RU2678061C2 - Continuous manufacturing process for rubber masterbatch and rubber masterbatch prepared therefrom - Google Patents

Abstract

FIELD: technological processes.SUBSTANCE: invention relates to a continuous manufacturing process for rubber masterbatch and rubber masterbatch prepared therefrom. Method comprises the following steps: step (1) of adding a filler to a rubber solution, forming a rubber/filler/solvent mixture by stirring, step (2) of coagulation of the rubber/filler/solvent mixture produced in step (1), resulting in a mixture of a rubber/filler composite and the solvent, and step (3) of removing the solvent and drying the mixture, resulting in a rubber/filler masterbatch. Method is carried out according to the wet compounding technology. Production process is continuous, highly efficient, low in cost.EFFECT: rubber masterbatch obtained according to the invention has excellent technological characteristics, physical and mechanical properties and provides high product quality.11 cl, 3 tbl, 4 ex

Description

The technical field to which the invention relates.

[0001] The present invention relates to the field of rubber production, in particular to a method for the production of rubber masterbatch in continuous mode and to a rubber masterbatch obtained by this method.

The background of the invention

[0002] In the production of the masterbatch of rubber, filler and additive in the rubber-filler-additive-solvent system, a very important step is the coagulation of the rubber-filler-additive complex from the solvent. WO 98/58985 describes a method carried out in a device comprising a large turbo dryer, the blades of which provide a rotational speed of 400 to 1200 rpm. The coagulation and drying processes with this method are slow, the process takes a lot of time and requires a lot of energy. The present invention relates to several high-speed methods of mixing and coagulation, in which a coagulation medium, including gas, in particular, a medium formed by having a high temperature gas and liquid, is subjected to instant mixing with a mixture of rubber, filler and additives in a high-energy turbulent state, and under the influence of high gas temperature and the difference in polarity between the liquid medium and the solvent, the rubber-filler-additive complex in a mixture of rubber, filler, additive and rust vitorite leads to desolvation (removal of solvent) to ensure coagulation. Under the influence of high-speed turbulence, the mixture and the coagulation medium, i.e., the desolvation medium, will be mixed in a very short time. Due to the greatly increased interface between the desolvation medium and the rubber-filler-additive-solvent complex, the coagulation rate of the rubber-filler-additive complex in the solvent turns out to be very high at a high temperature of the desolvation medium, during the coagulation process the solvent quickly evaporates, so that the particles of coagulated rubber have small sizes, which further accelerates the volatilization of the solvent and drying of the coagulated rubber. Therefore, compared with the prior art, the drying method disclosed in this application is characterized by high efficiency, cost-effectiveness in relation to energy costs and the ability to carry out the process in a continuous mode.

A brief description of the invention

[0003] Given the problems not solved in the prior art, one of the objectives of the present invention is to provide a method for the production of rubber masterbatch in continuous mode and rubber masterbatch obtained in this way. Another objective of the invention is to create a rubber product made using a rubber masterbatch according to the invention.

[0004] A method for producing a rubber masterbatch in continuous mode according to the invention has the following advantages:

[0005] (1) the production process is continuous and highly efficient,

[0006] (2) the drying is uniform and fast,

[0007] (3) the physical and mechanical properties of vulcanized rubber are greatly improved and the quality of the rubber product is greatly improved,

[0008] (4) in comparison with the coagulation technology with known wet compounding, the present invention does not impose special requirements on rubber and filler, thus providing a wide range of applications in relation to the types and composition of rubber, filler and additive,

[0009] (5) the device and method are very simple, ensure the continuity of the production process and are highly efficient, consume little energy, require less labor, thereby reducing costs, and

[0010] (6) The rubber masterbatch obtained by the proposed method has excellent technological characteristics, physical and mechanical properties, and ensures a high quality product.

[0011] In addition, the present invention relates to the following embodiments.

[0012] A method for producing a rubber masterbatch in a continuous mode, comprising the steps of:

[0013] stage (1), in which a filler is introduced into the rubber solution and, with stirring, a mixture of rubber, filler and solvent is obtained,

[0014] step (2), wherein the mixture of rubber, filler and solvent obtained in step (1) is subjected to coagulation to obtain a mixture of a rubber-filler complex and a solvent, and

[0015] stage (3), in which the solvent is removed and the mixture is dried to obtain a rubber masterbatch,

[0016] in this case, when performing the drying operation in step (3), the mixture obtained in step (2) is placed in a heated conveyor drying chamber and thermally dried in a vacuum or inert gas atmosphere, and the volatilized solvent and unreacted in the process for the synthesis of rubber, the monomer is sent to a condensation device and fractionation column for regeneration, or when performing the drying operation in step (3), the mixture obtained in step (2) is spray dried or instantly dried with Using as a heating medium of inert gas or water vapor, and the solvent and unreacted disappearing during synthesis of the rubber monomer sent to the condensation device and the fractionating column for regeneration.

[0017] It seems preferable that such a solution in which the coagulation operation performed in step (2) of the proposed method is implemented using at least one of the following technologies: flocculation to obtain flocculent formations, heating and desolvation, as well as a combination of these technologies.

[0018] It seems preferable that such a solution in which, ceteris paribus, the solvent removed in stage (3), regenerate.

[0019] It seems preferable to such a solution in which, ceteris paribus, one or more additives is selected from the following list: oil (liquid), anti-aging agent, crosslinking agent, active agent, antioxidant, agent that gives refractory properties, heat stabilizer , a light stabilizer, a dye, a pigment, a vulcanizing agent, a curing accelerator, while the above additives are added to stage (1) and (or) stage (2) of the proposed method.

[0020] It seems to be preferable that, ceteris paribus, water vapor is used as the heating medium, and the solid mixture obtained after drying contains water, followed by vacuum drying, thermal drying or extrusion thermal drying, as a result what get the masterbatch of rubber and filler.

[0021] It seems preferable to such a solution in which, ceteris paribus, nitrogen is used as an inert gas.

[0022] More preferable is a solution in which, ceteris paribus, thermal drying is implemented as oven drying or as atmospheric drying.

[0023] More preferable is such a solution in which, ceteris paribus, when implementing the above-mentioned extrusion thermal drying, water is first removed by extrusion, and then further drying (thermal) is performed.

[0024] More preferable is a solution in which, ceteris paribus, said further drying is atmospheric drying, oven drying, or mechanical drying.

[0025] More preferred is such a solution in which, ceteris paribus, said mechanical drying is drying using an open mill, plasticizer, closed mixer, closed continuous mixer, single screw extruder, or twin screw extruder.

[0026] In addition, the present invention provides for the creation of a rubber masterbatch obtained by the above method.

[0027] In addition, the present invention provides for the creation of a rubber product made using said rubber masterbatch.

[0028] A method for producing a rubber masterbatch in a continuous mode according to the invention comprises the following steps:

[0029] stage (1), in which a filler is introduced into the rubber solution and a mixture of rubber, filler and solvent is obtained with stirring,

[0030] step (2), wherein the mixture of rubber, filler and solvent obtained in step (1) is subjected to coagulation to obtain a mixture of a rubber-filler-solvent complex, and

[0031] stage (3), in which the solvent is removed and the mixture is dried to obtain a rubber masterbatch,

[0032] in this case, when performing the drying operation in step (3), the mixture obtained in step (2) is placed in a heated conveyor drying chamber and thermally dried in a vacuum or inert gas atmosphere, and the volatilized solvent and unreacted in the process for the synthesis of rubber, the monomer is sent to a condensation device and fractionation column for regeneration, or when performing the drying operation in step (3), the mixture obtained in step (2) is spray dried or instantly dried with Using as a heating medium of inert gas or water vapor, and the solvent and unreacted disappearing during synthesis of the rubber monomer sent to the condensation device and a fractionator for recovery for subsequent reuse.

[0033] Ceteris paribus, the coagulation operation performed in step (2) is carried out according to any technology known in the industry, for example, by flocculation to obtain flocculent formations, by heating or by desolvation, etc., or combine these technologies. A method for producing a rubber masterbatch in a continuous mode according to the invention may further comprise a step for regenerating the solvent removed in step (3) for reuse. In addition, at the stage (1) and (or) stage (2), one or more additives selected from the following list may be added: oil (liquid), anti-aging agent, crosslinking agent, active agent, antioxidant, refractory agent properties, thermal stabilizer, light stabilizer, dye, pigment, curing agent, curing accelerator.

[0034] Step (1) may be carried out in a manner known in the industry. The mixing in step (1) can be performed using a conventional mixing apparatus, for example, a paddle mixing apparatus, a capacitive mixing apparatus, a planetary mixing apparatus, a cranked mixing apparatus, etc.

[0035] Step (1) may further comprise a fine dispersion operation, which can be carried out as follows: the mixture obtained after mixing is discharged through the nozzle under high pressure and with high shear, so that dispersion of the filler and / or additive is improved, or the exhausted material is passed through a multi-pipe, causing the mixture solution to collide with the walls of the pipe, thus increasing the degree of dispersion of the filler and (or) additive, or Therians passed through a pipe whose internal diameter is changed repeatedly, so that its cross section that tapers or expands, - in order to change the shear stress with increasing thereby the degree of filler dispersion and (or) the additive. In this case, a pressure range from 0.1 MPa to 60 MPa is used, preferably from 10 MPa to 40 MPa.

[0036] The mixture obtained after fine dispersion can also be subjected to further fine dispersion in order to further increase the degree of dispersion of the filler and / or additive in the rubber solution:

[0037] (i) the mixture obtained after fine dispersion is continuously fed into a ball mill and / or colloidal mill for dispersion, so that uniform dispersion of the filler and / or additive in the rubber solution is ensured,

[0038] (ii) the mixture obtained after fine dispersion is continuously fed into the grinding device for grinding, so that adequate dispersion of the filler and / or additive in the rubber solution is ensured, while said grinding device has one or more sets of rotating with a high the speed of the flat grinding disks and fixed rods or fixed disks mounted on the nozzle jacket and interspersed with said flat grinding disks,

[0039] (iii) the mixture obtained after fine dispersion is continuously fed into the grinding device for grinding, while the grinding device has two blades rotating in opposite directions, perforated grooves are made in the blades, an increase in the degree of rotation of these blades under high pressure dispersing the filler and / or additive in a rubber solution, while using a pressure range from 0.1 MPa to 60 MPa, preferably from 10 MPa to 40 MPa,

[0040] (iv) the mixture obtained after fine dispersion is continuously fed into a multilayer slit disperser operating under high pressure and extruded under high pressure through a gap between the two layers, so that the degree of dispersion of the filler and / or additive in the rubber solution is increased provided due to the large shear forces that arise, while using a pressure range from 0.1 MPa to 60 MPa, preferably from 10 MPa to 40 MPa,

[0041] (v) the mixture obtained after fine dispersion is continuously fed into the power dispersant for dispersion, while the rotors of the power dispersant rotating at high speed have a large number of radially distributed slots or holes, the mixture collides with the stator surface at high speed, resulting in is an increase in the degree of dispersion of the filler and (or) additives in the rubber solution.

[0042] Two or more of the five fine dispersion methods described above can be used together.

[0043] The rubber solution for the preparation of rubber polymerized in solution can be obtained directly from the production line, and can also be prepared by dissolving any type of dry rubber in a rubber solution. When preparing a rubber solution with dry rubber, any type of rubber known in the industry, in particular, natural polymers or synthetic polymers, can be used as this dry rubber. Natural polymers can be used, for example, natural rubber, gutta-percha, guava, etc., and synthetic polymers can be used, for example, the material obtained by polymerization of a monomer in solution (i.e., rubber polymerized in solution), material obtained by polymerizing a monomer in an emulsion (i.e., rubber polymerized in an emulsion), and a material obtained by polymerizing a monomer per se. When the rubber solution for preparing the rubber polymerized in solution is obtained directly from the production line, this rubber polymerized in solution is a homopolymer or copolymer of monomers such as ethylene, propylene, butylene, pentene, hexene, heptene, or diene having a molecule from four to seven carbon atoms, or triene having from six to seven carbon atoms, or alkenes containing other atoms of functional groups, while the other atoms mentioned are a silicon atom, a fluorine atom, a chlorine atom , a nitrogen atom, an oxygen atom, a sulfur atom, an ester group, an amino ester group and a cyano group, also contain homopolymers or copolymers containing the above monomers, including but not limited to polybutadiene, polyisoprene, styrene-butadiene rubber, ethylene-propylene rubber, rubber, nitrile butadiene rubber, neoprene, silicone rubber, fluorine-containing rubber, polyurethane rubber, chlorosulfone-polyethylene rubber, acrylate rubber, etc. The molecular weight of the rubber is from 1,000 to 40,000,000, preferably from 5,000 to 30,000,000, even more preferably from 10,000 to 8,000,000.

[0044] Solvents in a rubber solution are solvents suitable for various types of rubber. In particular, an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a chlorohydrocarbon solvent, a ketone solvent, an ether solvent, or an ester solvent may be used, while the following substances may be used as the mentioned aliphatic hydrocarbon solvent: various types of solvent gasoline, cycloalkane, substituted cycloalkane and normal alkane as said aromatic hydrocarbon solvent can be used, inter alia, the following substances: benzene, toluene, xylene, and styrene, as said hloruglevodorodnogo solvent can be used, inter alia, the following substances: methylene chloride, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, tetrachlorethylene and chlorotoluene. The concentration of rubber in the solution is in the range from 1 mass. % to 60 mass. %, preferably from 5 wt. % to 40 mass. %, more preferably from 10 mass. % to 30 mass. %

[0045] As a filler, various types of solid powder reinforcing agents and fillers used in rubber, such as various types of carbon black, silica, metal oxides, salts, various resins, as well as nanoscale forms of the above fillers, can be used. The following substances can be used as the mentioned metal oxides, among others: aluminum oxide, magnesium oxide, zinc oxide, etc., the following substances can be used, among others, the following substances: calcium carbonate, pottery clay, and also nanoscale forms of the above fillers. The specific surface area of the filler is from 0.1 m ² / g to 800 m ² / g, preferably from 1 m ² / g to 500 m ² / g, more preferably from 5 m ² / g to 300 m ² / g . As for carbon black and silica (also known as “white carbon black”), they have an oil absorption of from 20 ml / 100 g to 250 ml / 100 g, preferably from 25 ml / 100 g to 200 ml / 100 g, more preferably - from 30 ml / 100 g to 150 ml / 100 g. The filler is used in an amount of from 5 to 300 mass parts per 100 mass parts of rubber, preferably from 10 to 200 mass parts per 100 mass parts of rubber, more preferably from in an amount of from 30 to 150 mass parts per 100 mass parts of rubber. As the filler, you can also use two or more of the above substances.

[0046] The category of fillers also includes modified surface fillers. Surface modification can be carried out, inter alia, by a chemical reaction by attaching certain functional groups to the surface of the filler or by mixing or absorption to ensure physical contact of the modifier with the surface of the filler. As for the modification, the modifier can be dissolved in a solvent, then mixed with a carrier to perform a liquid-phase modification, as described in the publication of W. Wang, G. Nance, A. Widal and other co-authors (Wang W, Nanse G, Vidal A et al.) in the source “KGK [J] ", 1994, 47: 493, in addition, the modifier can be mixed with filler and subjected to heating to perform solid-phase modification, as described in the publication of M.J. Wang, S. Wolfe (Wang MJ, Wolff S) in the source "RST [J]", 1992, 65: 715. Surface modification can also be performed before the filler is introduced into the rubber solution, or during the introduction of the surface modifier into the mixture of the rubber solution and filler. As a surface modifier, a surface modifier known in the industry, for example, an organic silane coupling agent, characterized by the following general formula can be used:

[0047]

[0048]

[0049] or

[0050] where, when q = 1, then A is —SCN, —SH, —Cl, —NH ₂ ;

[0051] and when q = 2, then A is —S _x -;

[0052] R and R 'are branched or linear alkyl or phenolic groups having from one to four carbon atoms, wherein the R and R' groups can be identical or different;

[0053] n = 0, 1 or 2;

[0054] Alk is a linear or branched alkyl having from one to six carbon atoms;

[0055] Alk _eny l is a linear or branched alkenyl having from one to six carbon atoms;

[0056] m is 0 or 1;

[0057] Ar is aryl having from six to 12 carbon atoms;

[0058] p = 0 or 1, while p and n cannot be zero at the same time;

[0059] the value of x can take values from 2 to 8;

[0060] the most used being bis (triethoxypropylsilane) tetrasulfide and bis (triethoxypropylsilane) disulfide, 3-seratio-propyltriethoxysilane, γ-mercaptotrimethoxysilane, a zirconic acid ester coupling agent, a titanate coupling agent, a coupling agent and a nitro compound. As the alcohol compound mentioned, monohydric alcohols, dihydric alcohols and polyhydric alcohols can be used, among others. As the mentioned alcoholic compound, the following substances can be used, among others: propyl alcohol, butyl alcohol, ethylene glycol, polyethylene glycol and their derivatives.

[0061] In step (1) of the proposed method, the filler and (or) additive can be added directly to the rubber solution, or the filler and (or) additive can be first added to the solvent, and the resulting mixture is mixed to obtain a uniform suspension, after whereupon a rubber solution is added to the resulting suspension with stirring, and the resulting mixture is stirred. As the aforementioned additive, one or more agents from the following list can be used: oil (liquid), an anti-aging agent, a crosslinking agent, an active agent, an antioxidant, a heat stabilizer, a light stabilizer, an agent that imparts refractory properties, a dye, a pigment, a curing agent, curing accelerator. The additive is added in conventional amounts, or the amount of additive can be adjusted according to specific requirements.

[0062] The coagulation performed in step (2) of the proposed method is implemented using at least one of the following technologies: flocculation to obtain flocculent formations, heating and desolvation, as well as combinations of these technologies.

[0063] It seems preferable to such a solution in which at the stage (2) of the proposed method, the mixture of rubber, filler and solvent obtained at the stage (1) of the proposed method is transferred to the coagulator and brought into contact with the coagulator and mixed with one or more fluid media selected from the following list: gaseous nitrogen, water vapor, water, filling aqueous suspension, oil (liquid), and then subjected to coagulation to obtain a mixture of a rubber-filler complex with a solvent.

[0064] The coagulator used in step (2) of the proposed method may be a tubular coagulator having one or more inlet ports, the flow direction of the material through these inlet ports may be parallel to the pipe axis of the tubular coagulator, and at the end of this pipe an outlet port is made which can be oriented at an angle from 1 ° to 180 °, preferably at an angle from 20 ° to 120 °, more preferably at an angle from 70 ° to 100 °, most preferably at an angle from 85 ° to 95 ° to the axis of the tubular pipe coagulator. If there are several inlet ports at a part of these inlet ports, the material feed direction is parallel to the axis of the pipe coagulator tube, while the material feed direction at the other inlet ports is oriented at an angle of 1 ° to 180 °, preferably at an angle of 20 ° to 120 ° more preferably at an angle of from 70 ° to 100 °, most preferably at an angle of from 85 ° to 95 ° to the axis of the cylindrical tube of the tubular coagulator, and the projection of the material supply direction through each inlet port to a cross section perpendicular the axis of the pipe may have a direction from radial to tangent with respect to the cross section, with radial and tangent directions being preferred. All inlet ports are located in the same plane perpendicular to the axis of the pipe, or the inlet ports are located in different planes.

[0065] In addition, the coagulator used in step (2) of the proposed method may be a coagulator containing two or more concentric pipes, each pipe having one or more inlet ports, and a material supply direction through these inlet ports parallel to the axis of the pipe or is the tangent direction of the pipe, and the outlet port is made at the end of the pipe. The fluid may be introduced through the inlet ports directly, or tangentially to the pipe wall. The ends of the inlet ports of each pipe may be located on the same plane, or the ends of the inlet ports of each pipe may be longer or shorter sequentially from the middle to the edges.

[0066] In addition, the coagulator used in step (2) of the proposed method may be a cylindrical coagulator having only one inlet port located on the upper end or wall of the cylinder, and the outlet port is located at the lower end of the cylinder. The fluid can be introduced into the coagulator through the inlet port, and can also be introduced into the coagulator tangentially to the cylinder wall.

[0067] In addition, the coagulator used in step (2) of the proposed method may be a structure having a cylindrical upper part and a conical lower part and provided with one or more inlet ports. The material feed direction through these inlet ports can be tangent to the cylinder wall, all inlet ports can be located in the same plane, or they can be located in different planes. In addition, the material feed direction through the inlet ports may be perpendicular to the axis of the cylinder, or may be oriented at an angle of 1 ° to 180 °, preferably at an angle of 20 ° to 120 °, more preferably at an angle of 70 ° to 100 °, most preferably at an angle of 85 ° to 95 ° to the axis of the cylinder. The projection of the material supply direction through each inlet port onto a cross section perpendicular to the axis of the cylinder may have a radial to tangent direction relative to the cross section, with tangential directions being preferred.

[0068] In step (2) of the proposed method, one or more fluids selected from the following list are supplied through said one or more inlet ports: nitrogen gas, water vapor, water, filling aqueous suspension, oil (liquid), and the mixture of rubber, filler and solvent is fed to the coagulator, while the temperature of nitrogen gas can be from 20 ° C to 300 ° C, the temperature of water vapor can be from 100 ° C to 300 ° C, the temperature of liquid water can be from 20 ° C to 100 ° C. As the oil (liquid), oil (liquid) known in the art, commonly used to produce oil-filled rubber, can be used. The oil (liquid) used in stage (2) may be the same as the oil (liquid) used in stage (1) of the proposed method, or may be different from it. The fillers used in stage (2) can also be the same as the fillers used in stage (1) of the proposed method, and differ from them.

[0069] To carry out the drying in step (3) of the proposed method, the mixture obtained in step (2) is placed in a heated conveyor drying chamber and thermally dried in a vacuum or in an atmosphere of an inert gas (such as nitrogen), and the volatile solvent and unreacted in the process of rubber synthesis, the monomer is sent to a condensing device and fractionation column for regeneration, or to carry out drying in stage (3) of the proposed method, the mixture obtained in stage (2) is spray dried or gnovennoy drying using as a heating medium of an inert gas (e.g., nitrogen) or steam as solvent and unreacted disappearing during synthesis of the rubber monomer sent to the condensation device and the fractionating column for regeneration.

[0070] When water is used as the heating medium, the solid mixture obtained after drying contains water, after which vacuum drying, thermal drying or extrusion thermal drying is performed to obtain a masterbatch of rubber and filler. Said vacuum drying may be carried out at ambient temperature, or may be freeze-drying or heating with vacuum. Thermal drying can be carried out according to known technologies, for example, as oven drying or as atmospheric drying. Extrusion thermal drying includes a preliminary stage, which consists in removing the heating medium by extrusion, and subsequent drying, which may be atmospheric drying, oven drying, or mechanical drying, while mechanical drying is drying using an open mill, plasticizer, closed mixer a closed continuous mixer, single screw extruder, or twin screw extruder.

[0071] The regeneration of the solvent can be carried out by any method known in the art, for example, the solvent that has transferred to the gas phase is regenerated by condensation on the surface or by condensation with mixing (contact condensation). When using condensation technology with mixing, water can be used as a cooling agent.

[0072] The technical results of the invention are listed below.

[0073] (i) The technical results of the invention include high modifiability: not only by the general mixing of the rubber solution, which is simple to implement and provides a slightly lower degree of dispersion of the filler and lower characteristics, with fillers and additives, but also with direct heating a masterbatch of rubber, filler and additives can be prepared, but also using a specially developed dispersant, a mixing coagulator and by mechanical drying, It is prepared by a master batch of rubber, filler and additives having a higher cost and better performance; masterbatch prepared in different ways can properly meet the requirements for the properties of different rubber products.

[0074] (ii) The technical results of the present invention include the use of a specially designed coagulator, which is a single device with one or more inlet ports and one outlet port. When a thin dispersed mixture of rubber, filler, additive and solvent is introduced into the coagulator at a high speed and in a state of high turbulence, due to the very high speed and in accordance with the general principles of hydromechanics and the principles of hydromechanics of turbulent states, the internal pressure of the mixture drops sharply. Under the action of a large shear, the mixture passes into a droplet state, in addition, at low pressure, a solvent with a low boiling point in the composition of the liquid mixture can reach the boiling point, as a result of which the solvent escapes with separation, thereby separating the solvent from the mixture. This separation of the solvent from the mixture can also be carried out by introducing droplets containing a large amount of solvent vapor from the coagulator through a narrow outlet port, and due to the increased flow rate, the pressure drops sharply, so that the rate and degree of transition of the solvent into the gas phase significantly increase. When this fluid of mixed composition is introduced into a drying plant containing a high temperature gas such as nitrogen, the increased temperature causes the solvent to diffuse rapidly from the mixture into the hot atmosphere, thereby greatly increasing the drying efficiency.

[0075] (iii) The aforementioned coagulation and desolvation operations contemplated by the present invention are that a mixture of rubber, filler, additive and solvent is introduced into the coagulator with several inlet ports through one or two of these inlet ports, and through the remaining one or more inlet ports inject nitrogen. When the introduced mixture and gas are in a high-energy and high-speed turbulent state, their mixing can be carried out for several milliseconds or several tens of milliseconds, and during this time the mixture passes into a droplet state. At low pressure and in a state of turbulence, the solvent in the composition of small droplets rapidly expands and passes into a gaseous state, so that the rubber, filler, and additive that are components of the mixture undergo rapid coagulation to form a dispersed three-phase (consisting of solid, liquid, and gas) mixture. During the process, when the temperature of the nitrogen introduced into the coagulator is high, the rate of expansion of the solvent and its transition to the gaseous state, as well as the rate of coagulation with the formation of a solid, are significantly increased, and the amount of liquid components is significantly reduced. In extreme situations, two phases remain: gas and solid, that is, only solid coagulation products and gaseous nitrogen and solvent vapors. When a three-phase or two-phase mixture passes through the narrow outlet port of the coagulator, due to the increased flow rate, the pressure of the fluid drops even more, so that the degree and rate of transition of the solvent to the gaseous state increases significantly and the amount of the liquid phase rapidly decreases. When the mixture fluid is introduced into a drying plant containing a gas having a high temperature, such as nitrogen, and due to the elevated temperature, the solvent remaining in the coagulation product based on rubber, filler and additive undergoes further rapid volatilization and diffuses into the atmosphere of hot gas, which greatly increases the drying efficiency.

[0076] (iv) One of the modes of the above coagulation and desolvation according to the invention is carried out when the additive contains oil (liquid), a mixture of rubber, filler, additive (which does not contain oil (liquid) or contains it only if required rubber compounds) and a solvent are introduced into the coagulator with several inlet ports through one or two of the mentioned inlet ports at high pressure and at high speed, and the oil (liquid) is introduced into the coagulator through the remaining one or more in the intake ports. The amount of oil (liquid) is defined as the difference between the amount required in the composition of the masterbatch and the amount of oil (liquid) used in the mixture of rubber, filler, additive and solvent. Under conditions of high-energy turbulence, the said mixture and oil (liquid) undergo rapid mixing and coagulation, and the low pressure under which the fluid is in a state of high-speed turbulence contributes to the rapid transition of the solvent into a gaseous state and its separation from the rubber-filler-additive complex. Oil (liquid) has a high heat capacity, so when its temperature rises, the process of transition of the solvent to the gaseous state is accelerated. When the resulting fog-like mixture of solid, liquid and gas is introduced through a narrow outlet port at a high speed into a drying unit that contains gas at high temperature, due to the reduced pressure of the fluid caused by the conditions of the discharge, the contact area of the dispersed fog-like solid-liquid phase with the gaseous phase increases even more, as a result of which the rate of transition of the solvent to the gaseous state increases, and at the same time The high-temperature atmosphere also significantly increases the efficiency of desolvation.

[0077] (v) One of the modes of the above coagulation and desolvation according to the invention is carried out by introducing into the coagulator with several inlet ports a mixture of rubber, filler, additive and solvent through one or two of the inlet ports under high pressure and high speed, and through the remaining one or more inlet ports, water vapor is introduced into the coagulator under high pressure. Under the desolvation action of water and high temperature, the rubber-filler-additive complex coagulates in the solvent for several milliseconds or several tens of milliseconds and at low pressure becomes fog-like, and the solvent volatilizes rapidly. Due to the latent heat of the vapor condensation process, the rate of transition of the solvent to the gaseous state is much higher than in the case of using hot nitrogen. But the resulting fog-like three-phase mixture of solid, liquid and gas is also introduced with water. When this mixture is injected at high speed and high pressure through the narrow outlet port of the coagulator into the atmosphere of a gas at a high temperature, due to the decreased pressure and a further increase in temperature, the water and solvent become gaseous and separated from the solid-state rubber-filler-additive complex and, passing into the gas phase, increase the drying efficiency of this complex.

[0078] (vi) One of the modes of the above coagulation and desolvation according to the invention is carried out by introducing into the mixer / coagulator with several inlet ports a mixture of rubber, filler, additive and solvent through one or two of these inlet ports at high pressure and at high speed and through the remaining one or more inlet ports at the same time, under high pressure and at high speed, water is introduced into the mixer / coagulator, namely, water at high temperature e. In a high-energy turbulent state and in combination with the desolvation effect of water on a rubber solution, the rubber-filler-additive complex coagulates for several milliseconds or several tens of milliseconds. Due to the low pressure in the high-energy turbulent liquid, in particular, when the water used is at a high temperature, the solvent quickly reaches the boiling point and evaporates, and the water also partially passes into a gaseous state. When a three-phase mixture of solid, liquid, and gas from the mixer / coagulator is introduced through a narrow outlet port under high pressure into a drying unit that contains air or nitrogen at high temperature, due to the reduced pressure due to the high speed, the fluid undergoes dispersion with transition into a fog-like state in an atmosphere of high temperature air or nitrogen. The huge specific surface area of the two-phase solid-liquid rubber-filler-additive complex, coagulating in fog and at low pressure, contributes to the further volatilization of water and solvent, thereby increasing the drying effect of the solid complex, eliminating water and solvent. If too much water gets into the mixer / coagulator, then the rubber-filler-additive complex obtained as a result of coagulation can be mixed in water. In this case, the complex containing water is removed from water by known methods, such as filtration, centrifugation, etc. followed by drying.

[0079] (vii) One of the modes of the above coagulation and desolvation according to the invention is carried out by introducing into the coagulator with several inlet ports a mixture of rubber, filler, additive and solvent through one or two of the inlet ports under high pressure and high speed, and through the remaining one or more inlet ports, at the same time, a high-pressure aqueous suspension, preferably a high-pressure water suspension, is introduced into the coagulator under high pressure and at a high speed Penzov kept at a high temperature. In a high-energy turbulent state and in combination with the desolvation effect of water on a rubber solution, the mixture of rubber, filler, additive and solvent is uniformly mixed with the aforementioned aqueous filler suspension, and the rubber-filler-additive complex coagulates for several milliseconds or several tens of milliseconds. Due to the fact that the state of high-energy turbulence provides reduced pressure, especially when using a filler aqueous suspension having a high temperature, the solvent easily reaches the boiling point and escapes, and the water partially passes into a gaseous state. After a three-phase mixture of solid, liquid and gas from the mixer / coagulator through a narrow outlet port under high pressure enters the collector device, due to the low pressure due to the high speed, the fluid in the atmosphere with a high temperature of air or nitrogen passes into a foggy dispersed state. On the one hand, due to the decreased pressure, and on the other hand, due to the significantly increased contact area between the solid and liquid phases and the gas, the solvent and water quickly diffuse into the gaseous phase. If too much water gets into the filling aqueous suspension, which is then discharged, then the water cannot completely evaporate, and the rubber-filler-additive complex obtained as a result of coagulation can be mixed in water, in which case the complex containing water eliminates water by known methods such as filtration, centrifugation, etc. followed by drying.

[0080] (viii) The technical results of the present invention are that when an inert gas having a high temperature is introduced into the coagulator, particles of the solid masterbatch resulting from coagulation and desolvation in the coagulator can be separated from the gaseous solvent by means of a separator to obtain a masterbatch. As a separator, for example, a cyclone separator can be used. With this technology, it is possible to carry out the entire process for the production of the masterbatch without contact with water.

[0081] (ix) The technical results of the invention are that when the rubber-filler-additive complex obtained by coagulation contains water, the water can be removed by filtration or extrusion, after which the complex is subjected to mechanical drying at high temperature. As the drying device, an open mill, a plasticizer, a closed mixer, a closed continuous mixer, a single screw extruder, or a double screw extruder can be used. This method also provides the opportunity to further increase the degree of dispersion of fillers and additives.

Detailed Description of the Invention

[0082] The invention is further described by way of embodiments, to which, however, the scope of the invention is not limited.

[0083] 1. The experimental data obtained in the embodiments of the invention are obtained using the following instruments and measurement methods.

[0084] Table 1. Instruments used to prepare rubber samples

[0085]

[0086] Table 2. Methods and apparatus for testing the physical properties of vulcanized rubbers

[0087]

[0088] 2. Examples and comparative examples

[0089] Starting materials:

[0090] Synthetic Polyisoprene Rubber, IR-70, “Qingdao Ikesa Material Co., Ltd.”,

[0091] Silicon Dioxide (“White Soot”), NEWSIL1165-MP, “Wuxi Quechen Silicone Chemical Co., Ltd.”,

[0092] Zinc Oxide, "Dalian Zinc Oxide Co., Ltd.",

[0093] Stearic acid, PF1808, "Malaysia Integrated Fortune Sdn. Bhd "

[0094] Anti-Aging Agent 4020, "Jiangsu Sinorgkem Technology Co., Ltd.",

[0095] Silane Crosslinking Agent Si69, Nanjing Shuguang Chemical Group Co., Ltd.,

[0096] CZ Curing Accelerator, “Shandong Sunsine Chemical Co., Ltd.”,

[0097] DPG Curing Accelerator, “Shandong Shanxian County Chemical Co., Ltd.”,

[0098] Sera, "Wudi Jinsheng Chemical Co., Ltd."

[0099] Comparative example 1

[0100] In a closed mixer containing 100 parts of synthetic cis-polyisoprene, 56 parts of silica ("white carbon") and 5.6 parts of silane crosslinking agent Si69 were loaded for compounding after these fillers were mixed in a rubber medium , 3.5 parts of zinc oxide, 2 parts of stearic acid and 2 parts of anti-aging agent 4020 were added, after which the system was compounded for 4 minutes, then the resulting mixture was unloaded from a closed mixer, rolled and loaded into an open type mill to obtain a pre-rubber blend. After aging for 8 hours, 2 parts of a CZ curing accelerator, 1 part of a DPG curing accelerator, and 1.8 parts of sulfur were added to this pre-rubber mixture in an open-type mill to form a rubber mixture. Then, the resulting rubber mixture was discharged from the open-type mill and kept for 8 hours, after which it was vulcanized using a “Flat Vulcanizer” at a temperature of 150 ° C until the optimum vulcanization point was reached, so that vulcanized rubber - 1 dry was obtained way.

[0101] Example 1

[0102] To 100 parts of a 12% solution of cis-polyisoprene in normal hexane were added 56 parts of silicon dioxide ("white carbon"), 5.6 parts of a silane crosslinking agent Si69 and 3.5 parts of zinc oxide, after which this system of rubber, silicon dioxide ("white carbon"), a crosslinking agent Si69 and normal hexane were pre-mixed in a paddle mixer, and then the resulting mixture was introduced through a pipe into a multi-pipe, causing the solution to collide with the walls of the pipe, thereby increasing the degree of dispersion filler. The mixture was then continuously fed into a fine dispersion milling device to provide a fine dispersed mixture. Then, a thin dispersed mixture was continuously introduced into the conical coagulator with four inlet ports through two of its inlet ports under a pressure of 30 MPa, and at the same time nitrogen was introduced through the other two inlet ports of the coagulator at a temperature of approximately 180 ° C. Then, the resulting mixture was continuously introduced into a drying device filled with nitrogen having a temperature of approximately 150 ° C, resulting in a mixture of rubber, silicon dioxide ("white carbon"), crosslinking agent Si69 and normal hexane, divided into small drops from 1 s to 10 s, the solvent evaporates, so that the formation of desolvated rubber particles occurs, and nitrogen and the solvent are separated from the rubber particles using a cyclone separator to obtain a powdered masterbatch - 1.

Example 2

To 100 parts of a 12% solution of cis-polyisoprene in normal hexane were added 56 parts of silicon dioxide ("white carbon"), 5.6 parts of a silane crosslinking agent Si69 and 3.5 parts of zinc oxide, after which this system of rubber, dioxide silicon ("white carbon"), a crosslinking agent Si69 and normal hexane were pre-mixed in a paddle mixer, and then the resulting mixture was introduced through a pipe into a multi-pipe, causing the mixture solution to collide with the pipe walls, thus increasing the degree of dispersion of the filler. The mixture was then continuously fed into a fine dispersion milling device to provide a fine dispersed mixture. Then, in order to coagulate the mixture, a thin dispersed mixture was continuously introduced into the conical coagulator with four inlet ports through two inlet ports at a pressure of 30 MPa, and at the same time, water having a temperature of approximately two was introduced through the other two inlet ports of the coagulator 95 ° C. The coagulated and disolvented rubber particles were filtered and then dried in vacuum drying at a vacuum of -0.08 MPa for 20 minutes, resulting in a masterbatch - 2.

Example 3

To 100 parts of a 12% solution of cis-polyisoprene in normal hexane were added 56 parts of silicon dioxide ("white carbon"), 5.6 parts of a silane crosslinking agent Si69 and 3.5 parts of zinc oxide, after which this system of rubber, dioxide silicon ("white carbon"), a crosslinking agent Si69 and normal hexane were pre-mixed in a paddle mixer, and then the resulting mixture was introduced through a pipe into a multi-pipe, causing the mixture solution to collide with the pipe walls, thus increasing the degree of dispersion of the filler. The mixture was then continuously fed into a fine dispersion milling device to provide a fine dispersed mixture. Then, in order to coagulate the mixture, a thin dispersed mixture was continuously introduced into the conical coagulator with four inlet ports through two inlet ports at a pressure of 30 MPa, and at the same time, water having a temperature of approximately two was introduced through the other two inlet ports of the coagulator 95 ° C. The coagulated and disolvented rubber particles were filtered and then dried in a single-screw extruder for 3 minutes, resulting in a masterbatch - 3.

To each of the masterbatches (-1, -2, and -3) described above, in a closed mixer, 2 parts of stearic acid and 2 parts of anti-aging agent 4020 were added and compounding was performed for 4 minutes, after which the rubber mixture was unloaded from the closed mixer, rolled and loaded into an open mill. After compounding and curing for 8 hours, 2 parts of the CZ curing accelerator, 1 part of the curing accelerator D and 1.8 parts of sulfur were added to the rubber mixture placed in the closed mixer, then the mixture was compounded for 1.5 minutes, after which the mixture was unloaded from the closed mixer. The resulting rubber material was loaded into an open-type mill, kept for 8 hours, and then subjected to vulcanization using a “Flat Vulcanizer” at a temperature of 150 ° C until the optimum vulcanization point was reached, so that wet-vulcanized rubbers were obtained - 1, -2 and -3, respectively.

As can be seen in Table 3, with the same composition, but different drying methods, different rubbers, vulcanized by a wet method, acquire different properties. Compared to the masterbatch obtained by the dry method, the wet masterbatch has a much better dispersion rate of the filler in the rubber medium, the tensile strength, rebound elasticity and abrasion resistance of vulcanized rubbers are significantly improved, while compression fatigue reduced.

Claims (16)

1. A method for the production of rubber masterbatch in continuous mode, containing the following stages: stage (1), in which a filler is introduced into the rubber solution and, with stirring, a mixture of rubber, filler and solvent is obtained, stage (2), in which the mixture of rubber, filler and solvent obtained in stage (1) is subjected to coagulation to obtain a mixture of a rubber-filler-solvent complex, and stage (3), in which the solvent is removed, and the mixture is dried to obtain a rubber masterbatch, moreover, when performing stage (2), one or more coagulant coagulation methods are used, including a heating method, a desolvation method, or a combination of these methods, in this case, when performing the drying operation in step (3), the mixture obtained in step (2) is placed in a heated conveyor drying chamber and thermally dried in vacuum or in an inert gas atmosphere, and the volatilized solvent and the monomer that did not react during the synthesis of rubber sent to a condensation device and fractionation column for regeneration, or when performing the drying operation in step (3), the mixture obtained in step (2) is spray dried or flash dried using using an inert gas or water vapor as the heating medium, and the volatilized solvent and the monomer that did not react during the synthesis of rubber are sent to a condensation device and a fractionation column for regeneration. 2. The method according to claim 1, wherein the solvent removed in step (3) is regenerated for reuse. 3. The method according to p. 1, in which one or more additives is selected from the following list: oil (liquid), anti-aging agent, a crosslinking agent, an active agent, an antioxidant, an agent that imparts refractory properties, a heat stabilizer, a light stabilizer, a dye, a pigment, a curing agent, a curing accelerator, while the listed additives are added at the stage (1) and (or) stage (2). 4. The method according to any one of paragraphs. 1-3, in which water vapor is used as the heating medium, the solid mixture obtained after drying contains water, and then vacuum drying, thermal drying or extrusion thermal drying is performed, whereby a masterbatch of rubber and filler is obtained. 5. The method according to any one of paragraphs. 1-3, in which nitrogen is used as an inert gas. 6. The method according to p. 4, in which thermal drying is carried out as oven drying or as atmospheric drying. 7. The method according to p. 4, in which during extrusion thermal drying, water is first removed by extrusion, and then thermal drying is performed. 8. The method of claim 7, wherein the thermal drying is atmospheric drying, oven drying, or mechanical drying. 9. The method of claim 8, wherein said mechanical drying is drying using an open type mill, a plasticizer, a closed mixer, a continuous continuous mixer, a single screw extruder or a double screw extruder. 10. Rubber masterbatch prepared by the method according to any one of paragraphs. 1-9. 11. A rubber product made from a rubber masterbatch according to claim 10.