Method for producing cis-1,4-polydienes

Abstract

The invention relates to the field of producing synthetic rubbers that can be used in the production of tyres / assorted industrial rubber products, as well as for modifying plastics. Described is a method for producing cis-1,4-polydienes by the (co)polymerization of conjugated dienes in a hydrocarbon solvent in the presence of a Ziegler-Natta catalyst consisting of a lanthanide carboxylate, an organoaluminium compound and a halogen-containing component, wherein the catalyst may be formed in two ways, i.e. pre-formed or formed in situ. The proposed solution also envisages the possibility of modifying the resultant rubber by the addition of compounds selected from among aminosilanes containing alkoxy groups and / or from among halogen-containing compounds. The invention broadens the existing range of methods for producing highly stereoregular conjugated diene (co)polymers and makes it possible to produce a wide variety of rubbers according to the desired properties and field of use.

Description

[0001] METHOD FOR PRODUCING CIS-1,4-POLYDIENES

[0002] AREA OF TECHNOLOGY

[0003] The proposed invention relates to the field of producing synthetic rubbers that can be used in the production of tires / various rubber products, as well as for modifying plastics. More specifically, the invention relates to a technology for synthesizing cis-1,4-polydienes by (co)polymerizing butadiene and isoprene in a hydrocarbon solvent in the presence of Ziegler-Natta catalysts based on rare earth elements. The proposed method makes it possible to obtain cis-1,4-polydienes with a high content of cis-1,4-units (more than 95%), a narrow (1.5-2.8) and wide (2.8-4.0) polydispersity coefficient, while the resulting rubber has improved processability, and products based on them are characterized by high performance properties.

[0004] LEVEL OF TECHNOLOGY

[0005] Stereoregular general-purpose rubbers are indispensable in the formulations of tire treads and sidewalls. At the same time, modern requirements for rubbers based on them are focused on processability, reduction of hysteresis losses and durability. The specified indicators are determined by the structure of polydiene macromolecules, namely, the microstructure - the content of cis-1,4-links, and the macrostructure - molecular weight distribution, linearity / branching.

[0006] From the prior art (RU 2638960 C2), a method for producing high-molecular polybutadiene with a cis-1,4-linkage content of more than 95% by abruptly increasing the Mooney viscosity is known. According to this method, 1,3-butadiene is polymerized at a temperature of 50 to 120°C, stopped by adding protic compounds to the polymerizate, and sulfur chlorides treated with a complex ester of a fatty acid of plant origin, which is epoxidized soybean oil, are added. The method makes it possible to increase the Mooney Viscosity index by at least 50% of the original polymer after polymerization, wherein gelation should be completely absent or only slight gelation should be ensured. At the same time, the solution does not indicate at what range of monomer concentration in the batch the polymerization is carried out using a catalyst, the preparation of which is included in the claims. The maximum concentration of butadiene described in the examples is 13% by weight., does not meet the requirements of modern rubber production, which has the ability to regulate this parameter based on the available solvent and the necessary technical and economic indicators of the process.

[0007] A method for producing cis-1,4-polybutadiene with a low degree of branching is known (US 7112632B2), which consists in polymerizing butadiene in an organic solvent at a temperature of 20-120 0C in the presence of a catalyst based on neodymium compounds, while modification is carried out with products from the group of unsaturated natural oils, oligomers or copolymers of butadiene and / or isoprene functionalized with epoxy, anhydride or ether groups at a temperature of 20-150 OC. This method ensures the production of rubber, which is characterized by a content of cis-1,4-units (at least 93%), narrow polydispersity (no more than 2.5) and low cold flow. However, the disadvantage of the solution is that the modified polymers are characterized by a high content of high-molecular fraction, which worsens the processability of the rubber and the dynamic properties of vulcanizates based on it.

[0008] Also known is a method for polymerizing a conjugated diene in an organic solvent (RU 2701930 C1), comprising the following stages: preparing a catalytic system, polymerizing the diene using the above catalytic system in an organic solvent, introducing a comonomer upon reaching at least 96% conversion of the conjugated diene, and introducing at least one branching agent, wherein the catalytic system comprises a lanthanide, a conjugated diene, an organoaluminum compound, and a halogen-containing component, the comonomer is selected from cyclic hydroxy acid esters containing from 2 to 10 carbon atoms in the cycle, and the branching agent is selected from the group of chlorine-containing silicon or tin compounds. The invention makes it possible to obtain a diene copolymer having improved processability at the rubber mixing stage and improved processability of rubber mixtures and improved interaction of the copolymer.At the same time, in this solution, the polymerization time is 1.5-3 hours, which indicates either insufficiently high activity of the proposed catalyst, or a low concentration of monomer in the batch, and leads to a deterioration in the technical and economic indicators of production, reducing the production of rubber.

[0009] A method is known for producing polybutadiene (WO 2009121516 A1) with a content of cis-1,4- units above 92%, a Mooney viscosity from 30 to 70, Mw / Mn from 1.5 to 4, a branching index (gM) from 0.4 to 0.9, characterized in that the polymerization of butadiene is carried out in an aliphatic and / or cycloaliphatic solvent system in the presence of a catalyst obtained in situ, where the catalytic system is obtained by dissolving neodymium carboxylate in a process solvent in the presence of an alkyl compound of aluminum under continuous temperature conditions in the range from 70 to 130 °C. The solution makes it possible to continuously obtain a polymer with a polydispersity in a wide range from 1.5 to 4.0. A disadvantage of the proposed method is the low level of stereoregularity of the resulting rubber. A decrease in the content of cis-1,4-links in the polymer leads to a deterioration in the strength and abrasion properties of vulcanizates based on it.

[0010] The closest in essence to the present invention is a method for producing a modified polydiene (RU 2803602 C1), comprising the stages of: i) preparing a catalytic complex comprising (A) a lanthanide compound, (B) a conjugated diene, (C) an organoaluminum compound and (D) a halogen-containing component; ii) polymerizing the conjugated diene in an organic solvent in the presence of the catalytic complex obtained in stage i); iii) upon reaching at least 96% conversion of the monomer, introducing a modifying agent into the polymer - low-molecular polybutadiene containing terminal alkoxysilane groups; iv) stopping the polymerizate obtained in stage iii), introducing an antioxidant and isolating the polymer. The modified polydiene obtained according to the invention is characterized by a Mooney viscosity of from 40 to 50 conventional Mooney units and a content of 1,4-cis-units of more than 96% by weight.The method, according to the prototype, allows to obtain polydiene, which has improved indicators of processing and distribution of filler in the polymer matrix. The patent does not specify the dosage of the catalyst in relation to the polymerized monomer, while the time of the polymerization process is quite long - 2 hours. In addition, the obtained polymer has limitations on viscosity (from 40 to 50 conventional units after modification), which sets the boundaries for improving the indicators of hysteresis losses of vulcanizates due to the reduction of free ends of the polymer.

[0011] The technical task of the present invention is to develop a new method for producing cis-1,4-polydienes with a high content of cis-1,4-polymer units with a narrow (1.5-2.8) and wide (2.8-4.0) polydispersity coefficient, whereby the resulting rubber has improved processability, and products based on them are characterized by high performance properties, in particular high strength, low rolling losses and high frost resistance of vulcanizates.

[0012] The problem is solved by using high-activity and stereoselective catalysts for polymerization of conjugated dienes, prepared in two ways: pre-formed, or formed in the process of dosing the catalyst components into the monomer solution. The first is characterized by high stability of active centers and allows for a flexible response to existing microimpurities in the polymerization system, while the second eliminates the stage of catalyst synthesis and maturation, which is important for existing production and allows for prompt regulation of viscosity in the process. Improvement of rubber processability can be achieved by obtaining cis-1,4-polydiene with moderately wide polydispersity due to an increase in the proportion of low-molecular fraction, but this method has limitations, since it affects the level of hysteresis losses of vulcanizates. If a comprehensive solution is required, it is possible to use modifiers of different directions of action both individually and jointly.Thus, products based on, for example, disulfur dichloride, react via double bonds of the polymer chain. During modification, SS bonds appear in the polymer structure, which are subsequently destroyed by mechanical action in rubber mixers, which contributes to an increase in the homogeneity of rubber mixtures, a decrease in loads on equipment, i.e. an increase in the processability of the polymer, even with an increased level of viscosity of the base rubber. At the same time, such products as aminosilanes containing alkoxy groups, tin halides react via the active centers of "living" polymer chains. As a result of such interactions, polydienes are obtained, containing functional groups of the modifier or metal atoms at the ends of the chains. It should be noted that the strength of the interaction of these groups with the surface of the filler in rubber mixtures (carbon black or silica filler) determines the effectiveness of the modification.Therefore, modification of reactive macromolecules, as a rule, pursues two goals: firstly, to improve the plastic-elastic properties of the ammonia rubber itself; secondly, to improve the performance properties of rubber compounds and vulcanizates based on modified polymers. Polybutadienes obtained using catalysts based on rare earth metals are characterized by a worse level of frost resistance than other polybutadienes, which is due to their high ability to crystallize and is explained by the high stereoregularity of their macromolecules. An effective way to improve low-temperature properties is the copolymerization of butadiene with a small amount of isoprene. Even with an isoprene content of 12-16% in the copolymer, the crystallization rate of the copolymer becomes equal to the crystallization rate of titanium SKD [F.E. Kuperman, New Rubbers for Tires, Moscow, 2009].Thus, the proposed solutions make it possible to regulate the technological parameters of the process to optimize its technical and economic indicators and to obtain a wide range of rubber depending on the required properties and area of ​​application.

[0013] BRIEF DESCRIPTION

[0014] According to the present invention, the method for producing cis-1,4-polydienes includes several stages: synthesis of a catalytic complex based on a rare earth metal carboxylate, carrying out the (co)polymerization process in a hydrocarbon solvent and, in some cases, modification. In this case, the catalyst is preliminarily obtained by mixing a rare earth metal carboxylate (A), an organoaluminum compound (B) and a halogen source (C) at a total molar ratio of components [A]:[B]:[C]= [1]:[5-150]:[1-6] in an aliphatic, naphthenic solvent or in mixtures thereof with the addition of a small amount of a conjugated diene (pre-forming), or in the process of polymer synthesis, introducing the catalyst components directly into the monomer solution (in situ). Next, the cis-1,4-polybutadiene polymer is mixed with a modifier and / or stopper in such a way that the total dosage of it / them to the polymer is 0-1.0% by weight.

[0015] Neodymium, praseodymium, gadolinium or their mixtures are used as rare earth metals in the composition of rare earth metal carboxylate.

[0016] The following are used as the organoaluminum component of the catalytic system, but are not limited to: diisobutylaluminum hydride (DIBAH), triethylaluminum (TEA), triisobutylaluminum (TIBA), isobutylaluminumoxane (IBAO), methylaluminoxane (MAO), including its modified grades, or mixtures of the specified components. The organoaluminum component of the catalytic system can be introduced at any stage of the pre-forming catalyst preparation, with aluminoxane used both in a mixture with standard organoaluminum compounds and individually, by introducing it as the final component during the formation of the complex.

[0017] The halogenating agent of the catalytic system may include, but is not limited to, ethyl aluminum sesquichloride (EAS), diethyl aluminum chloride (DEAC), ethyl aluminum dichloride (EADC), diisobutyl aluminum chloride (DIBAC), or mixtures thereof.

[0018] The polymerization is carried out continuously or periodically. The polymerization time is from 0.5 h to 2 h, preferably 1 h. The concentration of the monomer in the solvent is within the range of 10-50 wt.%, preferably 15-25 wt.%. The temperature of the batch is within the range of (-20) - 30 °C, preferably (-15) - 30 °C. The final temperature of the polymerization process varies within the range of 70 - 150 °C, preferably 70 - 125 °C.

[0019] The solvent is n-hexane, hexane isomers, cyclohexane or mixtures thereof.

[0020] Conjugated dienes that may include, but are not limited to, 1,3-butadiene, isoprene, or mixtures thereof.

[0021] The modifier is selected from compounds from the series of aminosilanes containing alkoxy groups, examples of which, but not limited to, are N-(3-triethoxysilylpropyl)cyclohexanamine, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-[3-diethoxy(methyl)silyl]propyl]-4-methylpentan-2-amine, N-[3-dimethoxy(methyl)silyl)propyl]cyclohexanamine, N-(6-aminohexyl)aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, or from a series of halogen-containing compounds - disulfur dichloride, phosphorus trichloride, phosphorus pentachloride, tin tetrachloride, or their mixtures.

[0022] The stopper is selected from the series neodecanoic acid, stearic acid, lauric acid, or water is used, preferably partially desalinated, but is not limited to them. The dosage of the stopper to the polymer is from 0 to 0.5% by weight in the case of neodecanoic, stearic and lauric acids or mixtures thereof, or in a mass ratio of polymerizate / water = 1 / 0.1 in the case of using water as a stopper.

[0023] The order of submission of modifiers and stopper can be any, in the form of modifier-stopper, modifier-stopper-modifier, stopper-modifier, modifier (without stopper), stopper (without modifier).

[0024] Mixing of the polymer with the modifier / stopper in a static mixer and / or mixing reactor is carried out as follows:

[0025] - the conversion of monomers before feeding the modifier is from 60 to 99%, preferably more than 95%;

[0026] - modification time is from 5 minutes to 3 hours;

[0027] - the modification temperature is from 70-150 °C, preferably 70-110 °C.

[0028] The resulting polymer has the following characteristics:

[0029] - Mn in the range from 7><104 to 48 x 104 g / mol

[0030] - Mw / Mn within the range from 1.5 to 4.0

[0031] - Mooney viscosity (ML 1+4, 100 oC) from 30 to 90 Mooney units

[0032] - content of cis-1, 4-links, not less than 95%.

[0033] Implementation of the invention.

[0034] Below are examples of specific implementation of the proposed invention. These examples are not intended to limit the scope of protection of the present invention and are provided to illustrate the invention.

[0035] Examples of the preparation of cis-1,4-polydienes are presented in Tables 1 and 2.

[0036]

[0037] y

[0038] F g

[0039]

[0040] O

[0041]

[0042]

[0043] Example 1

[0044] Preparation of catalyst.

[0045] The glass reactor is preliminarily prepared by heating in a vacuum and filled with nitrogen. Then, solutions of neodymium neodecanoate (A) - 1 ml (0.32 mmol), DIBAG (B) - 4.95 ml (4.73 mmol), conjugated diene and DEAC (C) - 0.94 ml (1.11 mmol) are introduced into the reactor with stirring. The molar ratio of the components is A:B:C = 1:15:3.5. The prepared complex is maintained at a temperature of 20-25 °C for at least 12 hours, but not more than 24 hours. The concentration of neodymium in the finished catalyst is 0.041 g-at / l.

[0046] Polymerization and modification.

[0047] In a pre-prepared metal reactor (washing with a solvent containing any organometallic compound), 750 ml of the batch (a mixture of nefras and butadiene-1,3), the monomer concentration in which is 15% by weight, are introduced with stirring. The reactor contents are brought to a temperature of 100C and 1.71 ml of the catalyst are introduced, while the butadiene-1,3 / Nd ratio is 20,000 mol / mol. After achieving the required conversion at a temperature of 95 °C, a modifier is introduced - disulfur dichloride in a dosage of 0.1 g / 100 g of polymer. Stirring of the reactor contents must be carried out for 30 minutes. Then the reactor is emptied, the polymer is filled with a non-staining antioxidant, degassed and dried to a constant weight.

[0048] Example 2

[0049] Preparation of catalyst.

[0050] The glass reactor is preliminarily prepared by heating in a vacuum and filled with nitrogen. Then, solutions of neodymium neodecanoate (A) - 1 ml (0.32 mmol), a mixture of DIBAG and MAO (B) 15.01 ml (6.33 mmol + 6.33 mol), a conjugated diene and EADC (C) - 0.94 ml (1.11 mmol by chlorine) are introduced into the reactor with stirring. The molar ratio of the components is A:B:C = 1:40:3.5. The prepared complex is maintained at a temperature of 20-25 °C for at least 12 hours, but not more than 24 hours. The concentration of neodymium in the finished catalyst is 0.018 g-at / l.

[0051] Polymerization and modification.

[0052] In a pre-prepared metal reactor (washing with a solvent containing any organometallic compound), 750 ml of the batch (a mixture of cyclohexane and butadiene-1,3), the monomer concentration in which is 15% by weight, are introduced with stirring. The reactor contents are brought to a temperature of 100C and 1.97 ml of the catalyst are introduced, while the butadiene-1,3 / Nd ratio is 40,000 mol / mol. After achieving the required conversion at a temperature of 95 °C, a modifier is introduced - 3-triethoxy-silyl-N-(1,3-dimethylbutylidene)propylamine in a dosage equal to 0.015 g / 100 g of polymer. Stirring of the reactor contents must be carried out for 30 min. Then a stopper - neodecanoic acid in an amount of 0.012 g / 100 g of polymer is introduced into the reaction mixture and stirred for 5-15 minutes. The reactor is then emptied, the polymer is loaded with a non-staining antioxidant, degassed and dried to constant weight.

[0053] Example 3

[0054] Preparation of catalyst.

[0055] The glass reactor is preliminarily prepared by heating in a vacuum and filled with nitrogen. Then, solutions of neodymium neodecanoate (A) - 1 ml (0.32 mmol), a mixture of DIBAG, TIBA and TEA (B) 6.37 ml (1.91 mmol + 4.11 mmol + 0.32 mmol), a conjugated diene and a mixture of EASC and EADC (C) - 0.67 ml (0.79 mmol no chlorine) are introduced into the reactor with stirring. The molar ratio of the components is A:B:C = 1:20:2.5.

[0056] The prepared complex is maintained at a temperature of 20-25 °C for a period of at least 12 hours, but no more than 24 hours. The concentration of neodymium in the finished catalyst is 0.032 g-at / l.

[0057] Polymerization.

[0058] In a pre-prepared metal reactor (washed with a solvent containing any organometallic compound) 750 ml of the batch (a mixture of hexane and isoprene), the monomer concentration in which is 18% by weight, are introduced with stirring. The reactor contents are brought to a temperature of 100C and 2.06 ml of the catalyst are introduced, while the isoprene / Nd ratio is 20,000 mol / mol. After achieving the required conversion, the reactor is emptied, the resulting polymerizate is intensively mixed with partially desalinated water, then the polymer is filled with a non-staining antioxidant, degassed and dried to a constant weight.

[0059] Example 4

[0060] Preparation of catalyst.

[0061] The glass reactor is preliminarily prepared by heating in a vacuum and filled with nitrogen. Then, solutions of neodymium neodecanoate (A) - 1 ml (0.32 mmol), MAO (B) 46.9 ml (47.43 mmol), conjugated diene and EASC (C) - 0.27 ml (0.32 mmol by chlorine) are introduced into the reactor with stirring. The molar ratio of the components is A:B:C = 1:150:1.0. The prepared complex is maintained at a temperature of 20-25 °C for at least 12 hours, but not more than 24 hours. The concentration of neodymium in the finished catalyst is 0.006 g-at / l.

[0062] Polymerization. 750 ml of the batch (a mixture of nefras, butadiene-1,3 and isoprene), the total concentration of monomers in which is 20% by weight, are introduced into a pre-prepared metal reactor (washed with a solvent containing any organometallic compound) with stirring. The reactor contents are brought to a temperature of minus 100C and 7.79 ml of the catalyst are introduced, while the ratio of butadiene-1,3 + isoprene / Nd1 is 35,000 mol / mol. After achieving the required conversion, the reactor is emptied, the resulting polymerizate is intensively mixed with partially desalinated water, then the polymer is filled with a non-staining antioxidant, degassed and dried to a constant weight.

[0063] Example 5

[0064] Preparation of catalyst.

[0065] The glass reactor is preliminarily prepared by heating in a vacuum and filled with nitrogen. Then, the solutions of gadolinium versatate (A) - 1 ml (0.29 mmol), a mixture of DIBAH and MAO (B) 28.31 ml (8.7 mmol + 14.49 mmol), a conjugated diene and a mixture of EASC and DIBAH (C) - 0.86 ml (1.01 mmol by chlorine) are introduced into the reactor with stirring. The molar ratio of the components is A:B:C = 1:80:3.5. The prepared complex is maintained at a temperature of 20-25 °C for at least 12 hours, but not more than 24 hours. The concentration of neodymium in the finished catalyst is 0.009 g-at / l.

[0066] Polymerization and modification.

[0067] In a pre-prepared metal reactor (washing with a solvent containing any organometallic compound), 750 ml of the batch (a mixture of cyclohexane and butadiene-1,3), the monomer concentration in which is 15% by weight, are introduced with stirring. The reactor contents are brought to a temperature of 5 °C and 3.28 ml of the catalyst are introduced, while the butadiene-1,3 / Nd ratio is 50,000 mol / mol. After achieving the required conversion at a temperature of 100 °C, the modifier -N-(6-aminohexyl) aminopropyltrimethoxysilane is introduced in a dosage equal to 0.011 g / 100 g of polymer. Stirring of the reactor contents must be carried out for 60 min. Then, a stopper - stearic acid in an amount of 0.02 g / 100 g of polymer is introduced into the reaction mixture and stirred for 5-15 min. The reactor is then emptied, the polymer is loaded with a non-staining antioxidant, degassed and dried to constant weight.

[0068] Example 6

[0069] Preparation of catalyst.

[0070] The glass reactor is preliminarily prepared by heating in a vacuum and filled with nitrogen. Then, solutions of neodymium neodecanoate (A) - 1 ml (0.32 mmol), a mixture of DIBAG, MAO (B) 7.95 ml (1.58 mmol + 4.75 mmol), a conjugated diene and DIBAC (C) - 0.27 ml (0.32 mmol by chlorine) are introduced into the reactor with stirring. The molar ratio of the components is A:B:C = 1:20:1. The prepared complex is maintained at a temperature of 20-25 °C for at least 12 hours, but not more than 24 hours. The concentration of neodymium in the finished catalyst is 0.032 g-at / l.

[0071] Polymerization and modification.

[0072] In a pre-prepared metal reactor (washing with a solvent containing any organometallic compound), 750 ml of the batch (a mixture of nefras and butadiene-1,3), the monomer concentration in which is 18% by weight, are introduced with stirring. The reactor contents are brought to a temperature of 0 °C and 3.57 ml of the catalyst are introduced, while the butadiene-1,3 / Nd ratio is 15,000 mol / mol. After achieving the required conversion at a temperature of 103 °C, a modifier is introduced - phosphorus trichloride in a dosage of 0.15 g / 100 g of polymer. Stirring of the reactor contents must be carried out for 60 min. Then the reactor is emptied, the polymer is filled with a non-staining antioxidant, degassed and dried to a constant weight.

[0073] Example 7

[0074] Preparation of catalyst.

[0075] The glass reactor is preliminarily prepared by heating in a vacuum and filled with nitrogen. Then, solutions of neodymium neodecanoate (A) - 1 ml (0.32 mmol), DIBAG (B) 4.98 ml (4.76 mmol), conjugated diene and EASC (C) - 0.67 ml (0.79 mmol by chlorine) are introduced into the reactor with stirring. The molar ratio of the components is A:B:C = 1:15:2.5. The prepared complex is maintained at a temperature of 20-25 °C for at least 12 hours, but not more than 24 hours. The concentration of neodymium in the finished catalyst is 0.042 g-at / l.

[0076] Polymerization.

[0077] In a pre-prepared metal reactor (washing with a solvent containing any organometallic compound) 750 ml of the batch (a mixture of hexane and butadiene-1,3), the monomer concentration in which is 15% by weight, are introduced with stirring. The reactor contents are brought to a temperature of 20 °C and 1.56 ml of the catalyst are introduced, while the butadiene-1,3 / Nd ratio is 20,000 mol / mol. After achieving the required conversion, the reactor is emptied, the polymer is filled with a non-staining antioxidant, degassed and dried to a constant weight.

[0078] Example 8

[0079] Preparation of catalyst.

[0080] The glass reactor is preliminarily prepared by heating in a vacuum and filled with nitrogen. Then, solutions of praseodymium neodecanoate (A) - 1 ml (0.32 mmol), a mixture of TIBA, IBAO (B) 39.95 ml (16.17 mmol + 16.17 mmol), a conjugated diene and EASC (C) - 0.27 ml (0.32 mmol) are introduced into the reactor with stirring. The molar ratio of the components is A:B:C = 1:100: 1. The prepared complex is maintained at a temperature of 20-25 °C for at least 12 hours, but not more than 24 hours. The concentration of neodymium in the finished catalyst is 0.008 g atm / l.

[0081] Polymerization and modification.

[0082] In a pre-prepared metal reactor (washing with a solvent containing any organometallic compound), 750 ml of the batch (a mixture of hexane and butadiene-1,3), the monomer concentration in which is 13% by weight, are introduced with stirring. The reactor contents are brought to a temperature of 30 °C and 3.95 ml of the catalyst are introduced, while the butadiene-1,3 / Nd ratio is 40,000 mol / mol. After achieving the required conversion at a temperature of 103 °C, a modifier solution - N-(3-triethoxysilylpropyl)cyclohexanamine is introduced in a dosage of 0.014 g / 100 g of polymer. Stirring of the reactor contents must be carried out for 60 min. Then a stopper - stearic acid is introduced in an amount of 0.05 g / 100 g of polymer and stirred again for 5-15 min. After which, the second modifier, disulfur dichloride, is added to the reaction mixture in an amount of 0.12 g / 100 g of polymer and stirred for another 120 minutes.The reactor is then emptied, the polymer is loaded with a non-staining antioxidant, degassed and dried to constant weight.

[0083] Example 9

[0084] Preparation of catalyst.

[0085] The glass reactor is preliminarily prepared by heating in a vacuum and filled with nitrogen. Then, solutions of neodymium and gadolinium neodecanoate (A) - 1 ml (0.30 mmol), DIBAG and TIBA (B) - 4.5 ml (2.44 mol + 1.52 mmol), conjugated diene and EASC (C) - 0.9 ml (1.06 mmol for chlorine) are introduced into the reactor with stirring. The molar ratio of the components is A:B:C = 1:13:3.5. The prepared complex is maintained at a temperature of 20-25 °C for at least 12 hours but not more than 24 hours. The concentration of neodymium in the finished catalyst is 0.042 g-at / l.

[0086] Polymerization and modification.

[0087] In a pre-prepared metal reactor (washing with a solvent containing any organometallic compound) 750 ml of the batch (a mixture of hexane and butadiene-1,3), the monomer concentration in which is 15% by weight, are introduced with stirring. The reactor contents are brought to a temperature of 200C and 1.66 ml of the catalyst are introduced, while the ratio of butadiene-1,3 / Nd is 20,000 mol / mol. After achieving the required conversion after bringing the temperature to 70 °C, a modifier is introduced - tin tetrachloride in a dosage of 0.25 g / 100 g of polymer.

[0088] The reactor contents must be stirred for 30 minutes. Then the reactor is emptied, the polymer is filled with a non-staining antioxidant, degassed and dried to a constant weight.

[0089] Example 10

[0090] Preparation of catalyst.

[0091] The glass reactor is preliminarily prepared by heating in a vacuum and filled with nitrogen. Then, solutions of a mixture of neodymium and gadolinium neodecanoate (A) - 1 ml (0.3 mmol), a mixture of DIBAG and modified MAO (B) 5.75 ml (4.54 mmol + 1.51 mmol), a conjugated diene and a mixture of EASC and DEAC (C) - 0.76 ml (0.90 mmol by chlorine) are introduced into the reactor with stirring. The molar ratio of the components is A:B:C = 1:20:3.0. The prepared complex is maintained at a temperature of 20-25 °C for at least 12 hours, but not more than 24 hours. The concentration of neodymium in the finished catalyst is 0.037 g-at / l.

[0092] Polymerization.

[0093] In a pre-prepared metal reactor (washed with a solvent containing any organometallic compound), 750 ml of the batch (a mixture of hexane and butadiene-1,3), the monomer concentration in which is 15% by weight, are introduced with stirring. The reactor contents are brought to a temperature of 150C and 1.28 ml of the catalyst are introduced, while the butadiene-1,3 / Nd ratio is 30,000 mol / mol. After achieving the required conversion, the reactor is emptied, the resulting polymerizate is intensively mixed with partially desalinated water, then the polymer is filled with a non-staining antioxidant, degassed and dried to a constant weight.

[0094] Example 1 1 Polymerization. 750 ml of a batch (a mixture of hexane and butadiene-1,3), the monomer concentration of which is 20% by weight, are introduced into a pre-prepared metal reactor (washed with a solvent containing any organometallic compound) with stirring. The reactor contents are brought to a temperature of 0 °C and solutions of DIBAG (B) 0.65 ml (0.62 mmol), neodymium neodecanoate (A) 0.39 ml (0.125 mmol) and EASC (C) 0.26 ml (0.31 mmol for chlorine) are introduced sequentially. The molar ratio of the components is A:B:C = 1:5:2.5, the butadiene-1,3 / Nd ratio is 15,000 mol / mol. After achieving the required conversion, the reactor is emptied, the resulting polymer is intensively mixed with partially desalinated water, then the polymer is added with a non-staining antioxidant, degassed and dried to a constant weight.

[0095] Example 12

[0096] Polymerization and modification.

[0097] In a pre-prepared metal reactor (washed with a solvent containing any organometallic compound), 750 ml of the batch (a mixture of hexane and butadiene-1,3), the monomer concentration in which is 15% by weight, are introduced with stirring. The contents of the reactor are brought to a temperature of 0 °C and solutions of a mixture of DIBAG + TIBA (B) 1.52 ml (1.19 mmol + 0.21 mmol), neodymium neodecanoate (A) 0.22 ml (0.070 mmol) and a mixture of EASC + EADC (C) 0.18 ml (0.21 mmol for chlorine) are successively introduced. In this case, the molar ratio of the components is A:B:C = 1:20:3, the ratio of butadiene-1,3 / Nd is 20,000 mol / mol. After reaching the required conversion at a temperature of 90 °C, a stopper - neodecanoic acid in an amount of 0.5 g / 100 g of polymer is introduced, and then a modifier solution - disulfur dichloride is introduced at a rate of 0.3 g / 100 g of polymer. The reactor contents must be stirred for 15 minutes.The reactor is then emptied, the polymer is loaded with a non-staining antioxidant, degassed and dried to constant weight.

[0098] Example 13

[0099] Polymerization and modification.

[0100] In a pre-prepared metal reactor (washing with a solvent containing any organometallic compound), 750 ml of the batch (a mixture of hexane and butadiene-1,3), the monomer concentration in which is 18% by weight, are introduced with stirring. The contents of the reactor are brought to a temperature of 0 °C and solutions of a mixture of DIBAG + MAO (B) 1.44 ml (0.84 mmol + 0.42 mmol), neodymium neodecanoate (A) 0.13 ml (0.042 mmol) and DIBAC (C) 0.1 1 ml (0.13 mmol by chlorine) are successively introduced. In this case, the molar ratio of the components is A:B:C = 1:30:3, the ratio of butadiene-1,3 / Nd is 40,000 mol / mol. After achieving the required conversion, at a temperature of 102 0C, a solution of the modifier - 3-aminopropyltrimethoxysilane in an amount of 0.012 g / 100 g of polymer. The contents of the reactor must be stirred for 5 minutes. Then, a stopper - lauric acid in an amount of 0.03 g / 100 g of polymer is added and stirred again for 5-15 minutes.The reactor is then emptied, the polymer is loaded with a non-staining antioxidant, degassed and dried to constant weight.

[0101] Example 14

[0102] Polymerization. 750 ml of the batch (a mixture of hexane and butadiene-1,3), the monomer concentration in which is 25% by weight, are introduced into a pre-prepared metal reactor (washed with a solvent containing any organometallic compound) with stirring. The reactor contents are brought to a temperature of -10 °C and solutions of DIBAG (B) 4.90 ml (4.69 mmol), neodymium neodecanoate (A) 0.3 ml (0.09 mmol) and a mixture of EASC and DEAC (C) 0.17 ml (0.20 mmol by chlorine) are successively introduced. In this case, the molar ratio of the components is A:B:C = 1:50:2.0, the butadiene-1,3 / Nd ratio is 25,000 mol / mol. After achieving the required conversion, the reactor is emptied, the resulting polymer is intensifiably mixed with partially desalinated water, then the polymer is added with a non-staining antioxidant, degassed and dried to a constant weight.

[0103] Example 15

[0104] Polymerization and modification.

[0105] In a pre-prepared metal reactor (washed with a solvent containing any organometallic compound), 750 ml of the batch (a mixture of hexane and butadiene-1,3), the monomer concentration in which is 15% by weight, are introduced with stirring. The reactor contents are brought to a temperature of 10 °C and solutions of a mixture of TIBA and IBAO (B) 1.71 ml (0.47 mmol + 0.94 mmol), neodymium and praseodymium neodecanoate (A) 0.15 ml (0.047 mmol) and DEAC (C) 0.14 ml (0.17 mmol for chlorine) are successively introduced. In this case, the molar ratio of the components is A:B:C = 1:30:3.5, the butadiene-1,3 / Nd ratio is 30,000 mol / mol.

[0106] After achieving the required conversion at a temperature of 95 °C, a modifier solution is introduced - N-(2-aminoethyl)-3-aminopropyltrimethoxysilane in a dosage of 0.027 g / 100 g of polymer. The reactor contents must be stirred for 45 minutes. Then, a stopper - stearic acid is introduced in an amount of 0.1 g / 100 g of polymer and stirred again for 5-15 minutes. After which the second modifier - phosphorus pentachloride in an amount of 0.3 g / 100 g of polymer is added to the reaction mixture and stirred for another 45 minutes. Then the reactor is emptied, the polymer is filled with a non-staining antioxidant, degassed and dried to a constant weight.

[0107] Example 16 Polymerization. 750 ml of the batch (a mixture of hexane, butadiene-1,3 and isoprene), the total concentration of monomers in which is 20% by weight, are introduced into a pre-prepared metal reactor (washed with a solvent containing any organometallic compound) with stirring. The reactor contents are brought to a temperature of 0 °C and solutions of DIBAG (B) 1.99 ml (1.23 mmol), praseodymium neodecanoate (A) 0.25 ml (0.082 mmol) and EASC (C) 0.21 ml (0.25 mmol for chlorine) are introduced sequentially. In this case, the molar ratio of the components is A:B:C = 1:15:3.0, the ratio of butadiene-1,3 + isoprene / Nd is 22,000 mol / mol. After achieving the required conversion, the reactor is emptied, the resulting polymer is intensively mixed with partially desalinated water, then the polymer is added with a non-staining antioxidant, degassed and dried to a constant weight.

[0108] Example 17

[0109] Polymerization and modification.

[0110] In a pre-prepared metal reactor (washed with a solvent containing any organometallic compound), 750 ml of the batch (a mixture of hexane and butadiene-1,3), the monomer concentration in which is 20% by weight, are introduced with stirring. The reactor contents are brought to a temperature of 0 °C and solutions of the mixture of DIBAG (B) 1.5 ml (1.20 mmol), gadolinium neodecanoate (A) 0.41 ml (0.120 mmol) and EADC (C) 0.4 ml (0.47 mmol by chlorine) are successively introduced. In this case, the molar ratio of the components is A:B:C = 1:10:4, the butadiene-1,3 / Nd ratio is 15,000 mol / mol. After achieving the required conversion, at a temperature of 102 0C, a solution of the modifier - N-[3-diethoxy(methyl)silyl]propyl]-4-methylpentan-2-amine in an amount of 0.03 g / 100 g of polymer. The reactor contents must be stirred for 5 minutes. Then a stopper is added - neodecanoic acid in an amount of 0.05 g / 100 g of polymer and stirred again for 5-15 minutes.The reactor is then emptied, the polymer is loaded with a non-staining antioxidant, degassed and dried to constant weight.

[0111] Example 18

[0112] Polymerization.

[0113] 750 ml of the batch (a mixture of hexane and isoprene), the total concentration of monomers in which is 18% by weight, are introduced into a pre-prepared metal reactor (washed with a solvent containing any organometallic compound) with stirring. The reactor contents are brought to a temperature of 10 °C and solutions of DIBAG (B) 2.72 ml (1.68 mmol), neodymium and gadolinium neodecanoate (A) 0.28 ml (0.084 mmol) and DIBAC (C) 0.16 ml (0.19 mmol for chlorine) are introduced sequentially. In this case, the molar ratio of the components is A:B:C = 1:20:2.5, the isoprene / Nd ratio is 16,000 mol / mol. After achieving the required conversion, the reactor is emptied, the resulting polymer is intensively mixed with partially desalinated water, then the polymer is added with a non-staining antioxidant, degassed and dried to a constant weight.

Claims

CLAUSES OF THE INVENTION 1. A method for producing cis-1,4-polydienes by polymerization / copolymerization of conjugated dienes in a hydrocarbon solvent in the presence of a catalyst obtained by mixing a rare earth metal carboxylate (A), an organoaluminum compound (B) and a halogen source (C) at a total molar ratio of components [A]:[B]:[C]= [1]:[5-150]:[1-6], characterized in that said catalyst is prepared either in advance in an aliphatic, naphthenic solvent or in mixtures thereof with a conjugated diene, or during the polymer synthesis process, introducing the components directly into the monomer solution, in addition, the cis-1,4-polydiene polymer is mixed with a modifier and a stopper in such a way that its / their total dosage to the polymer is 0-1.0% by weight.

2. The method according to claim 1, in which neodymium, praseodymium, gadolinium or mixtures are used as the rare earth metal in the carboxylate composition.

3. The method according to claim 1, in which diisobutylaluminum hydride, triethylaluminum, triisobutylaluminum, isobutylaluminumoxane, methylaluminoxane, including its modified grades, or mixtures of the said components are used as the organoaluminum component of the catalytic system.

4. The method according to claim 1, in which the organoaluminum component of the catalytic system can be introduced at any stage of the catalyst preparation, wherein alumoxane is used both in a mixture with standard organoaluminum compounds and individually, by introducing it as the final component in the formation of the complex.

5. The method according to claim 1, in which ethyl aluminum sesquichloride, diethyl aluminum chloride, ethyl aluminum dichloride, diisobutylaluminum chloride or mixtures thereof are used as the source of halogen of the catalytic system.

6. The method according to claim 1, wherein the concentration of monomer in the solvent is in the range of 10-50% by weight, preferably 15-25% by weight.

7. The method according to claim 1, wherein the temperature of the batch is in the range of (-20) - 30 °C, preferably (-15) - 30 °C, while the final temperature of the polymerization process varies in the range of 70 - 150 °C, preferably 70 - 125 °C.

8. The method according to claim 1, wherein the solvent used is n-hexane, hexane isomers, cyclohexane or mixtures thereof.

9. The method according to claim 1, wherein butadiene-1,3, isoprene or mixtures thereof can be used as the conjugated diene.

10. The method according to claim 1, in which the modifier used is a compound from the series of aminosilanes containing alkoxy groups, such as N-(3-triethoxysilylpropyl)cyclohexanamine, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-[3-diethoxy(methyl)silyl]propyl]-4-methylpentan-2-amine, N-[3-dimethoxy(methyl)silyl)propyl]cyclohexanamine, N-(6-aminohexyl)aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, or from a series of halogen-containing compounds - disulfur dichloride, phosphorus trichloride, phosphorus pentachloride, tin tetrachloride, or mixtures thereof.

11. The method according to paragraphs 1-10, in which compounds from the series neodecanoic acid, stearic acid, lauric acid can be used as a stopper, and its dosage to the polymer is from 0 to 0.5% by weight.

12. The method according to paragraphs 1-9, in which the order of feeding the modifiers and stopper can be any, in the form of modifier-stopper, modifier-stopper-modifier, stopper-modifier, modifier without stopper.

13. The method according to paragraphs 1-11, in which the mixing of the polymer with the modifier / stopper in a static mixer and / or mixing reactor is carried out as follows: - the conversion of monomers before feeding the modifier is from 60 to 99%, preferably more than 95%; - modification time ranges from 5 minutes to 3 hours; - the modification temperature is from 70-150 °C, preferably 70-110 °C.

14. The method according to paragraphs 1-9, in which water, preferably partially desalinated, is used as a stopper, and its dosage in a weight ratio is polymer / water = 1 / 0.

1.

15. The method according to claim 1, wherein the process of obtaining cis-1,4-polydiene can be carried out in a continuous or periodic mode.

16. The method according to paragraph 1, characterized in that the resulting polymer has the following characteristics: - Mn in the range from 7x 104 to 48* 104 g / mol; - Mw / Mn within the range from 1.5 to 4.0; - Mooney viscosity (МЫ+4,100°С) from 30 to 90 Mooney units; - the content of cis-1,4-links is not less than 95%.

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