chlorine, bromine or iodine; k, l, m, n may be the same or different and preferably 20<k<900, 1<l<200, 40<(m+n)<4500, more preferably 40<k<400, 2<l<100 , 100<(m+n)<2000, most preferably 150<k<250, 3<l<20, 700<(m+n)<1000. In this case, the order of the polymer chain links can be changed arbitrarily.

The halogen in the structure of the modified diene-containing (co)polymer is chlorine, bromine or iodine. Preferably, the modified diene-containing (co)polymer contains bromine atoms as the halogen.

In accordance with the present invention, a modified diene-containing (co)polymer is obtained using a modifying system, which is used as a carboxylic acid and a halogenating agent.

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 of the modified diene-containing (co)polymer steps.

In another aspect of the present invention, a method for producing a modified diene-containing (co)polymer is claimed, comprising the following steps:

a dissolution step, optionally including preliminary grinding of the original diene-containing (co)polymer, followed by dissolution in a solvent;

a modification step comprising adding the components of the modifying system to the solvent solution of the original diene-containing (co)polymer obtained in step a) to obtain an acyloxyhalogenated diene-containing (co)polymer;

a washing and separation step in which water is added to the reaction mass obtained in step b), and the aqueous and organic layers are separated;

an optional isolation step comprising precipitating or degassing the acyloxyhalogenated diene-containing (co)polymer from the organic layer obtained in step c);

an optional step of filtering and then drying the isolated acyloxyhalogenated diene-containing (co)polymer;

an optional dissolution step comprising pre-grinding the acyloxyhalogenated diene-containing (co)polymer followed by dissolution in a solvent;

a step of halogenating the acyloxyhalogenated diene-containing (co)polymer comprising adding a halogenating agent and optionally an aliphatic alcohol to the solution obtained in step f);

a neutralization and separation step comprising adding an aqueous solution of a neutralizing agent to the reaction mass obtained in step g) 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 h);

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

wherein the method is characterized in that in stage b) of the modification, a carboxylic acid and a halogenating agent are used as a modifying system in a molar ratio of carboxylic acid:halogenating agent from 1:1 to 1000:1, preferably from 1:1 to 100:1, more preferably from 1:1 to 10:1.

Stage a) dissolution

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

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

Suitable conjugated dienes are C4 to C12 conjugated dienes, for example selected from the group consisting of 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. Preferably, 1,3-butadiene or isoprene is used.

Suitable comonomers in the original diene-containing (co)polymer are vinylaromatic compounds such as those selected from the group consisting of styrene, α-methylstyrene, ortho-, meta- and para-methylstyrene, 3-vinyltoluene, ethylvinylbenzene, 4-cyclohexylstyrene, para-tert -butylstyrene, methoxystyrenes, vinylmesitylene, divinylbenzene, 1-vinylnaphthalene, 2,4,6-trimethylstyrene, 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 initial diene-containing (co)polymers have 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 from 5000 to 200000 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 a content 1,2-units from at least 10 to 100 wt.%, preferably at least 50 to 99 wt.%, more preferably from 60 to 80 wt.% on the polybutadiene part of the (co)polymer.

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 such as knife, hammer, impact crushers, jet and screw mills, and similar equipment.

When dissolving the initial 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°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 initial diene-containing (co)polymer, and which are inert under the conditions of step b) of modification 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 organic solvent to 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 duration of the dissolution process is not more than 60 minutes, in particular, 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, not more than 13 minutes, not more than 11 minutes, no more than 9 minutes, no more than 7 minutes, no more than 5 minutes.

Obtained at the specified stage a) dissolution of the mass is a solution of the original diene-containing (co)polymer in an organic solvent.

Stage b) modifications

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

In accordance with the present invention, a carboxylic acid and a halogenating agent are used as a modifying system in a molar ratio of carboxylic acid:halogenating agent from 1:1 to 1000:1, preferably from 1:1 to 100:1, more preferably from 1:1 to 10 :one.

Chlorine, bromine or iodine is used as the halogen in the halogenating agent. However, the preferred halogen in the halogenating agent in step b) is bromine.

The halogenating agent is, but is not limited to, a bromimide, such as N-bromosuccinimide, N-bromophthalimide, or a bromamide, such as N-bromoacetamide, or a bromourea, such as tetrabromoglycoluril, as such, or as solutions in solvents at concentrations from 1% to 50%.

As a carboxylic acid, acids such as C1-C8 alkyl carboxylic acids, for example, acetic acid, propionic acid, 2-ethylhexanoic acid, C1-C8 halogenated acids, for example, bromoacetic acid, 2-bromopropionic acid, C6 -C8 arylcarboxylic acids, eg benzoic acid, 4-methylbenzoic acid, C6-C8 halogenated arylcarboxylic acids, eg 4-bromobenzoic acid, or combinations thereof. Preferably, acetic acid, propionic acid, bromoacetic acid, benzoic acid, or 4-bromobenzoic acid is used as the carboxylic acid. The presence of additional halogen atoms in the acid further improves the flame retardant properties of the modified diene-containing (co)polymer.

The molar ratio of halogenating agent:double bond of the original diene-containing (co)polymer in step b) is from 0.001:1 to 0.1:1, more preferably from 0.01:1 to 0.05:1, most preferably from 0.01 :1 to 0.02:1.

The order of adding the components of the modifying system to the solution of the original diene-containing (co)polymer obtained in step a) can be any. Preferably, the carboxylic acid is first added to the original diene-containing (co)polymer solution, followed by the addition of the halogenating agent.

As an organic solvent for dissolving the halogenating agent, an ether solvent, 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, for example, bromobenzene, chlorobenzene and dichlorobenzene or mixtures thereof, preferably having a purity of 99% or more. 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.

Step b) modification 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, step b) of modification of the original diene-containing (co)polymer is carried out without access to light, for example, by carrying out the modification 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 of non-selective photocatalytic halogenation reactions occurring. .

The modification step is carried out at a temperature of 0 to 100°C, preferably 20 to 80°C, more preferably 40 to 60°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 duration of stage b) modification can be any sufficient to achieve the desired degree of modification of the original diene-containing (co)polymer, as 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 modification step b) contains an acyloxyhalogenated diene-containing (co)polymer with an acyloxyhalogenation degree of at least 0.01%, preferably at least 0.1%, most preferably at least 1%.

Additional stages c) washing and separation, d) isolation, e) filtration and subsequent drying are carried out in order to completely remove the residues of the modifying system, which lead to undesirable side reactions in the subsequent halogenation stage.

Step c) washing and separation

In step c) washing and separation, water is added to the reaction mass obtained in step b) containing the acyloxyhalogenated diene-containing (co)polymer, followed by separation of the aqueous layer and the organic layer containing the acyloxyhalogenated diene-containing (co)polymer.

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

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, resulting in the separation of the reaction mass into two layers: an organic layer containing an acyloxyhalogenated diene-containing (co )polymer, and an aqueous layer.

At the same time, the permissible residual content of the halogenating agent in the organic layer after washing with water is from 0 to 0.5 wt.%, preferably less than 0.2 wt.%, more preferably less than 0.05 wt.%.

Preferably, the washing 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.

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

Step d) isolation

Step d) separating the obtained acyloxyhalogenated diene-containing (co)polymer from the organic layer from step c) is carried out in two ways - by precipitation, or by degassing the acyloxyhalogenated diene-containing (co)polymer.

In one embodiment of the invention, the method for producing a modified diene-containing (co)polymer is implemented through the stage of precipitation of the obtained acyloxyhalogenated diene-containing (co)polymer.

In such an embodiment, an alcohol precipitant is added to the organic layer obtained in step c) containing the acyloxyhalogenated diene-containing (co)polymer. The weight ratio of alcohol-non-solvent:acyloxyhalogenated 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 precipitating 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, or isobutanol. Preferably, methanol or ethanol is used as the precipitating alcohol.

In another embodiment of the present invention, the method for producing a modified diene-containing (co)polymer is implemented through the stage of degassing the obtained acyloxyhalogenated diene-containing (co)polymer.

In such an embodiment, water is added to the organic layer obtained in step c), followed by distillation of the water-solvent mixture at elevated temperature and reduced pressure in order to isolate the acyloxyhalogenated diene-containing (co)polymer and remove water and/or its vapors, solvent and /or its vapor.

In the context of the present invention, water is, but is not limited to, distilled, deionized, demineralized, osmotic, or 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. The use of water with a temperature above 30°C leads to boiling and subsequent rapid evaporation of the solvent, which, in turn, undesirably changes the physical and mechanical characteristics of the resulting acyloxyhalogenated 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 to 150°C, preferably 50 to 100°C, most preferably 80 to 95°C.

The degassing step is maintained at a pressure of less than 800 mbar, preferably less than 300 mbar, more preferably less than 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 e) filtration and drying

At the stage e) filtration and drying to purify the acyloxyhalogenated diene-containing (co)polymer from residual solvent and precipitant 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 the like. equipment.

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

To remove water and/or its vapors, solvent and/or its vapors from the obtained acyloxyhalogenated diene-containing (co)polymer, the said (co)polymer is dried. The drying process of the acyloxyhalogenated diene-containing (co)polymer is carried out by physical methods commonly used for the separation and purification of organic substances, in particular, such as 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 to 105° C. and a pressure of 20 to 1 kPa.

Step f) Dissolution

In one embodiment of the invention, in the optional step f) of dissolving the acyloxyhalogenated diene-containing (co)polymer obtained in step e), its preliminary grinding is carried out, followed by dissolution in an organic solvent with stirring.

Grinding of the acyloxyhalogenated diene-containing (co)polymer is carried out by any of the methods known in the art, for example, using crushers such as knife, hammer, impact mills, or mills, such as jet or screw mills.

When dissolving the acyloxyhalogenated diene-containing (co)polymer, mixing is 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 up to 30°С.

Suitable solvents for use in said step f) include, but are not limited to, organic solvents, preferably 99% pure or greater, and 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. Preferred organic solvents of step f) 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 the subsequent step g) of halogenation of the acyloxyhalogenated diene-containing (co)polymer. Preferably, tetrahydrofuran, chloroform, dichloromethane, dichloroethane, cyclohexane, toluene is used as said solvent, most preferably tetrahydrofuran, chloroform, dichloromethane is used.

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

The duration of the dissolution process is at most 60 minutes, preferably at most 50 minutes, in particular at most 40 minutes, at most 30 minutes, at most 25 minutes, at most 20 minutes, at most 15 minutes, at most 13 minutes, at most 11 minutes, no more than 9 minutes, no more than 7 minutes, no more than 5 minutes.

The mass obtained from dissolution step f) above is a solution of the acyloxyhalogenated diene-containing (co)polymer in an organic solvent.

Stage g) halogenation

In step g) halogenation, the halogenating agent and optionally an aliphatic alcohol are added to the solution obtained in step f).

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

The preferred halogenating agent in step g) of the halogenation of the present invention is elemental bromine (Br ₂ ) as such, as well as in 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. 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 in step g). At the same time, 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 thermal stability of the resulting modified diene-containing (co)polymer.

As aliphatic alcohol in stage g) halogenation, alcohols with a content of carbon atoms from 1 to 6 are used, such as methanol, ethanol, propanol, isopropanol, n-butanol, iso-butanol, sec-butanol, pentanol, isoamyl alcohol, hexanol, but are not limited to them. Preferably, propanol, n-butanol, iso-butanol, sec-butanol, pentanol are used as the aliphatic alcohol, more preferably n-butanol, iso-butanol and sec-butanol are used.

The molar ratio of acyloxyhalogenated diene-containing (co)polymer:halogenating agent:aliphatic alcohol in halogenation step g) 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. In one of the embodiments of the invention, when elemental bromine and quaternary ammonium bromide or quaternary phosphonium bromide are used together as a halogenating agent, the mole ratio of elemental bromine:bromine atoms in quaternary ammonium bromide or quaternary phosphonium bromide is from 1:1 to 1:4, more preferably 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 solution obtained in step f) can be any. Preferably, an aliphatic alcohol is first added to the acyloxyhalogenated diene-containing (co)polymer solution, 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.

Elemental bromine is preferably added as 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 dosing rate of more than 50 ml/min, as well as a single addition of the entire volume of a solution of elemental bromine (Br ₂ ) to the solution obtained in step f), leads to crosslinking of the (co)polymer, local overheating of the reaction mass, and an increase in its viscosity, which in turn turn leads to the production of a modified diene-containing (co)polymer with an undesirably low (less than 35 wt.%) content of halogen atoms.

The halogenating agent is dissolved in an organic solvent, or a mixture of organic solvents, 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 f) to dissolve the acyloxyhalogenated diene-containing (co)polymer.

The halogenation step g) 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 step g) halogenation of the acyloxyhalogenated diene-containing (co)polymer obtained in step b) is carried out in the absence of light, for example, by carrying out a 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 likelihood reactions of non-selective photocatalytic halogenation.

Stage g) 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, 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 convenient time sufficient to achieve the desired degree of halogenation of the acyloxyhalogenated diene-containing (co)polymer described above. Preferably, the partial halogenation time is at least 15 minutes, in particular 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 in step g) contains the target product, a modified diene-containing (co)polymer containing acyloxyhalogenated diene units and halogen atoms.

Step h) neutralization and separation

Stage h) of the proposed method for obtaining a modified diene-containing (co)polymer according to the present invention includes neutralizing the reaction mass obtained in stage g) containing a modified diene-containing (co)polymer by adding an aqueous solution of a neutralizing agent, followed by washing the neutralized reaction mass with water and separating the aqueous layer and an organic layer containing a modified diene-containing (co)polymer.

As the neutralizing agent in step h), aqueous basic solutions known from the prior art are used, for example, but not limited to sodium hydroxide, sodium thiosulfate, sodium bisulfite, sodium dithionite, sodium hypophosphite, sodium ascorbate, sodium carbonate. Preferably, an aqueous solution of sodium hydroxide is used.

The molar ratio of neutralizing agent to the amount of halogenating agent added in step g) 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 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, as a result of which the reaction mass is divided into two layers: an organic layer containing a modified diene-containing (co)polymer, and an aqueous layer.

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

Step i) isolation

Step i) separating the obtained modified diene-containing (co)polymer from the organic layer from step h) is carried out in two ways, by precipitation or by degassing the modified diene-containing (co)polymer.

In one embodiment of the invention, the method for producing a modified diene-containing (co)polymer is implemented through the stage of deposition of the resulting modified diene-containing (co)polymer. In such an embodiment, to isolate the modified diene-containing (co)polymer obtained in step g) to the organic layer obtained in step h) containing the modified diene-containing (co)polymer, an alcohol-non-solvent is added. 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, isopropanol, butanol, isobutanol. Preferably, methanol and ethanol are used as the precipitating alcohol.

In another embodiment of the present invention, the method for producing a modified diene-containing (co)polymer is implemented through the step of degassing the resulting modified diene-containing (co)polymer. According to such an embodiment, in step i) isolation, water is added to the organic layer obtained in step h), and then the water-solvent mixture is distilled off at elevated temperature and reduced pressure to isolate the target modified diene-containing (co)polymer and remove water therefrom, and /or its vapors, the solvent and/or its vapors.

In the context of the present invention, water is, but is not limited to, distilled, deionized, demineralized, osmotic, or 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. In the case of using water with a temperature above 30°C, boiling occurs and subsequent rapid evaporation of the solvent, which leads to an undesirable 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 to 150°C, preferably 50 to 100°C, most preferably 80 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 time of the degassing step is at least 30 minutes, more preferably at least 60 minutes, most preferably at least 120 minutes.

Stage j) filtration and drying

At stage j) of filtration and drying 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 filter septa, suction filters, and the like. equipment.

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

To remove water and/or its vapors, solvent and/or its vapors from the obtained modified diene-containing (co)polymer, the said (co)polymer is dried. The drying process of the modified diene-containing (co)polymer is carried out by physical methods commonly used for the separation and purification of organic substances, in particular, solvent distillation under reduced pressure, drying in a vacuum oven, and also using drying reagents that remove moisture due to adsorption, formation hydrates or chemical reaction with water and solvents.

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

In addition, according to another embodiment of the present invention, the modified diene-containing (co)polymer can be obtained by a method which includes the following steps:

the stage of dissolution, including optional preliminary grinding of the original diene-containing (co)polymer, and its subsequent dissolution in a solvent;

a partial halogenation step using a halogenating agent and optionally an aliphatic alcohol to a degree of halogenation of at least 60%, preferably at least 90%, most preferably at least 95%;

a washing and separation step comprising adding water to the reaction mass obtained in step b) and separating the aqueous and organic layers;

a modification step comprising adding components of the modifying system to the organic layer obtained in step c) containing a partially halogenated diene-containing (co)polymer;

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;

a separation step comprising precipitating or degassing the modified diene-containing (co)polymer from the organic layer obtained in step e);

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

wherein the method is characterized in that in stage b) of the modification, a carboxylic acid and a halogenating agent are used as a modifying system in a molar ratio of carboxylic acid:halogenating agent from 1:1 to 1000:1, preferably from 1:1 to 100:1, more preferably from 1:1 to 10:1.

Stage a) dissolution

In step a) of said additional embodiment of the invention, an optional preliminary grinding of the original diene-containing (co)polymer is carried out, and its subsequent dissolution in an organic solvent with stirring.

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

When dissolving the initial diene-containing (co)polymer, mixing is 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 up to 30°С.

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) partial halogenation of the original diene-containing (co)polymer. Preferably, tetrahydrofuran, chloroform, dichloromethane, dichloroethane, cyclohexane, toluene is used as the solvent, most preferably tetrahydrofuran, chloroform, dichloromethane is used.

The weight ratio of organic solvent to 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 duration of the dissolution process is not more than 60 minutes, in particular, 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, not more than 13 minutes, not more than 11 minutes, no more than 9 minutes, no more than 7 minutes, no more than 5 minutes.

Obtained at the specified stage a) dissolution of the mass is a solution of the original diene-containing (co)polymer in an organic solvent.

Step b) partial halogenation

In step b) partial halogenation, the halogenating agent and optionally an aliphatic alcohol are added to the starting diene-containing (co)polymer solution obtained in step a).

The degree of halogenation of the partially halogenated diene-containing (co)polymer obtained in step b) is at least 60%, preferably at least 90%, most preferably at least 95%.

The partial halogenation step b) is carried out essentially in the absence of water in the system, namely the allowable water content is from 0 to less than 0.5 wt.%, more preferably from 0 to less than 0.3 wt.%, even more preferably from 0 to less than 0.1 wt.%.

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

The preferred halogenating agent is elemental bromine (Br ₂ ) 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. 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 in step b) of the partial halogenation. At the same time, 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 thermal stability of the resulting modified diene-containing (co)polymer.

As aliphatic alcohol, alcohols with a content of carbon atoms from 1 to 6, such as methanol, ethanol, propanol, iso-propanol, butanol, iso-butanol, pentanol, hexanol, are used, but are not limited to them. Preferably, propanol, butanol, iso-butanol, pentanol are used as the aliphatic alcohol, more preferably butanol, iso-butanol 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 from 1:2:3 to 1:4:3, most preferably from 1: 2.5:3 to 1:3:3. Moreover, 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 initial diene-containing (co)polymer solution obtained in step a) can be any. Preferably, an aliphatic alcohol is first added to the original diene-containing (co)polymer solution, 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 in stage b) partial halogenation 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 from 0.80 to 50 ml/min, preferably from 1 to 10 ml/min, more preferably from 1, 5 to 5 ml/min. A dosing rate of more than 50 ml/min, as well as a single addition of the entire volume of a solution of elemental bromine (Br ₂ ) to the solution obtained in step a), leads to cross-linking of the (co)polymer, local overheating of the reaction mass, and an increase in its viscosity, which in turn turn leads to the production of a modified diene-containing (co)polymer with an undesirably low (less than 35 wt.%) content of halogen atoms

As an organic solvent for dissolving the halogenating agent, a solvent or a mixture of solvents is chosen, preferably having a purity of 99% or more, and representing a simple 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.

Step b) partial halogenation 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 stage of partial halogenation of the original diene-containing (co)polymer solution obtained in step a) 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 partial halogenation step b) 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 partial halogenation step may be any convenient time sufficient to achieve the desired degree of halogenation of the initial diene-containing (co)polymer described above. Preferably, the partial 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.

Step c) washing and separation

In stage c) washing and separation, water is added to the reaction mass obtained in stage b) containing a partially halogenated diene-containing (co)polymer, and then the aqueous layer and the organic layer containing the partially halogenated diene-containing (co)polymer are separated.

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

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, resulting in separation of the reaction mass into two layers: an organic layer containing a partially halogenated diene-containing (co)polymer, and an aqueous layer.

While the allowable residual content of the halogenating agent in the organic layer after washing with water is from 0 to 0.5 wt.%, preferably less than 0.2 wt. %, more preferably less than 0.05 wt.%.

Preferably, the washing 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.

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

Stage d) modifications

In step d) modification, the components of the modifying system are added to the organic layer obtained in step c) containing a partially halogenated diene-containing (co)polymer.

In accordance with the present invention, a carboxylic acid and a halogenating agent are used as a modifying system in a molar ratio of carboxylic acid:halogenating agent from 1:1 to 1000:1, preferably from 1:1 to 100:1, more preferably from 1:1 to 10 :one.

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

The halogenating agent may be, but is not limited to, a bromimide, such as N-bromosuccinimide, N-bromophthalimide, or a bromamide, such as N-bromoacetamide, or a bromourea, such as tetrabromoglycoluril, as such, as well as solutions in solvents with concentration from 1% to 50%.

As a carboxylic acid, acids such as C1-C8 alkyl carboxylic acids, for example, acetic acid, propionic acid, 2-ethylhexanoic acid, C1-C8 halogenated acids, for example, bromoacetic acid, 2-bromopropionic acid, C6 -C8 arylcarboxylic acid, eg benzoic acid, 4-methylbenzoic acid, C6-C8 halogenated arylcarboxylic acids, eg 4-bromobenzoic acid, or combinations thereof. Preferably, acetic acid, propionic acid, bromoacetic acid, benzoic acid, 4-bromobenzoic acid are used as the carboxylic acid. The presence of additional halogen atoms in the acid further improves the flame retardant properties of the modified diene-containing (co)polymer.

The molar ratio of halogenating agent:double bond of the partially halogenated diene-containing (co)polymer is from 0.001:1 to 0.1:1, more preferably from 0.01:1 to 0.05:1, most preferably from 0.01:1 up to 0.02:1.

The order in which the modifying system components are added to the organic layer obtained in step c) containing the partially halogenated diene-containing (co)polymer is arbitrary. Preferably, the carboxylic acid is added first, and then the halogenating agent is added.

The halogenating agent is dissolved in an organic solvent, 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, for example, cyclohexane , aromatic hydrocarbons such as toluene, halogenated aromatic hydrocarbons such as bromobenzene, chlorobenzene and dichlorobenzene, or a mixture thereof. 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 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, modification step d) of the partially halogenated diene-containing (co)polymer 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 likelihood of non-selective reactions occurring. photocatalytic halogenation.

Modification step d) is carried out at a temperature of 0 to 100°C, preferably 20 to 80°C, more preferably 40 to 60°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 duration of the modification step can be any sufficient to achieve the desired degree of modification of the initial diene-containing (co)polymer, as described above. Preferably, the duration of step d) of the modification 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 in stage d) of the modification contains the desired modified diene-containing (co)polymer containing acyloxyhalogenated diene units and halogen atoms, with a degree of acyloxyhalogenation of at least 0.01%, preferably at least 0.1%, most preferably at least 1 %.

Step e) neutralization and separation

Step e) according to this embodiment of the invention comprises neutralizing the reaction mass obtained in step d) 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, aqueous basic solutions known from the prior art are used, but are not limited to, for example, solutions of sodium hydroxide, sodium thiosulfate, sodium bisulfite, sodium dithionite, sodium hypophosphite, sodium ascorbate, sodium carbonate. Preferably, an aqueous solution of sodium hydroxide is used.

The molar ratio of the amount of neutralizing agent added in step e) to the amount of halogenating agent added in step b) is usually 1:1 to 3:1, preferably 1:1 to 2:1, more preferably 1:1.

Preferably, the neutralization in step e) 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 the 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 equipment known from the prior art, for example, using a separating funnel, separator, sump.

Step f) isolation

Step f) separating the obtained modified diene-containing (co)polymer from the organic layer from step e) can be carried out in two ways - precipitation, or degassing of the modified diene-containing (co)polymer.

In one embodiment of the invention, the method for producing a modified diene-containing (co)polymer is implemented through the stage of deposition of the resulting modified diene-containing (co)polymer. In such an embodiment, to isolate the modified diene-containing (co)polymer obtained in step d) to the organic layer obtained in step e) containing the modified diene-containing (co)polymer, an alcohol-non-solvent is added. The weight ratio of alcohol-non-solvent:modified diene-containing (co)polymer is in the range of 15:1 to 1:1, preferably 10:1 to 3:1, more preferably 5:1 to 4:1.

Suitable precipitating 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, or isobutanol. Preferably, methanol or ethanol is used as the precipitating alcohol.

In another embodiment, the method for producing a modified diene-containing (co)polymer is carried out through the stage of degassing the obtained modified diene-containing (co)polymer, while in stage f) isolation, water is added to the organic layer obtained in stage e), and then the water-solvent mixture is distilled off 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, or bidistilled water.

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

According to the present invention, the temperature of the water added in step f) is at most 30°C, preferably at most 25°C, more preferably at most 20°C. The use of water with a temperature above 30°C leads to boiling and subsequent rapid evaporation of the solvent, which, in turn, undesirably changes the physico-mechanical characteristics of the obtained 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 to 150°C, preferably 50 to 100°C, most preferably 80 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 in step f) is at least 30 minutes, more preferably at least 60 minutes, most preferably at least 120 minutes.

Stage g) filtration and drying

At stage g) filtration and drying 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 filter septa, suction filters and similar equipment .

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

To remove water and/or its vapors, solvent and/or its vapors from the obtained modified diene-containing (co)polymer, the said (co)polymer is dried. The drying process of the modified diene-containing (co)polymer is carried out by physical methods commonly used for the separation and purification of organic substances, for example, solvent distillation under reduced pressure, drying in a vacuum oven, and also 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 to 105° C. and a pressure of 20 to 1 kPa.

In addition, according to another embodiment of the present invention, a modified diene-containing (co)polymer containing acyloxyhalogenated diene units and halogen atoms is obtained by reacting a hydroxyhalogenated diene-containing (co)polymer with an acylating agent.

Thus, another proposed in accordance with the present invention, the method of obtaining a modified diene-containing (co)polymer containing acyloxyhalogenated diene units, includes the following steps:

obtaining a hydroxyhalogenated diene-containing (co)polymer;

a step of dissolving the hydroxyhalogenated diene-containing (co)polymer obtained in step a) in a solvent;

an acylation step comprising adding the components of the acylating system to the solution obtained in step b);

a washing and separation step comprising adding water to the reaction mass obtained in step c) 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 d);

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

Stage a) obtaining a hydroxyhalogenated diene-containing (co)polymer

A hydroxyhalogenated diene-containing (co)polymer containing hydroxyhalogenated diene units and halogen atoms can be obtained by any of the methods known from the prior art, allowing the introduction of hydroxyl groups and halogen atoms into the structure of the diene-containing (co)polymer, for example, by the method disclosed in the application WO2016123263 .

In particular, the original diene-containing (co)polymer to obtain hydroxyhalogenated diene-containing (co)polymer are 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 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 is 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 diene-containing (co)polymer, (co)polymers such as butadiene, butadiene-styrene and butadiene-styrene-isoprene are used, most preferably butadiene-styrene copolymer, which is di- and tri-block 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 initial diene-containing (co)polymers have 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 from 5000 to 200000 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.

Step b) Dissolution

In step b) dissolution, optionally, the hydroxyhalogenated diene-containing (co)polymer obtained in step a) is pre-milled, followed by its dissolution in an organic solvent with stirring.

Grinding, if necessary, hydroxyhalogenated diene-containing (co)polymer is carried out by any methods known from the prior art, for example, using knife, hammer, impact crushers, jet or screw mills, and similar equipment.

When dissolving the hydroxyhalogenated diene-containing (co)polymer, mixing can be carried out by any method known in the 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°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 acylation conditions of the hydroxyhalogenated diene-containing (co)polymer and are inert under the conditions of step c) of the acylation of the hydroxyhalogenated 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 organic solvent to 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 duration of step b) of the dissolution is at most 60 minutes, in particular at most 50 minutes, at most 40 minutes, at most 30 minutes, at most 25 minutes, at most 20 minutes, at most 15 minutes, at most 13 minutes, at most more than 11 minutes, no more than 9 minutes, no more than 7 minutes, no more than 5 minutes.

The mass obtained from the dissolution step b) above is a solution of a hydroxyhalogenated diene-containing (co)polymer in an organic solvent.

Step c) acylation

In step c) of the acylation, the components of the acylating system are added to the solution of the hydroxyhalogenated diene-containing (co)polymer obtained in step b).

In step c), the acylation reaction of hydroxyl groups in the molecule of the hydroxyhalogenated diene-containing (co)polymer occurs with the replacement of hydrogen atoms of hydroxyl groups by acyl groups to form acyloxy groups.

In accordance with the present invention, an activated carboxylic acid derivative and a base are used as the acylating system.

As an activated carboxylic acid derivative, carboxylic acid anhydrides, carboxylic acid halides, carboxylic acid imidazolides are used. Preferably, anhydrides and carboxylic acid halides are used. Most preferably, anhydrides and acid chlorides of carboxylic acids are used. These derivatives can be dissolved in any suitable solvent, however, it is preferable to use the same solvent as used in step b) to dissolve the hydroxyhalogenated diene-containing (co)polymer. The concentration of the solution may be from 1% to 99%, preferably from 2 to 80%.

A base is an organic or inorganic compound that has basic properties and is capable of neutralizing the acid released by the reaction. The inorganic base is, for example, an alkali metal hydroxide, an alkali metal carbonate, or an alkali metal phosphate. Preferably, an organic base containing a free amino group is used to ensure efficient diffusion to the polymer molecules. Most preferred are tertiary amines, eg triethylamine or tributylamine, and nitrogenous heterocycles, eg pyridine or 4-dimethylaminopyridine. The organic base may be dissolved in a suitable solvent, however, it is preferred to use the same solvent as used in step b) to dissolve the hydroxyhalogenated diene-containing (co)polymer. The concentration of the solution may be from 1% to 99%, preferably from 2 to 80%.

The molar ratio of activated carboxylic acid derivative:base is 1:1 to 1:10, preferably 1:1 to 1:5, more preferably 1:1.1 to 1:3. In some cases, for example, in the case of using acid imidazolides, the base is not used.

The components of the acylating system are added to the hydroxyhalogenated diene-containing (co)polymer obtained in step b) in random order. Preferably, the carboxylic acid is first added to the hydroxyhalogenated diene-containing (co)polymer solution, followed by the addition of the base, or the carboxylic acid and the base are added together, or the base is added first, then the acid.

The acylation 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 corrosive environments.

Preferably, the acylation step of the hydroxyhalogenated diene-containing (co)polymer is carried out in the absence of light, for example, by carrying out the acylation 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 of non-selective photocatalytic halogenation reactions.

The acylation step is carried out at a temperature of 0 to 100°C, preferably 0 to 80°C, more preferably 20 to 60°C, and atmospheric pressure.

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

The duration of step c) of the acylation may be any sufficient to achieve the desired degree of acylation of the hydroxyhalogenated diene-containing (co)polymer as described above. Preferably, the duration of step c) 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 the acylation step c) contains the desired modified diene-containing (co)polymer with an acyloxyhalogenation degree of at least 0.01%, preferably at least 0.1%, most preferably at least 1%.

Step d) washing and separation

Stage d) washing and separation is carried out by adding water to the reaction mass obtained in stage c) containing the modified diene-containing (co)polymer, followed by separation of the aqueous layer and the organic layer containing the modified diene-containing (co)polymer.

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

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, resulting in separation of the reaction mass into two layers: an organic layer containing a modified diene-containing (co )polymer, and an aqueous layer.

Preferably, the washing 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.

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

Step e) isolation

Step e) separating the obtained modified diene-containing (co)polymer from the organic layer from step d) is carried out in two ways - by precipitation or by degassing the modified diene-containing (co)polymer.

In one embodiment of the invention, an alcohol-precipitant is added to the organic layer obtained in step d) 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, isopropanol, butanol, isobutanol. Preferably, methanol and ethanol are used as the precipitating alcohol.

In another embodiment of the invention, the process is carried out through the step of degassing the resulting modified diene-containing (co)polymer. At the same time, water is added to the organic layer obtained in step d), followed by distillation of the water-solvent mixture at elevated temperature and reduced pressure in order to isolate the modified diene-containing (co)polymer and remove water and/or its vapors, solvent and/or its vapors.

In the context of the present invention, water is, but is not limited to, distilled, deionized, demineralized, osmotic, or 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. The use of water with a temperature above 30°C leads to boiling and subsequent rapid evaporation of the solvent, which, in turn, undesirably changes the physical and mechanical characteristics of the obtained 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 are, but are not limited to, continuous or batchwise agitators provided with a jacket.

The temperature of the degassing step is 20 to 150°C, preferably 50 to 100°C, most preferably 80 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 is at least 30 minutes, more preferably at least 60 minutes, most preferably at least 120 minutes.

Stage f) filtration and drying

At stage f) filtration and drying 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 filter septa, suction filters and other similar equipment.

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

To remove water and/or its vapors, solvent and/or its vapors from the obtained modified diene-containing (co)polymer, the said (co)polymer is dried. Drying of the modified diene-containing (co)polymer is carried out by physical methods commonly used for the separation and purification of organic substances, for example, solvent distillation under reduced pressure, drying in a vacuum oven, and 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 to 105° C. and a pressure of 20 to 1 kPa.

According to one embodiment of the present invention, the present invention is explained in more detail in FIG. 1, which shows a block diagram for the production of a modified diene-containing (co)polymer, where 101 is a block for dissolving the original diene-containing (co)polymer, 102 is a block for modifying the original diene-containing (co)polymer, 103 is a washing and separation block, 104 is an isolation block , 105 - filtration unit, 106 - drying unit, 107 - dissolution unit of acyloxyhalogenated diene-containing (co)polymer, 108 - partial halogenation unit of acyloxyhalogenated diene-containing (co)polymer, 109 - neutralization and separation unit, 110 - isolation unit, 111 - filtration unit , 112 - drying block.

According to the presented method, the crushed, if necessary, initial 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 initial diene-containing (co)polymer (3). Further, the specified solution of (co)polymer (3) enters in modification 102 , into which the modifying system (4) is also supplied. After that, the acyloxyhalogenated diene-containing (co)polymer (5) obtained in block 102 is sent to the washing and separation unit 103 , into which water is supplied (6), after which the organic layer (8) containing the acyloxyhalogenated diene-containing (co)polymer is separated, and water layer (7). Next, the organic layer (8) containing the acyloxyhalogenated diene-containing (co)polymer enters the separation unit 104 . Next, the isolated acyloxyhalogenated diene-containing (co)polymer (9) is sequentially (9, 10) fed to the filtration unit 105 and to the drying unit 106 in order to obtain the acyloxyhalogenated diene-containing (co)polymer (11).

After that, the crushed (not shown in the diagram) acyloxyhalogenated diene-containing (co)polymer (11) is sent to the dissolution unit 107 , where it is mixed with an organic solvent (12) to obtain a solution of acyloxyhalogenated diene-containing (co)polymer (13). Next, the dissolved (co)polymer (13) enters the partial halogenation unit 108 , which is also fed with a halogenating agent (14) and, optionally, an aliphatic alcohol (15). After that, the modified diene-containing (co)polymer (16) obtained in block 108 is sent to the neutralization and separation unit 109 , into which a neutralizing agent (17) is supplied, followed by water (17) for washing the neutralized reaction mass, after which the organic layer is separated (20) containing a modified diene-containing (co)polymer, and an aqueous layer (19). Then, the organic layer (20) containing the modified diene-containing (co)polymer enters the recovery unit 110 to recover the modified diene-containing (co)polymer. Next, the isolated modified diene-containing (co)polymer (21) is sequentially (21, 22) fed to the filtration unit 111 and to the drying unit 112 in order to obtain the final product - a modified diene-containing (co)polymer (23).

According to yet another embodiment, the present invention is explained in more detail in FIG. 2, which shows a block diagram for the production of a modified diene-containing (co)polymer, where 201 is a block for dissolving the original diene-containing (co)polymer, 202 is a block for partial halogenation of the dissolved original diene-containing (co)polymer, 203 is a washing and separation block, 204 - a block for modifying a partially halogenated diene-containing (co)polymer, 205 - a neutralization and separation block, 206 - a separation block, 207 - a filtration block, 208 - a drying block. The method for producing a modified diene-containing (co)polymer may also include an organic solvent regeneration unit with its subsequent recycling to the initial diene-containing (co)polymer dissolution unit 101 (not shown in Fig. 1).

According to the presented method, the initial diene-containing (co)polymer (1) crushed, if necessary, is sent to the dissolution unit 201 , 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 partial halogenation unit 202 , which is also fed with a halogenating agent (4) and, optionally, an aliphatic alcohol (5). After that, the partially halogenated diene-containing (co)polymer (6) obtained in block 202 is sent to the washing and separation unit 203 , into which water (7) is supplied, after which the organic layer (9) containing the partially halogenated diene-containing (co)polymer is separated. , and the water layer (8). Next, the organic layer (9) containing the partially halogenated diene-containing (co)polymer enters the modification unit 204 , which is also fed with the modifying system (10). After that, the modified diene-containing (co)polymer (11) obtained in block 204 is sent to the neutralization and separation unit 205 , into which a neutralizing agent (12) is supplied, followed by water (13) for washing the neutralized reaction mass, after which the organic layer is separated (15) containing a modified diene-containing (co)polymer, and an aqueous layer (14). Then, the organic layer (15) containing the modified diene-containing (co)polymer enters the recovery unit 206 '. Next, the isolated modified diene-containing (co)polymer (16) is sequentially (16, 17) fed to the filtration unit 207 and to the drying unit 208 in order to obtain the final product - the modified diene-containing (co)polymer (18). Also, the method for producing a modified diene-containing (co)polymer may include an organic solvent recovery unit, followed by its recycling to the initial diene-containing (co)polymer dissolution unit 201 (not shown in FIG. 2).

According to yet another embodiment, the present invention is explained in more detail in FIG. 3, which shows a block diagram for the production of a modified diene-containing (co)polymer, where 301 is a block for the preparation of a hydroxyhalogenated diene-containing (co)polymer, 302 is a block for dissolving a hydroxyhalogenated diene-containing (co)polymer, 303 is a block for acylation of a hydroxyhalogenated diene (co)polymer, 304 - washing and separation unit, 305 - isolation unit, 306 - filtration unit, 307 - drying unit. The method for producing a modified diene-containing (co)polymer may also include an organic solvent recovery unit with its subsequent recycling to the initial diene-containing (co)polymer dissolution unit 301 (not shown in FIG. 3).

According to the presented method, crushed, if necessary, the original diene-containing (co)polymer (1) is sent to the unit for producing hydroxyhalogenated diene-containing (co)polymer 301 . Next, the obtained hydroxyhalogenated diene-containing (co)polymer (2) is sent to the dissolution unit 302 , which is also supplied with a solvent (3), to obtain a solution of hydroxyhalogenated (co)polymer (4). Said (co)polymer solution (4) enters the acylation unit 303 , which is also fed with the acylating system (5). After that, the modified diene-containing (co)polymer (6) obtained in block 303 is sent to the washing and separation unit 304 , into which water is supplied (7), after which the organic layer (9) containing the modified diene-containing (co)polymer is separated, and water layer (8). Next, the organic layer (9) containing the modified diene-containing (co)polymer enters the separation unit 305 . Next, the isolated modified diene-containing (co)polymer (10) is sequentially (10, 11) fed to the filtration unit 306 and to the drying unit 307 in order to obtain the target product - a modified diene-containing (co)polymer (12).

Shown in FIG. 1, Fig. 2 and FIG. 3 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, 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 expandable polystyrene at the stage of its production by a method comprising obtaining 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 (see, for example, US5086078).

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 parts by weight, more preferably not less than 1 part by weight, otherwise, the effectiveness of improving the flame retardant 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, such as antistatic agents, stabilizers, dyes, lubricants, fillers, anti-agglomerators.

According to the present invention, expandable polystyrene compositions find use in the manufacture 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 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 is used as a flame retardant (flame retardant) in expandable polystyrene, as it is characterized by high thermal stability, namely, a 5% weight loss temperature of at least 180 ° C, measured by thermogravimetric analysis , does not affect the process of polymerization and formation of polystyrene granules, which is confirmed by the granulometric composition of the resulting polystyrene. In addition, the flame retardant (flame retardant) obtained in accordance with the present invention imparts flame retardant properties to expandable polystyrene and does not affect its other characteristics and properties.

In addition, the flame retardant (flame retardant) produced in accordance with the present invention imparts flame retardant properties to the expandable polystyrene, making 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 (according to 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.

Implementation of the invention

Methods for studying a modified diene-containing (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°С to 600°С, heating rate 10°С/min.

Infrared spectroscopy (IR)

The presence of functional groups in the modified diene-containing (co)polymer samples was determined by IR spectroscopy.

The spectra were obtained using a Varian Excalibur HE 3600 IR-Fourier spectrometer, Pike Miracle ATR attachment (crystal material - ZnSe/diamond). Scan range: 4000-400 cm ^-1 , number of scans - 32, spectral resolution 4 cm ^-1 . Samples were analyzed without preliminary sample preparation.

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. 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 were determined by low-temperature GPC in accordance with ISO16014-3 on an Agilent 1200 liquid chromatograph, refractometric detector.

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 was carried out according to relative calibration according to polystyrene standards (EasiVial PS-H 4ml, Agilent Technologies) using Mark-Houwink constants for rubber 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.

Determination of the yellowness index of polystyrene granules

Determination of the yellowness index of polystyrene granules containing a flame retardant (flame retardant) was carried out by spectroscopy in the visible region of the spectrum on an SP62 X-Rite spectrophotometer in accordance with ASTM D 6290-13.

Research conditions: The sample tube was filled with sample granules to the top. The tube filled with beads was placed in the center of the sensor port for measurement. Cover the sample vial with an opaque, light-blocking fixture or cap. Illumination source - D65 (daylight), viewing angle 10°, including reflected light (spin). To determine the yellowness index, the necessary readings of the three-color diagram X, Y, Z were obtained. The number of parallel measurements was 3.

The yellowness index value was obtained in accordance with ASTM E 3013-10.

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.

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 bottom 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 the filter paper for no more than 2 s, and also do not result in to ignite the filter paper.

Example 1 . Obtaining a modified butadiene-styrene copolymer containing acetoxybrominated diene units (1% modifying system containing acetic acid)

In a dark glass flask with a volume of 250 ml add a solution of the original butadiene-styrene copolymer brand SBS R 30-00 A (SIBUR) in dichloromethane (10 g of copolymer per 100 g of dichloromethane). Next, 0.074 g (1.2 mmol) of acetic acid is added to the flask. Then turn on the stirring and set the bath temperature to 35°C.

Next, a solution of 0.22 g (1.2 mmol) of N-bromosuccinimide in dichloromethane is prepared and added dropwise to the flask, after which the reaction mass is stirred for 2 hours. Then add to it 0.5 g of 20 mol.% sodium hydroxide solution and carry out neutralization for 30 minutes. Then the reaction mass is washed with a threefold volume excess of water, the obtained acetoxybrominated butadiene-styrene copolymer is precipitated with isopropyl alcohol and dried in a vacuum oven at 60°C and 0.5 kPa.

The resulting acetoxybrominated butadiene-styrene copolymer powder was dissolved in 100 g of dichloromethane and placed in a dark 250 ml flask. Turn on stirring and set the bath temperature to 35°C. 7.5 g of butanol are added. Then a solution of bromine in dichloromethane (18.9 g of bromine per 18.9 g of dichloromethane) is dosed into the flask and the solution is stirred for 30 minutes at 35°C. Then the reaction mass is washed with a threefold volume excess of distilled water.

After completion of the reaction, 20 g of 20 mol.% sodium hydroxide solution is added to the flask and neutralization is carried out for 60 minutes. Then the reaction mass is washed with a threefold volume excess of water, followed by precipitation of the resulting acetoxybrominated styrene-butadiene copolymer with isopropyl alcohol. Next, the resulting acetoxybrominated butadiene-styrene copolymer 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°C and 0.5 kPa.

The characteristics of the acetoxybrominated styrene-butadiene copolymer prepared in Example 1 are shown in Table. one.

Examples 2-7. Obtaining acetoxybrominated butadiene-styrene copolymers and benzoyloxybrominated butadiene-styrene copolymers with varying the amount of modifying system

Examples 2-7 are carried out similarly to Example 1, except that the amount of modifying system was varied. In Table. 2 shows the quantities of the modifying system.

In addition, in example 7, the process of introducing benzoic groups into the structure of the copolymer took place within 8 hours at 38°C.

Characteristics of the modified styrene-butadiene copolymers obtained according to Examples 2-3 are presented in Table. one.

Characteristics of the modified styrene-butadiene copolymers obtained according to Examples 4-7 are presented in Table. 3.

Table 1. Characteristics of modified styrene-butadiene copolymers containing acetoxy groups

Example No. The amount of the modifying system, mol.% Weight average molecular weight
10 ³ , g/mol Decomposition temperature (5% weight loss),
°С Example 1 one 103 238 Example 2 5 103 237 Example 3 ten 104 238

The presence of acetoxy groups in the structure of the resulting modified styrene-butadiene copolymer is confirmed by the IR spectrum by the appearance of an absorption band at 1740 cm ^-1 .

It can be seen from the data in Table 1 that the thermal stability characteristics of the acetoxy-modified brominated styrene-butadiene copolymer remain constant.

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

Table 2. Amount of starting materials for Examples 2-7.

Example No. The amount of modifying system used (acetyl), mole %. The amount of used modifying system (benzoyl), % mol. Amount of acetic acid, g The amount of benzoic acid, g Amount of N-bromosuccinimide, g The amount of bromine, g 2 5 - 0.4 - 1.09 18.12 3 ten - 0.74 - 2.19 17.16 four - one - 0.15 0.22 18.49 5 - 5 - 0.75 1.09 17.74 6 - ten - 1.5 2.19 16.81 7 - ten - 1.5 2.19 16.81

Table 3. Characteristics of modified styrene-butadiene copolymers containing benzoyloxy groups

Example No. The amount of used modifying system (benzoyl), % mol. groups, mol.% Weight average molecular weight
10 ^-3 , g/mol Decomposition temperature (5% weight loss),
°С The content of links according to the NMR spectrum, % mol. Styrene 1,2-butadiene 1,4-butadiene bromine butadiene benzoic groups Example 4 one 105 216 22.1 - - 77.6 0.2 Example 5 5 104 228 21.4 77.6 0.2 Example 6 ten 104 235 21.5 - - 77.6 0.8 Example 7 ten* 104 238 21.5 - - 77.5 1.5

* the process of modification of the copolymer was held for 8 hours at 38°C.

From the data of Table 3, it can be seen that the thermal stability characteristics of the brominated copolymer modified with benzoyloxy groups gradually increase with increasing degree of modification (Examples 4-7). With an increase in the duration of the synthesis, the degree of modification increases (Examples 6, 7). At the maximum amount of the modifying system, the thermal stability reaches the thermal stability of the acetoxybrominated butadiene-styrene copolymer.

Example 8 (comparative) . Obtaining a brominated butadiene-styrene copolymer without a modifying system.

In a dark glass flask with a volume of 250 ml add a solution of the original butadiene-styrene copolymer brand SBS R 30-00 A (SIBUR) in dichloromethane (10 g of copolymer per 100 g of dichloromethane). Turn on stirring and set the bath temperature to 35°C. 7.5 g of butanol are added. Then a solution of bromine in dichloromethane (18.9 g of bromine per 18.9 g of dichloromethane) is dosed into the flask and the solution is stirred for 30 minutes at 35°C.

After completion of the reaction, 20 g of 20 mol % sodium hydroxide solution is added to the flask and neutralization is carried out for 60 minutes. Then the reaction mass is washed with a threefold volume excess of water, followed by precipitation of the resulting brominated styrene-butadiene copolymer with isopropyl alcohol. Next, the obtained brominated styrene-butadiene copolymer 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°C and 0.5 kPa.

The decomposition temperature (5% weight loss) was 212°C.

Thus, it can be noted that the decomposition temperature of the unmodified brominated copolymer is substantially lower than that of the copolymers of the invention.

Example 9 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, with stirring, was added 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 and 7, and 0.21 parts of the flame retardant (flame retardant) synergist (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 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) is added to the reaction mass - the step of foaming the polystyrene. After reaching 115°C in the flask maintain a constant temperature for 3 hours, after which the mixture is cooled to a temperature of 25°C for 3 hours.

Table 4. Granulometric composition of polystyrene containing a flame retardant (flame retardant)

Granule size, mm Example 1 Example 7 2.00 1.53 0.41 1.60 14.90 6.82 1.00 76.77 62.97 0.70 6.06 20.69 0.40 0.58 5.94 0.2 - 2.93 bottom 0.16 0.23 Sum of fractions 97.73 90.48

Modified copolymers of butadiene and styrene, obtained according to Examples 1 and 7, when introduced into polystyrene, do not affect the granulometric composition, a stable suspension is formed and granules of the required sizes are obtained, fully satisfying TU 2214-019-53505711-2010 (Table 4).

Table 5 presents the results of a comparison of the yellowness index (average yellowness) for expanded polystyrene beads containing flame retardants (flame retardants) according to Examples 1 and 7 and HBCD. From the data of Table 5 it can be seen that, although the color of PSV containing flame retardants according to the invention (according to Examples 1, 7) is slightly higher than products with HBCD, however, it is possible to significantly reduce the color compared to unmodified brominated flame retardant (according to Example 8).

Table 5. Comparison of indicators of the yellowness index of foamed polystyrene granules containing flame retardants (flame retardants)

Flame retardant (flame retardant) Average yellowness HBCD 1.42-2.1 Example 1 3.2 Example 7 3.0 Example 8 7.0

Example 10 . Obtaining acetoxybrominated butadiene-styrene copolymer by acylation of hydroxybrominated copolymer

A solution of a hydroxybrominated copolymer prepared analogously to WO2016123263 from a starting SBS R 30-00 A styrene-butadiene copolymer (SIBUR) in dichloromethane (10 g of copolymer per 100 g of dichloromethane) is added to a 250 ml flask. Next, 1 g (12.7 mmol) of pyridine is added to the flask, followed by 1 g (12.7 mmol) of acetic acid chloride. Then turn on the stirring and set the bath temperature to 30°C. The reaction mass is stirred for 2 hours. Next, the reaction mass is washed three times with 100 ml of water, the polymer is precipitated with isopropyl alcohol and dried in a vacuum oven at 60°C and 0.5 kPa.

The decomposition temperature of the product (5% weight loss) was 250°C.

Without wishing to be bound by any theory, the present inventors believe that the presence of acyloxyhalogenated diene units, in addition to halogen atoms in the modified diene-containing (co)polymer, provides better compatibility of the (co)polymer flame retardant (flame retardant) with the polystyrene matrix. Also, acyloxyhalogenated groups give the flame retardant (flame retardant) high heat resistance.

As a result, when a flame retardant (fire 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 two types of functional groups, namely acyloxy groups and halogen atoms, simultaneously present in the 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.

Claims (92)

1. A modified diene-containing (co)polymer containing halogen atoms and acyloxyhalogenated diene units in its structure, 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 least 35 wt.%. 2. Modified diene-containing (co)polymer according to claim 1, which contains acyloxyhalogenated diene units, in an amount of from 0.01 to 10 wt.%, preferably in an amount of from 0.1 to 5 wt.%, more preferably in an amount of from 1 up to 3 wt.%. 3. The modified diene-containing (co)polymer according to claim 1, wherein the acyloxyhalogenated diene units are acyloxybrominated diene units. 4. Modified diene-containing (co)polymer according to claim 1, characterized by a temperature of 5% weight loss of at least 220°C, preferably at least 230°C. 5. 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. 6. Modified diene-containing (co)polymer according to claim 1, in which the content of halogen atoms is at least 60 wt.%, preferably at least 75 wt.%. 7. Modified diene-containing (co)polymer according to any one of paragraphs. 1-6, where the (co)polymer is a modified butadiene, butadiene-styrene or butadiene-styrene-isoprene (co)polymer, preferably a modified butadiene-styrene copolymer. 8. A method for producing a modified diene-containing (co)polymer according to any one of claims 1 to 7, including the following steps: a) the step of dissolving the initial diene-containing (co)polymer in a solvent; b) a modification step by adding the components of the modifying system to the solvent solution of the initial diene-containing (co)polymer obtained in step a) to obtain an acyloxyhalogenated diene-containing (co)polymer; c) a washing and separation step comprising adding water to the reaction mass obtained in step b) and separating the aqueous and organic layers; d) optionally, a separation step comprising precipitation or degassing of the acyloxyhalogenated diene-containing (co)polymer from the organic layer obtained in step c); e) optionally, the step of filtering and then drying the isolated acyloxyhalogenated diene-containing (co)polymer; f) optionally, a dissolution step comprising pre-grinding the acyloxyhalogenated diene-containing (co)polymer followed by dissolution in a solvent; g) a step of halogenating the acyloxyhalogenated diene-containing (co)polymer, comprising adding a halogenating agent and optionally an aliphatic alcohol to the solution obtained in step f); h) a neutralization and separation step comprising adding an aqueous solution of a neutralizing agent to the reaction mass obtained in step g) and separating the aqueous and organic layers; i) a separation step comprising precipitating or degassing the modified diene-containing (co)polymer from the organic layer obtained in step h); j) step of filtering and subsequent drying of isolated modified diene-containing (co)polymer, wherein the method is characterized in that in step b) of modification, a carboxylic acid and a halogenating agent are used as a modifying system in a molar ratio of carboxylic acid:halogenating agent from 1:1 to 1000:1. 9. The method according to claim 8, characterized in that the molar ratio of carboxylic acid:halogenating agent in the modifying system in step b) is from 1:1 to 100:1, preferably from 1:1 to 10:1. 10. The method according to claim 8, characterized in that chlorine, bromine or iodine is used as the halogen in the modifying system in step b), bromine is preferably used. 11. The method according to claim 8, characterized in that the halogenating agent in the modifying system in step b) is a bromimide, for example, N-bromosuccinimide or N-bromophthalimide, a bromamide, for example, N-bromoacetamide, bromourea, for example, tetrabromoglycoluril, or their solutions in solvents with a concentration of 1% to 50%. 12. The method according to claim 8, characterized in that C1-C8 alkylcarboxylic acids, such as acetic acid, propionic acid, 2-ethylhexanoic acid, C1-C8 halogen-containing acids, such as such as bromoacetic acid, 2-bromopropionic acid, C6-C8 arylcarboxylic acids such as benzoic acid, 4-methylbenzoic acid, C6-C8 halogenated arylcarboxylic acids such as 4-bromobenzoic acid, or combinations thereof, preferably acetic acid, propionic acid are used , bromoacetic acid, benzoic acid, or 4-bromobenzoic acid. 13. The method according to p. 8, characterized in that the initial diene-containing (co)polymer is a polymers and copolymers of a conjugated diene. 14. The method according to p. 13, characterized in that the conjugated diene is a conjugated diene selected from the group consisting of 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, preferably 1,3-butadiene or isoprene. 15. The method according to p. 13, characterized in that vinylaromatic compounds selected from the group consisting of styrene, α-methylstyrene, ortho-, meta- and para-methylstyrene, 3- vinyltoluene, ethylvinylbenzene, 4-cyclohexylstyrene, para-tert-butylstyrene, methoxystyrenes, vinylmesitylene, divinylbenzene, 1-vinylnaphthalene, 2,4,6-trimethylstyrene, or mixtures thereof, preferably styrene or α-methylstyrene. 16. The method according to claim 8, characterized in that the initial diene-containing (co)polymer is a butadiene, butadiene-styrene or butadiene-styrene-isoprene (co)polymer, preferably a butadiene-styrene copolymer. 17. The method according to p. 8, 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. 18. The method according to claim 8, 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. 19. The method according to p. 8, characterized in that the content of 1,2-units in the original diene-containing (co)polymer is at least 10 to 100 wt.%, preferably at least 50 to 99 wt.%, more preferably from 60 to 80 wt.% on the polybutadiene part of the (co)polymer. 20. The method according to any one of paragraphs. 8-19, characterized in that the original diene-containing (co)polymer is pre-crushed. 21. The method according to claim 8, characterized in that the molar ratio of halogenating agent:double bond of the original diene-containing (co)polymer in step b) is from 0.001:1 to 0.1:1, more preferably from 0.01:1 to 0.05:1, most preferably 0.01:1 to 0.02:1. 22. The method according to claim 8, characterized in that step b) of the modification is carried out at a temperature of from 0 to 100°C, preferably from 20 to 80°C, more preferably from 40 to 60°C. 23. The method according to claim 8, characterized in that the degree of acyloxyhalogenation obtained in step b) modification of the acyloxyhalogenated diene-containing (co)polymer is at least 0.01%, preferably at least 0.1%, most preferably at least 1%. 24. The method according to claim 8, characterized in that in step g) of the halogenation, chlorine, bromine or iodine, preferably bromine, is used as the halogen in the halogenating agent. 25. The method according to claim 8, characterized in that the halogenating agent in stage g) halogenation is selected from the group consisting of bromine as such, a solution of bromine in an organic solvent with a bromine content of not more than 70 wt.%, preferably not more than 60 wt. %, more preferably not more than 50 wt.%, quaternary ammonium bromides, quaternary phosphonium bromides, or mixtures thereof. 26. The method according to claim 25, characterized in that elemental bromine and quaternary ammonium bromides, such as phenyltriethylammonium bromide, benzyltrimethylammonium bromide, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetra-n -butylammonium bromide, or mixtures thereof, or quaternary phosphonium bromides such as tetramethylphosphonium bromide, tetraethylphosphonium bromide, tetrapropylammonium bromide, tetra-n-butyl-ammonium tribromide, or mixtures thereof. 27. The method according to p. 8, characterized in that stage g) halogenation is carried out in the presence of an aliphatic alcohol. 28. The method according to p. 27, characterized in that the mole ratio of acyloxyhalogenated diene-containing (co)polymer:halogenating agent:aliphatic alcohol in step g) 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. 29. The method according to p. 27, characterized in that methanol, ethanol, propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, pentanol, isoamyl alcohol, hexanol are used as aliphatic alcohol in stage g) of halogenation . 30. Process according to claim 8, characterized in that step g) of 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. 31. A method for producing a modified diene-containing (co)polymer according to any one of claims 1 to 7, including the following steps: a) the step of dissolving the initial diene-containing (co)polymer in a solvent; b) a partial halogenation step using a halogenating agent to a degree of halogenation of at least 60%; c) a washing and separation step by adding water to the reaction mass obtained in step b) and separating the aqueous and organic layers; d) a modification step comprising adding components of the modifying system to the organic layer obtained in step c) containing a partially halogenated diene-containing (co)polymer; 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 separation step comprising precipitating or degassing the modified diene-containing (co)polymer from the organic layer obtained in step e); g) step of filtering and subsequent drying of the modified diene-containing (co)polymer, wherein the method is characterized in that in step d) of the modification, a carboxylic acid and a halogenating agent are used as the modifying system in a molar ratio of carboxylic acid:halogenating agent from 1:1 to 1000:1. 32. The method according to p. 31, characterized in that the initial diene-containing (co)polymer is a polymers and copolymers of a conjugated diene. 33. The method according to p. 32, characterized in that the conjugated diene is a conjugated diene selected from the group consisting of 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, preferably 1,3-butadiene or isoprene. 34. The method according to p. 32, characterized in that vinylaromatic compounds selected from the group including styrene, α-methylstyrene, ortho-, meta- and para-methylstyrene, 3-vinyltoluene are used as a comonomer in the initial diene-containing (co)polymer , ethylvinylbenzene, 4-cyclohexylstyrene, p-tert-butylstyrene, methoxystyrenes, vinylmesitylene, divinylbenzene, 1-vinylnaphthalene, 2,4,6-trimethylstyrene, or mixtures thereof, preferably styrene or α-methylstyrene. 35. The method according to p. 31, characterized in that the initial diene-containing (co)polymer is a butadiene, butadiene-styrene or butadiene-styrene-isoprene (co)polymer, preferably a butadiene-styrene copolymer. 36. The method according to p. 31, 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. 37. The method according to p. 31, characterized in that the original 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. 38. The method according to p. 31, characterized in that the content of 1,2-units in the original diene-containing (co)polymer is at least 10 to 100 wt.%, preferably at least 50 to 99 wt.%, more preferably from 60 to 80 wt.% on the polybutadiene part of the (co)polymer. 39. The method according to any one of paragraphs. 31-38, characterized in that the original diene-containing (co)polymer is pre-crushed. 40. The method according to p. 31, characterized in that the molar ratio of carboxylic acid:halogenating agent in the modifying system is from 1:1 to 100:1, preferably from 1:1 to 10:1. 41. The method according to p. 31, characterized in that chlorine, bromine or iodine, preferably bromine, is used as the halogen in the modifying system in step d) . 42. The method according to p. 31, characterized in that the halogenating agent in the modifying system in stage d) is a bromimide, for example, N-bromosuccinimide or N-bromophthalimide, bromamide, for example, N-bromoacetamide, bromourea, for example, tetrabromoglycoluril, as as such, or in the form of solutions in solvents with a concentration of from 1% to 50%. 43. The method according to p. 31, characterized in that C1-C8 alkylcarboxylic acids, such as acetic acid, propionic acid, 2-ethylhexanoic acid, C1-C8 halogen-containing acids, such as as bromoacetic acid, 2-bromopropionic acid, C6-C8 arylcarboxylic acids such as benzoic acid, 4-methylbenzoic acid, C6-C8 halogenated arylcarboxylic acids such as 4-bromobenzoic acid, or combinations thereof, preferably acetic acid, propionic acid, bromoacetic acid, benzoic acid, 4-bromobenzoic acid, or combinations thereof. 44. Process according to claim 31, characterized in that the degree of halogenation in step b) of partial halogenation is at least 90%, preferably at least 95%. 45. The method according to claim 31, characterized in that in step b) of partial halogenation, chlorine, bromine or iodine, preferably bromine, is used as the halogen in the halogenating agent. 46. The method according to p. 31, characterized in that the halogenating agent in stage b) 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 ammonium bromides, quaternary phosphonium bromides, or mixtures thereof. 47. The method according to p. 45, characterized in that elemental bromine and quaternary ammonium bromides, such as phenyltriethylammonium bromide, benzyltrimethylammonium bromide, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetra-n-butylammonium bromide, are preferably used simultaneously as a halogenating agent, or mixtures thereof, or quaternary phosphonium bromides such as tetramethylphosphonium bromide, tetraethylphosphonium bromide, tetrapropylammonium bromide, tetra-n-butyl ammonium tribromide, or mixtures thereof. 48. The method according to p. 31, characterized in that stage b) halogenation is carried out in the presence of an aliphatic alcohol. 49. The method according to p. 48, 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. 50. The method according to p. 48, characterized in that methanol, ethanol, propanol, iso-propanol, butanol, iso-butanol, pentanol, hexanol are used as aliphatic alcohol in stage b) of partial halogenation. 51. The method according to p. 31, characterized in that stage b) partial 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. 52. The method according to p. 31, characterized in that the degree of acyloxyhalogenation obtained in stage d) modification of the modified diene-containing (co)polymer is at least 0.01%, preferably at least 0.1%, more preferably at least 1 %. 53. A method for producing a modified diene-containing (co)polymer according to any one of claims 1 to 7, including the following steps: a) obtaining a hydroxyhalogenated diene-containing (co)polymer; b) the step of dissolving the hydroxyhalogenated diene-containing (co)polymer obtained in step a) in a solvent; c) an acylation step comprising adding the components of the acylating system to the solution obtained in step b); d) a washing and separation step comprising adding water to the reaction mass obtained in step c) and separating the aqueous and organic layers; e) a separation step comprising precipitating or degassing the modified diene-containing (co)polymer from the organic layer obtained in step d); f) a step of filtering and then drying the isolated modified diene-containing (co)polymer. 54. The method of claim 53, wherein the acylating system of step c) comprises an activated carboxylic acid derivative and a base. 55. The method according to p. 53, characterized in that the molar ratio of activated carboxylic acid derivative:base is from 1:1 to 1:10, preferably from 1:1 to 1:5, more preferably from 1:1.1 to 1 :3. 56. The method according to claim 53, characterized in that carboxylic acid anhydrides, carboxylic acid halides, carboxylic acid imidazolides, preferably carboxylic acid anhydrides and carboxylic acid halides, more preferably carboxylic acid anhydrides and acid chlorides are used as the activated carboxylic acid derivative. 57. The method according to p. 53, characterized in that the base may be an organic or inorganic base. 58. The method of claim 57 wherein the inorganic base may be an alkali metal hydroxide, an alkali metal carbonate, or an alkali metal phosphate. 59. The method according to p. 57, characterized in that the organic base contains a free amino group, and may be tertiary amines such as triethylamine, tributylamine, nitrogenous heterocycles such as pyridine, 4-dimethylaminopyridine. 60. The method according to any one of paragraphs. 53-59, characterized in that in step b) the hydroxyhalogenated diene-containing (co)polymer is pre-crushed. 61. The method according to p. 53, characterized in that the degree of acyloxyhalogenation obtained in stage c) acylation of the modified diene-containing (co)polymer is at least 0.01%, preferably at least 0.1%, more preferably at least 1 %. 62. The use of a modified diene-containing (co)polymer according to any one of paragraphs. 1-7 as a flame retardant (flame retardant). 63. Use according to claim 62, characterized in that the modified diene-containing (co)polymer is used as a flame retardant (flame retardant) in expandable polystyrene. 64. Expandable polystyrene containing a modified diene-containing (co)polymer according to any one of paragraphs. 1-7 as a flame retardant (flame retardant). 65. Expandable polystyrene according to claim 64, 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. 66. Polymer composition based on expandable polystyrene for construction, including a modified diene-containing (co)polymer according to any one of paragraphs. 1-7 as a flame retardant (flame retardant) and additives that provide a set of technological, physical, mechanical and operational characteristics. 67. The polymer composition according to claim 66, in which the additives are antistatic agents, stabilizers, dyes, lubricants, fillers, anti-agglomerators.

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