SU907011A1 - Process for producing static carbochain polymers - Google Patents

Description

The invention relates to the synthesis of macromolecular compounds, in particular to a method for producing static carbochain copolymers, and can be used in the petrochemical industry as additives to rubber mixtures for the production of vulcanizates with high dynamic properties, high tear resistance, abrasion, etc., as well as modifying additives to polystyrene, increasing its resistance to shock loads.

A method is known for producing static carbochain copolymers by solo- _(by limerization of dienes and vinyl aromatic monomers under the action of organolithium catalysts in neutral hydrocarbon media in the presence of compounds that solvate lithium counterion well (esters, thioethers, tertiary amines) [1].

However, the introduction of highly solvating additives sharply increases up to 2 of the side vinyl units in the copolymer, which impairs its properties. The closest to the proposed method is the production of static carbochain copolymers by copolymerization of butadiene or isoprene with styrene in an inert hydrocarbon solvent at 10-100 ° C in the presence of lithium catalysts . As the latter, an organolithium catalyst modified with potassium metal, rubidium or cesium is used. To obtain a modified catalyst, an appropriate metal is introduced into a solution of an organolithium compound, which necessarily contains an aromatic additive, and the reaction mixture is heated almost to its melting point. The reaction mixture is intensively stirred to disperse the metal and then the reaction is carried out for several hours at 50-80 ° C until the metal is completely dissolved. The ratio of organolithium compound and modifying metal is 1: (0.0050.2) mol, the ratio of monomer and catalyst is 0.01-100 mmol of catalyst per 1 mol of monomer, depending on the desired molecular weight of the copolymer.

Thus, the modification is carried out by replacing a part of the organolithium catalyst with an organopotassium one by metallization of an aromatic additive (2].

However, this does not increase the normality of the catalyst, and part of the organolithium compound is irretrievably lost.

The disadvantages of this method are also the long time to obtain the catalyst (37 h), the increased synthesis temperature (50 -60 ° C) and the use of potassium, rubidium or cesium as modifiers, which have a high cost and exceptional fire hazard.

The purpose of the invention is to simplify the technology for the preparation of the catalyst and increase efficiency.

This goal is achieved by the method of producing static carbochain copolymers by copolymerization of butadiene or isoprene with s'-styrene in an inert hydrocarbon solvent at 10-100 ° C in the presence of lithium catalysts selected from the group consisting of co-extrusion or extrusion of lithium metal with sodium or potassium at a weight ratio of L i: Na (K) 1 00: (50 “0, 1) and a low molecular weight living product of the polymerization of butadiene or isoprene under the action of lithium alkyls with the addition of sodium or potassium at mol alkyl the ratio m Li: Na (K) of 1: (1-50).

I

The introduction of modifying additives can be carried out in various ways. When copolymerizing under the action of lithium metal, modifying sodium or potassium is preliminarily introduced by joint pressing or extrusion in a plastic state at temperatures below their melting points. The obtained mixed metal is crushed into pieces of arbitrary size and the pressing or extrusion operation is repeated several times in order to more finely and evenly distribute the modifying additive in the mass of lithium metal.

The degree of mixing of metals can be controlled visually or using optical devices, since alternating ч x layers have different colors. The thickness of these layers is uncritical and can range from 1 to 300-500 microns.

Metals as they dissolve and wear as a result of their transformation into living ones, the polymers must remain in contact with each other. The proposed method of introducing a modifying additive allows to vary its content over a wide range, since it cannot be achieved in another way, for example by fusion, due to incompatibility with lithium. Thus, the amount of introduced sodium or potassium is in the range of 50-0.1 wt.% With respect to lithium, the preferred interval for obtaining the composition of the copolymer closest to static, for sodium 18-13 wt.?, For potassium 2-0.1 weight.%.

The introduction of modifying additives c / soluble organolithium catalyst, for example butyl lithium, is as follows. First, a low molecular weight living prepolymer is prepared by polymerization of diene, styrene, or a mixture thereof in the presence of an organolithium catalyst and sodium or potassium metal. During this polymerization, part of the added metal turns into a living polymer and passes into a solution, which is then used as a catalyst for copolymerization of the bulk of the monomers. Thus, the resulting catalytic solution, in addition to the organolithium compound introduced initially, also contains a disodium or dipotassium living polymer, the amount of which with respect to lithium can be regulated ^{45 by} prepolymerization under appropriate conditions. For the proposed method, such conditions are the concentration of butyllithium 0.50.005 mol / l, the concentration of mono ⁵⁰ measure 0.5-mol / l, temperature 1090 ° C, the molar ratio of organolithium compounds to sodium or potassium in the range of 1: (50-1) . The prepolymerization time depends on the polymerizing system and can range from 10-15 minutes to 2-3 hours. The monomer can be introduced during the synthesis of the catalyst immediately or gradually, the degree of conversion is 10-100%. After removal of the catalytic solution, the modifying additive can be used repeatedly, up to its complete dissolution, while, in contrast to the known method, the loss of the organolithium catalyst does not occur.

The copolymerization of dienes with styrene under the action of a modified catalyst is carried out periodically or continuously at 10-100 ° C. Aromatic or cycloaliphatic solvents are preferred as the medium, but mixed solvents containing aliphatic hydrocarbons are also possible. The concentration of the sum of monomers 0.5 ~ 5 mol / l, the styrene content of 1585 wt.%.

The ratio of monomer to catalyst depends on the type of catalyst. When copolymerizing on a mixed metal, it is usually necessary to have a large excess of it with respect to the monomer in order to provide the necessary initiation rate and a sufficient number of active sites; therefore, the ratio of monomer to catalyst is selected in the range of 1-15 parts by weight. bi, metal per 100 parts by weight sum of monomers. Due to the fact that the mixed metal is used in coarse-grained form (pieces, granules of size '3-10 mm) and its dispersion during copolymerization is insignificant, at the end of the process it can be easily separated from the polymer solvent and used repeatedly, up to its complete dissolution Thus, the degree of use of the metal is quite high and can reach 60-70% depending on its composition and copolymerization conditions (mixing intensity, temperature and concentration of monomers).

The ratio of the sum of monomers to the soluble modified copolymerization catalyst is determined in the usual manner depending on the desired molecular weight. In this case, the molecular weight is directly proportional to the weight of the polymerized monomers and inversely proportional to the number of moles of the catalyst taken; the correction for the difunctionality of the modifying additive is small. The ratios used are in the range of 10 to 0.2–5 mmol of catalyst per

100 · parts by weight monomers. Example 1

A. Preparation of the catalyst.

0.274 g of lithium metal cut into 3x3x3 mm pieces is pressed with 0.061 g of sodium under a layer of hydrocarbon solvent. The resulting plate is cut into pieces of the same size, mixed and pressed again. The operation is repeated 5 times. Obtain 0.335 g of bimetal containing 18.2 wt.% Sodium. The degree of distribution of sodium is estimated by the thickness of its layers in lithium, clearly visible on the cut. The layer thickness is from 3 ~ 5 microns to 20-50 microns. When grinding the catalyst to a size of 3x3x3 mm, its composition in pieces is preserved. The uniformity of the composition is controlled in a solvent with a density close to that of the metal being mixed, for example, a mixture of hexane with toluene.

The resulting bimetal has good mechanical strength, is ductile and does not crumble upon deformation, since the layers of lithium and sodium are firmly bonded by adhesive forces. It does not lose shape under the influence of small mechanical forces, even when heated to 100 ° C, i.e. higher than the melting point of sodium (97.7 ° C).

B. Copolymerization. A mixture of 2.7 ml of styrene and 6.4 g of butadiene in 30 ml of toluene is polymerized in a glass ampoule containing 0.335 g of the obtained catalyst and 5 ml glass beads with a diameter of 3 mm. Temperature poly _(merizatsii 20 ° C. The constant stirring of the contents ¹¹ and the activation of the catalyst is carried out by shaking the vial. After 1 h, the polymer sample is taken for the composition of the mic. Rostruktury diene portion and exit.

The output during this time is 15%. The composition of the copolymer according to IR spectroscopy of 39.7% styrene (the initial composition of the monomers had 39 »0% styrene). The microstructure of the diene part of the copolymer 28.5% CIS-1,4; 38.4% trans-1.4 and 33.1% 1.2 units.

The copolymerization of the remaining monomers is carried out at 25 ° C for

including the characteristic viscosity of the polymer 7 "3 DL / g The polymer is readily soluble in toluene, cyclohexane, and a mixture of toluene with heptane in a ratio of 2: 1. According to gel permeation chromatography, its molecular weight distribution is unimodal and close to 1, 2-1, 3.

B. Comparative copolymerization on unmixed metals.

The copolymerization of 1.63 g of styrene and 2.11 g of butadiene in 15 ml of toluene is carried out as in step B. The catalyst is 0.259 g of finely chopped lithium and ι

Oh, 040 g of sodium. Metals are not processed before use. The copolymerization is carried out at 20 ° C for 1 h. The copolymer yield during this time is 8.6%, the old la content in the copolymer is 55.5% (in the initial mixture 43.6%). The microstructure of polybutadiene units consists of 1, 6%

1,4-cis ·, 58., 8 1,4-trans and 39.6% 1,2. The copolymer has a bimodal molecular weight distribution, polydispersity factor 3.67

With a close sodium content in the catalyst (.18.2 and 13.4%, respectively), styrene and 2 butadiene copolymerization on pre-mixed metals proceeds with very close copolymerization constants and the best microstructure of polybutadiene units. 3

Example 2

A. Preparation of the catalyst.

8.7 g of lithium and 1.3 g of sodium in the form of pieces of arbitrary shape and size 3x5x5 mm. They are loaded into a device that allows ₃ to squeeze them together in the form of a wire with a diameter of 0.8 mm. The mixing of metals and the formation of strong adhesive layers between them occurs during their plastic flow near ₄ , behind the holes of the die. The resulting bimetallic wire is cut into: pieces 0.5 ~ 1.0 cm long. If necessary, finer mixing of metals is repeated. 4.

B. Copolymerization. In Example 1-B, a mixture of 1.81 g of styrene (34.8%) · and 3.4 g of isoprene in 10 ml of toluene is copolymerized under the action of 0.285 g of the obtained catalyst. The polymerization temperature 5 of 15 ° C; 4 hours yield 12.7%. The microstructure of polyisoprene consists of 63.6% cis-1.4; 18.2% trans-1.4 and 18.2% vinyl units in position 3.4. The molecular weight ₅ distribution of 1.64.

Example ·

A, preparation of the catalyst. 10 g of lithium and 0.0397 g of potassium are mixed by pressing under a layer of hydrocarbon solvent according to the procedure of Example 1-A. For a more even distribution of potassium and lithium, the mixing is carried out gradually, first with 1/3 “1/4 of the total amount of lithium taken. Since potassium is more plastic than sodium and is better, it flows under pressure, when pressed, its distribution is finer, void filling, etc.

The number of pressing cycles is not less than 10. The mixed metal at this potassium content (0.397%) is almost uniform and has mechanical properties almost the same as pure lithium, but it oxidizes much faster in air.

B. Copolymerization. A mixture of 1.812 g of styrene (.336.4%) and 3.16 g of butadiene in 20 ml of cyclohexane at 20 ° C is subjected to copolymerization under the influence of 0.198 g of the obtained mixed metal. After 3 hours, the copolymer yield was 20%, and the styrene content was 40.0%. The microstructure of polybutadiene units 45.0% CIS-1,4; 44.1% trans-1.4 and 10.9% 1.2. After removal of the polymer solution, the metal can be reused as a catalyst.

Example 4. The catalyst prepared according to method 1-A, copolymerization according to method 1-B, the composition of the copolymer is determined at sufficiently small yields.

The styrene content in the copolymer, which is closest to the initial one, is realized when the sodium content in lithium is about 13% and potassium in lithium in the range of 2-0.1%. With the same catalyst composition, varying the copolymerization temperature causes a change in both the styrene content in the copolymer and the microstructure of the polydi (ene units).

·,

Potassium is a significantly stronger modifying additive than sodium, therefore, to obtain a composition close to statistical, it is necessary to introduce less. Its optimum content in lithium is about 0.5%, which corresponds to a molar ratio of lithium - potassium of 1: 0,0009, i.e. significantly less than in the known method (-0.005-0.2).

Example 5

A. Preparation of the catalyst.

0.438 g of sodium is introduced into a glass ampoule with a capacity of 100 ml in the form of a bite 9 907011 KOV with a size of 3x3x3 mm, 12.5 ml of 0.7 N. a solution of butyl lithium and 15 ml of isoprene (molar ratio of butyl lithium to sodium 1: 2.17). Prepolymerization. carried out for 3 hours with constant stirring and 40 ° C, part of the sodium is dissolved. The obtained yellowish viscous solution was diluted with 30 ml of heptane and used as a catalyst for copolymerization, its concentration was 0.194 N, the characteristic viscosity of the polyisoprene isolated from it was 0.078 dl / g, the microstructure consists of 65.9%

1.4 cis units; 23.2% 1,4-trans and 1ί 10.9% 3.4.

B. A mixture of 4.49 g of ioprene and 1.54 g of styrene (25.5%) in 18 ml of benzene is subjected to copolymerization under the influence of 0.2 ml of prepared catal-2 (mash at 20 ° C. A sample of the copolymer taken after 1 h (yield 10%), shows 23.5% styrene in the copolymer.The microstructure of the diene part has a composition of 47.2% cis-1.4; 25.4% trans-1.4 2! and 27.4% 3.4.

B. The mixture of 0.906 g of styrene (31.5%) and 1.97 g of butadiene in 20 ml of toluene is copolymerized under the influence of 0.2 ml of 0.5 N. ethyl lithium and 0.10 g of finely cut sodium (molar ratio of ethyl lithium to sodium 1:43) at 20 ° С. After 40 minutes, the copolymer yield was 10.4%; styrene content 24.5%. The microstructure of the diene part has a composition of 22% _3;

1.4- cis, 49.0% 1.4-trans and 29.0%

1,2. Thus, copolymerization in the presence of a modifying additive without preliminary initiation leads to a noticeable ₄ decrease in the styrene content in the copolymer, despite a larger excess of sodium.

Example 6. A mixture of 4.71 g of styrene (.75.1%) and 1.564 g of isoprene in 30 ml of benzene at 20 ° C was polymerized. The catalyst was prepared according to method 5 ^_ A. Yield of the copolymer after 30 min 10%, styrene content 66.4%, microstructure of polyisoprene units 11.5%

1,4-cis, 52.3% 1.4-trans and 36.2% 3.4.

Therefore, an increase in the styrene content in the initial mixture significantly affects the configuration of the polyisoprene units in the copolymer.

PRI me R 7. '

A. Preparation of the catalyst. 2.45 g of isoprene are pre-polymerized in 10 ml of heptane under the influence of 5.0 ml of 0.846 n. a solution of sec-butyl lithium in the presence of 0.15 g of finely chopped metallic potassium (molar ratio of sec-butyl lithium potassium 0.908). The polymerization temperature was 20 ° C, the duration was 1 hour. Unreacted isoprene was distilled off, the solvent was added to 18 ml, and the resulting solution was drained from excess potassium. The normality of the resulting catalytic solution of 0.250. The remaining allium potassium potassium is used repeatedly to modify the catalyst, up to its complete dissolution.

B. A mixture of 0.906 g of styrene (339.9%) and 1.427 g of butadiene in 20 ml of toluene in the presence of 0.35 ml of the obtained catalyst is copolymerized. The temperature is 20 ° C. After 2 hours, the yield was 15.0%, the styrene content in the copolymer was 31.1%, the microstructure of butadiene units consisted of 39.4% 1,4-cis; 45.8% 1.4-trans and 14.8% 1.2.

The results of examples 1-7 are shown in the table.

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In 907 '

Therefore, the invention provides:

1. The possibility of using for the static copolymerization of styrene and dienes, both a soluble lithium-organic catalyst and a heterogeneous mixed metal containing a modifying additive. When using metal as a catalyst, 1 number of technological stages is reduced (there are no stages of catalyst synthesis and its modification). In addition, the copolymerizable system is well protected from impurities, since catalyst 1 is introduced in excess and is reused.

2. Use as a modifying additive along with potassium cheaper and more affordable sodium. 2

3. In the case of the use of potassium - a significant reduction in its consumption. The optimal ratio of modifying potassium to organolithium compound (0.0007: 1 according to the known 2! Method of 0.016: 1).

4. Reducing the synthesis time of the catalyst to 2-3 hours upon receipt of the prepolymer from n-butyllithium, sodium 3 and diene; up to 15-20 min in the case of the use of sec-butyl lithium, potassium and

14 styrene. Preparation of a mixture of metals can be carried out in 10-15 minutes.

Claims (2)

The invention relates to the synthesis of high-molecular compounds, in particular to a method for producing static chain-chain copolymers, and can be used in the petrochemical industry as additives to rubber compounds to obtain vulcanizates with enhanced dynamic properties, high tear resistance, abrasion and so on. d. and also as modifying additives to polystyrene, which increase its resistance to shock loads.  A known method for producing static chain-chain copolymers by copolymerizing dienes and vinyl aromatic monomers under the action of lithium organic catalysts in neutral hydrocarbon media in the presence of compounds that solvate well the lithium counterion of 1 esters, thio ethers, tertiary amines) l.  However, the introduction of highly solvating additives dramatically increases the proportion of side vinyl units in the copolymer, which degrades its properties. The closest to the present invention is a method for producing static chain-chain copolymers by copolymerizing butadiene or isoprene with styrene in an inert hydrocarbon solvent in the presence of lithium catalysts. Organic lithium catalyst modified with metallic potassium, ruPidium, or cesium are used.  To obtain a modified catalyst, the corresponding metal is introduced into a solution of an organolithium compound, which necessarily contains an aromatic additive, and the reaction mixture is heated to almost its melting temperature.  The reaction mixture is vigorously stirred to disperse the metal, and then the reaction is carried out for several hours at 50-80 ° C until the metal is completely dissolved.  The ratio of organo lium carbon to the modifying metal is 1: (O, 005-0.2) mol, the ratio of monomer and catalyst is 0.01-100 mmol of catalyst per 1 mol of monomer, depending on the desired molecular weight of the copolymer.  Thus, the modification is carried out by replacing part of the organolithium catalyst with an organic potassium by metallizing the aromatic additive 2.  However, this does not increase the catalyst normality and part of the organolithium compound is irretrievably lost.  The disadvantages of this method are also the long preparation time of the catalyst (3-7 h}, elevated synthesis temperature (50-60 ° CJ) and using potassium, rubidium or cesium as high-energy modulators, having high cost and exceptional fire risk.  The purpose of the invention is to simplify the catalyst production technology and increase efficiency.  This goal is achieved by the method of obtaining static chain-chain copolymers by copolymerizing butadiene or isoprene with styrene in an inert hydrocarbon solvent at 0-100 ° C in the presence of lithium catalysts selected from the group containing co-extrusion or extrusion of metallic lithium with sodium or potassium in a weight ratio Li: Na (K) 100: (50-0.1) and a low molecular weight living product of polymerization of butadiene or isoprene under the action of lithium alkyls with the addition of sodium or potassium at a molar rate in relation to Li alkyl: Na (K) 1: (l-50).  The introduction of modifying agents can be carried out in various ways.  When copolymerized by lithium metal, modifying sodium or. Potassium is introduced beforehand by their joint pressing or extrusion in a plastic state at temperatures below their melting points.  The resulting mixed metal is crushed into pieces of arbitrary size and the pressing or extrusion operation is repeated several times in order to more finely and evenly distribute the modifying additive in the lithium metal mass 4 The degree of metal mixing can be controlled visually or with the help of optical devices, since alternating I h layers have different colors.  The thickness of these layers is non-critical and can be from 1 to 300-500 microns.  Metals, as they dissolve and deteriorate as a result of transformation (living into polymers, must remain in contact with each other).  The proposed method for the introduction of a modifying additive makes it possible to vary its content over a wide range, since it cannot be achieved by another method, for example by fusion, due to incompatibility with lithium.  Thus, the amount of sodium or potassium is in the range of 50-0.1 weight.  in relation to lithium, the preferred range for obtaining a copolymer composition that is closest to static for sodium is 18-13 weight. for potassium 2-0.1 weight. .  The introduction of the modifying additive d soluble organolithium catalyst, such as utility, is carried out as follows.  A low molecular weight living prepolymer is first prepared by polymerizing a diene, styrene, or a mixture thereof in the presence of an organolithium catalyst and metallic sodium or potassium.  In the course of this polymerization, a part of the added metal is converted into a living polymer and transferred into a solution, which is further used as (a catalyst for the copolymerization of the main mass of monomers.  Thus, the resulting catalytic solution, in addition to the monolithium compound introduced initially, also contains a disodium or dipotassium living polymer, the amount of which can be adjusted with respect to lithium, and the prepolymerization wire under appropriate conditions.  For the proposed method, such conditions are butyllithium concentration O ,, 005 mol / l, monomer concentration 0.3-10 mol / l, temperature 1090 ° C, molar ratio of organolithium compound to sodium or potassium in the range of 1: (50-1 ).  The time of prepolymerization depends on the polymerizable system and can range from 10-15 minutes to 2-3 hours.  The introduction of monomer in the synthesis of katalisatopa can be carried out immediately or gradually.  59 degree of conversion 10-100.  The modifying additive after removal of the catalytic solution can be used repeatedly, up to its complete dissolution, while in contrast to the known method of loss of the organolithium catalyst does not occur.  The copolymerization of dienes with styrene G1OD by the action of a modified catalyst is carried out periodically or continuously at 10-100 ° C.  The use of aromatic or cycloaliphatic solvents is preferable as a medium; however, it is also possible to use also mixed solvents containing aliphatic hydrocarbons.  The concentration of the total monomers 0, mol / l, the styrene content by weight. %  The ratio of monomer to catalyst depends on the type of catalyst.  When copolymerization on a mixed metal, as a rule, a large excess of it is needed relative to the monomer in order to provide the necessary initiation rate and a sufficient number of active sites, therefore the ratio of monomer and catalyst. selected in the range of 1-15 wt. h  bi, metal per 100 weight. h  monomer amounts.  Due to the fact that the mixed metal is used in a coarse-dispersed form (pieces, granules with a size of mm) and dispersing it when copolymerization is insignificant, at the end of the process it can be easily separated from the polymer solvent and used many times, until it is completely dissolved.  Thus, the degree of use of the metal is quite high and can reach 60-70 depending on its composition and copolymerization conditions (mixing intensity, temperature and concentration). ac monomers).  The ratio of the sum of monomers to the soluble modified copolymerization catalyst is determined in the usual manner depending on the desired molecular weight.  In this case, the molecular weight is directly proportional to the weight of the polymerized monomers and inversely proportional to the number of moles of the catalyst taken, the correction for the dysfunctionality of the modifying additive is small.  The ratios used are in the range of 16 le 0.2-5 mmol of catalyst per 100.  weight. h  monomer.  Example 1  BUT.  Preparation of the catalyst.  0, g of lithium metal, cut into 3x3x3 mm pieces, is pressed with 0.0–1 g of sodium under a layer of a hydrocarbon solvent.  The resulting plate is cut into pieces of the same size, mixed and pressed again.  The operation is repeated 5 times.  Get 0,335 g of a bimetal containing 18.2 weight.  on three .  The degree of distribution of sodium is estimated by the thickness of its layers in lithium, clearly visible on the cut.  Layer thickness from 3-5 microns to 20-50 microns.  When grinding the catalyst to a size of 3x3x3 mm, its composition in pieces is preserved.  The control of the homogeneity of the composition is carried out in a solvent with a bladder with respect to the metal being mixed with a density, for example a mixture of hexane and toluene.  The resulting bimetal has good mechanical strength, is plastic, and does not crumble during deformation, since the layers of lithium and sodium are firmly bound by adhesive forces.  It does not lose its shape under the action of small mechanical forces, even 6V of the child is heated to 100 ° C, t. e.  above the melting point of sodium (97.7 ° C).  B.  Copolymerization.  In a glass ampoule containing 0.335 g of the obtained catalyst and 5 ml of glass beads with a diameter of 3 mm, a mixture of 2.7 ml of styrene and 6.4 g of butadiene and 30 ml of toluene is polymerized.  Polymerization temperature 20С.  Constant mixing of the contents and activation of the catalyst is carried out by shaking the ampoule.  After 1 h, a polymer sample is taken for analysis of the composition, microstructure of the diene part and exit.  Over this time, 15%.  The composition of the copolymer according to infrared spectroscopy of styrene (the initial composition of the monomers had styrene).  The microstructure of the diene part of the copolymer 28.5 cis-b; 38, it% TpaHc-1, i and 33, U 1,2 links.  The remaining monomers are copolymerized at 25 ° C for 2k hours.  The characteristic viscosity of the polymer is dl / g.  The polymer is highly soluble in toluene, cyclohexane, and toluene mixtures with heptane in the ratio of 2: 1; its molecular mass distribution according to gel permeation chromatography is unimodal and close to 1.2-1.3.  AT.  Comparative copolymerization on unmixed metals.  The copolymerization of 1.63 g of styrene and 2.11 g of butadiene in 15 ml of toluene is carried out as in paragraph B.  Catalyst 0.259 g of chopped lithium and 0, g of sodium.  Metals are not subjected to any processing before use. Copolymerization is carried out at 20 ° C for 1 hour.  The copolymer yield during this time is 8.6, the styrene content in the copolymer is 55.5 (in the initial mixture 3, the microstructure of polybutadienes. s units consists of 1, 6% 1, -cis-, 58. , 8 1, A-trans and 39.6% 1.2.  The copolymer has a bimodal molecular weight distribution, the polydispersity factor is 3.67 When the sodium content in the catalyst is close (, 18.2 and 13, respectively), the copolymerization of styrene and butadiene on pre-mixed metals proceeds with very close copolymerization constants and the best microstructure of polybutadiene units, Example 2, A.  Preparation of the catalyst.  8.7 g lithium and 1.3 g sodium in the form of pieces of arbitrary shape and size 3x5x5 mm. they are loaded into a device that allows them to be extruded together in the form of a wire with a diameter of 0.8 mm.  The mixture of metals and the formation of strong adhesive layers between them occurs when they are plastic flow near the orifices of the spinneret.  The resulting bi | metal wire is cut into pieces 0.5–1.0 cm long.  If necessary, a thinner mixture of metals, the operation is repeated, B.  Copolymerization.  In Example 1-B, a mixture of 1.81 g of styrene (3, and 3, g of isoprene in 10 (lp of toluene under the action of 0.285 g of the obtained catalyst) is copolymerized.  Polymerization temperature 15 ° С; access in 4 hours 12.7.  The microstructure of polyisoprene consists of 63.6 cis-1,4; 18.2 trans-1.4 and 18.2 vinyl units in the three ,.  Molecular weight distribution 1.64.  PRI me R 3.  A, catalyst preparation.  10 g of lithium and 0.0397 g of potassium by the method of Example 1-A are compacted by compression under a layer of a hydrocarbon solvent.  For a more even distribution of potassium and lithium, the mixing is carried out gradually, first with 1/31 / of the total amount taken.  Since potassium is more plastic than sodium and is better, it flows under pressure, when pressed, its finer distribution occurs, the filling of voids, etc. d.  The number of pressing cycles is not less than 10. The mixed metal with such a potassium content (0.397) is practically homogeneous and has almost the same mechanical properties as pure lithium, however, it oxidizes much faster in air, B.  Copolymerization. A mixture of 1.812 g of styrene (336,) and 3.16 g of butadiene in 20 ml of cyclohexane is copolymerized under the action of 0.19 V g of the resulting mixed metal.  After 3 h, the output of the copolymer is 20, the styrene content is (0.0, the microstructure of the polybutadiene units is 5.0,; kk, no trans-1, A, and 10.9 1.2.  The metal, after removing the polymer solution, can be reused as a catalyst.  Example: The catalyst was prepared according to method 1-A, copolymerization according to method 1-B, determination of the composition of the copolymer. produced at sufficiently low yields.  The styrene content in the copolymer, which is closest to the initial one, occurs when the sodium content in lithium is about 13 and potassium in lithium is in the range of 2-0.1. For the same catalyst composition, the variation of the copolymerization temperature causes a change in both the styrene content in the copolymer and the polydiene microstructure. links.  Potassium is a much stronger modifying additive than sodium, therefore, to obtain a composition that is close to statistical, it is necessary to introduce it less.  Its optimal content in lithium is about 0.5, which corresponds to a molar ratio of lithium to potassium of 1: 0.0009, t. e.  significantly less than in the known method (-0.005-0.2;.  Example 5 A, Preparation, Catalyst.  Into a glass vial with a capacity of 100 ml, 0.438 gnatri were introduced in the form of pieces of 3x3x3 mm, 12.5 ml of 0.7 n butyl lithium solution and 15 ml of isoprene (molar ratio of butyl lithium and sodium 1: 2.17).  The prepolymerization is carried out for 3 hours with constant stirring and kQ ° C, part of the sodium dissolves.  The resulting yellowish viscous solution is diluted with 30 ml of heptane and used as a copolymerization catalyst, its concentration OjISt n.  , the characteristic viscosity of the polyisoprene extracted from it is 0.078 dl / g, the microstructure consists of b5.9 1, -cys units; 23.2 1, -trans and 10.9 ° W ,.  B.  Copolymerization is carried out with a mixture of +, 9 g of iyoprene and 1.5 g of styrene (25.5%) in 18 ml of benzene under the action of 0.2 ml of the prepared catalyst at 20 ° C. The copolymer sample taken after 1 h (yield 10 %), shows styrene in the copolymer.  The microstructure of the diene part has a composition of 47.2% cis-1; 25, trans-1, and 27, W ,.  AT.  A mixture of 0.90 g of styrene (31.5%) and 1.97 g of butadiene in 20 ml of toluene will be copolymerized under the action of 0.2 ml of 0.5N.  ethyl lithium and 0.10 g of finely divided sodium (molar ratio of ethyl lithium and sodium T. ) at, After 0 min, the copolymer yield is 10%, the styrene content is 2.5%.  The microstructure of the diene part has a composition of 22% 1, - -cis-, i9.0. % B-trans and 29.0% 1.2.  Thus, conducting merization nozzles in the presence of a modifying additive without prior initiation leads to a noticeable decrease in the styrene content in the copolymer, despite a greater excess of sodium.  110 Example 6.  A mixture of 4.71 g of styrene (175.1%) and 1.56 g of isoprene is polymerized in 30 ml of benzene at.  The catalyst obtained by the method.  The copolymer yield after 30 min is 10%, the styrene content is 66, the microstructure of the polyisoprene units is 11.5% 1, -cis-, 52.3% 1, -trans and 36.2% 3 ,.  Therefore, an increase in the styrene content in the starting mixture noticeably affects the configuration of the polyisoprene units in the copolymer.  PRI me R 7.   BUT.  Preparation of the catalyst.  Pre-polymerized 2,  isoprene in 10 ml of heptane under the action of ml 0, n.  a solution of atorbutilliti in the presence of 0.15 g of finely chopped metallic potassium (the molar ratio of intrinsic butyl lithium potassium is 0.9P8).  Polymerization temperature, duration 1 hour  The unreacted isoprene is distilled off and the solvent is added to 18 ml or the resulting solution is taken up with an excess of potassium.  The normality of the resulting catalytic solution is 0.250.  The remaining metallic potassium is used to modify the catalyst many times, until it is completely dissolved.  B.  A mixture of 0.90 g of styrene (339.9%) and 1, g of butadiene in 20 ml of toluene will be copolymerized in the presence of 0.35 ml of the obtained catalyst.  Temperature 20 ° С.  After 2 h, the yield is 15.0%, the styrene content, in the copolymer 31.1%, the microstructure of the butadiene units consists of 39, 1, -cis; , 8% 1, -trans and T, 8% 1.2.  The results for examples 1-7 are shown in table.  13 Therefore, the invention provides: 1. The possibility of using for the static copolymerization of styrene and dienes, both a soluble lithium organic catalyst and a heterogeneous mixed metal containing a modifying additive.  When a metal is used as a catalyst, the number of process steps is reduced (there are no stages for catalyst synthesis and its modification).  In addition, the copolymerization system is well protected against impurities, since the catalyst is introduced in excess and is used multiple times.  2 The use of cheaper and more affordable sodium as a modifying additive along with potassium.  3 In the case of potassium, a significant reduction in its consumption.  The optimum ratio of modifying potassium to organolithium compound (0.0007: 1 by the known method is 0.016: 1).  j.  Reduction in catalyst synthesis time to 2-3 hours in the preparation of a prepolymer from n-butyl lithium, sodium, and diene; up to 15-20 minutes in the case of using sec-butyl lithium, potassium, and 1I styrene.  Preparation of a mixture of metals can be carried out in 10-15 minutes.  Claims of Invention A method for producing static chain-chain copolymers by copolymerizing butadiene or isoprene with styrene in an inert hydrocarbon solvent at 10-25 in the presence of -.  lithium catalysts, in that, in order to simplify the process and increase the efficiency of the process, a catalyst selected from the group containing the product of co-pressing or extrusion of lithium metal with sodium or potassium with a weight ratio of Li: Na (K) 100: (50-0.1) and a low molecular weight living polymerization product of butadiene or isoprene under the action of lithium alkyls with the addition of sodium or potassium at a molar ratio of Li alkyl: M, e (K) 1: (1-50).  Sources of information taken into account during the examination 1. Patent of Great Britain No. 1461373.  cl.  C 3 P, published.  1976.   2. USSR author's certificate №, cl. C 08 F 36/04, 1972 (prototype).