WO2015018278A1

WO2015018278A1 - Continuous manufacturing process for rubber masterbatch and rubber masterbatch prepared therefrom

Info

Publication number: WO2015018278A1
Application number: PCT/CN2014/082710
Authority: WO
Inventors: 王梦蛟; 宋建军; 戴德盈
Original assignee: 怡维怡橡胶研究院有限公司
Priority date: 2013-08-05
Filing date: 2014-07-22
Publication date: 2015-02-12
Also published as: RU2678061C2; CN103600434A; ZA201601523B; RU2016107597A3; RU2016107597A; CN103600434B; SG11201600905PA

Abstract

Disclosed are a continuous manufacturing process for a rubber masterbatch and a rubber masterbatch prepared therefrom. The manufacturing process comprises the following steps: step 1): a filler is added to a rubber solution, forming a rubber/filler/solvent mixture by stirring; step 2): the rubber/filler/solvent mixture in step 1) is subjected to coagulation, resulting in a mixture of a rubber/filler composite and the solvent; and step 3): the solvent is removed and the mixture is dried, resulting in a rubber/filler masterbatch. The present invention also relates to a masterbatch prepared using the above-mentioned process and a rubber article prepared using the masterbatch. Compared to the drying technologies in wet mixing in the prior art, the present invention has no specific requirements of rubber and filler, with a wider scope of usage. The production process is continuous, highly efficient, low in energy consumption and labour, and thus low in cost. The masterbatch prepared using this process has superior processing properties, physical and mechanical properties, and product quality.

Description

Description Continuous manufacturing method of rubber masterbatch and rubber masterbatch prepared by the method

3⁄4 ^ field

The invention relates to the field of rubber, in particular to a continuous manufacturing method of rubber masterbatch and a rubber masterbatch prepared by the method.

Background: fcfe^

In rubber/filler/additive/solvent systems, the agglomeration of t-gl/fillers/additives from solvents is an important step in the manufacture of rubber/fillers/additive masterbatches. The process described in W098/58985 is carried out in a large bladed worm gear dryer at 3⁄4⁄4⁄4⁄4 rpm, which is slower in coagulation and dryness, longer in process and higher in energy consumption. . The invention relates to several high-speed mixing/coacervation methods, wherein the coalescence medium comprises a gas, in particular a high-temperature gas and a liquid and a rubber/filler/additive mixture are instantaneously mixed in a high-energy turbulent state, due to the high temperature effect of the gas and the liquid medium and the solvent electrode The difference in properties, the rubber/filler/additive in the rubber/filler/additive/solvent mixture will cause a problem of desolvation in the solvent. Due to the high-speed turbulence effect, the mixing of the mixture and the condensed medium, the solvent-removing medium, can be completed in a very short time. Since the interface between the solvent-removing medium and the rubber/filler/addition agent/solvent is greatly increased, the aggregation speed of the rubber/filler/additive in the solvent is very fast. If the temperature of the solvent-removing medium is high, the solvent will be rapidly in the coagulation process. Volatilization causes the coacervate to be small, so the solvent volatilization and drying of the coacervate are further accelerated. Therefore, the drying method designed by the present application is characterized by high efficiency, energy saving, and continuous operation as compared with the prior art.

Summary of the invention

In view of the problems of the prior art, it is an object of the present invention to provide a continuous manufacturing method of a rubber masterbatch and a rubber masterbatch prepared by the method. Another object of the present invention is to provide a rubber article prepared using the rubber masterbatch of the present invention.

The advantages of the continuous manufacturing method of the rubber masterbatch of the leg of the invention are:

1) continuous and efficient;

2) drying evenly and at a fast rate;

3) significantly improve the physical and mechanical properties of the vulcanizate and the quality of the rubber product;

4) Compared with the suspected polycondensation technology in the existing wet mixing, the present invention has no requirements for t rubber and filler, and a wide range of applications for the types and contents of fillers and additives;

5) The production equipment and process are very simple, continuous, efficient, low energy consumption, and low labor, so the cost is low;

6) The masterbatch prepared by this method is superior in processability, physical and mechanical properties, and product quality. The invention further relates to the following embodiments:

A continuous manufacturing method of a t-size masterbatch comprises the following steps: Step 1): adding the filler to the rubber solution, and stirring the ship to form a mixture;

Coagulating the rubber J3⁄4/filler/solvent mixture in step 1) to obtain a mixture of the rubber face filler composite and the solvent;

Step 3): removing the solvent and drying the mixture of the M; to obtain a rubber-filled masterbatch;

Wherein, the drying in the step 3) means that the mixture obtained in the step 2) is transferred into a heated conveyor belt dryer, heated and dried under vacuum or an inert gas, and the solvent and the rubber are unreacted in the synthesis of the rubber. The monomer enters the condenser and the fractionation column for recovery; or the drying in step 3) means that the mixture obtained in the step 2) is spray-dried or flashed, and the heating medium used is an inert gas or water vapor, which is volatilized. Unreacted monomers in the solvent and rubber synthesis enter the condenser and the column for recovery.

Preferably, the agglomeration described in the step 2) may be one, a plurality, or a combination of a flocculant flocculation method, a heating method, and a solvent removal method.

Preferably, the solvent removed in step 3) is optionally recovered and recycled.

Preferably, wherein one or more selected from the group consisting of oil, antioxidant, pourant, active agent, antioxidant, flame retardant, heat stabilizer, light are optionally added in step 1) and/or step 2) Additives for stabilizers, dyes, pigments, vulcanizing agents and accelerators.

Preferably, steam is used as the heating medium, and the dried solid mixture contains water, and then dried under vacuum, heated and dried to obtain a rubber filler masterbatch.

Preferably, wherein the inert gas is nitrogen.

More preferably, wherein the heat drying is drying or air drying.

More preferably, wherein the extrusion heat drying is performed by first removing water after extrusion and then drying.

More preferably, the drying step is air drying, drying or mechanical drying.

More preferably, the mechanical drying is carried out using an open mill, a kneader, an internal mixer, a continuous internal mixer, a single screw extruder, and twin screw extrusion.

The invention also provides a t-size masterbatch prepared according to the above method.

Further, the present invention also provides a rubber article prepared by using the above masterbatch.

The continuous manufacturing method of the rubber master batch of the present invention comprises the following steps:

Step 1): adding the filler to the rubber solution, and stirring the ship to form a mixture;

Wherein, the drying in the step 3) means that the mixture obtained in the step 2) is transferred into a heated conveyor belt dryer, heated and dried under vacuum or an inert gas, and the solvent and the rubber are unreacted in the synthesis of the rubber. Monomer enters cold The recovery in the condenser and the fractionation column; or the drying in the step 3) means that the mixture obtained in the step 2) is spray-dried or flashed, and the heating medium used is an inert gas or water vapor, and the solvent and rubber which are volatilized are used. The unreacted monomer in the synthesis enters the condenser and the column for recovery.

The agglomeration method described in the step 2) may be carried out by any one of a method known in the art, such as a flocculant flocculation method, a heating method, a solvent removal method, or the like. The continuous process for the preparation of the t-size masterbatch of the present invention optionally further comprises the step of recovering the solvent removed in step 3) for recycling. Further, in step 1) and/or step 2), one or more selected from the group consisting of oils, antioxidants, coupling agents, active agents, antioxidants, flame retardants, heat stabilizers, light stabilizers, Additives for dyes, pigments, vulcanizing agents and accelerators.

Step 1) can be carried out using methods well known in the art. The agitation described in step 1) can be accomplished using a conventional agitator including, but not limited to, a blade agitated tank agitator, a spur mixer, and the like.

Step 1) may further comprise a fine dispersion step, wherein the fine dispersion of M may be carried out as follows: The mixture obtained by the above agitation is sprayed through a nozzle under high pressure and high shear to improve the filler and/or the additive. Dispersing; causing the above-mentioned effluent to pass through a multi-bend tube to cause the mixture to collide with the tube wall in the tube to increase the dispersibility of the filler and/or the additive; or to cause the effluent to pass through a tube having a plurality of tubes To shift the shear stress to increase the dispersion of the filler and/or additive. The pressure used ranges from 0.1 MPa to 60 MPa, preferably 10 MPa to 0 MPa.

The mixture formed after the fine dispersion can also further improve the dispersion of the filler and/or the additive in the rubber solution by the following fine dispersion:

i. The mixture of the finely dispersed M is continuously added to the ball mill and/or the colloid mill for dispersion to uniformly disperse the filler and/or the additive in the rubber solution;

将. The finely dispersed mixture is continuously added to a grinder for grinding to sufficiently disperse the filler and/or the additive in the rubber solution, the grinder having one or more sets of high-speed rotating flat grinding discs and fixed in the grinding A fixing pin or plate on the casing and between the flat grinding discs.

Iii. continuously adding the finely dispersed mixture to a grinder for grinding two blades having opposite directions of rotation, the vanes having fine pore flow grooves, which can be filled by rotating blades under high pressure And/or the degree of dispersion of the additive in the rubber solution. The pressure used ranges from 0.1 MPa to 60 MPa, preferably 10 MPa to 40 MPa.

Iv. The mixture after finely dispersing the legs is continuously added to the multi-layer high-pressure slit disperser, and the mixture is extruded under high pressure from the slit between the two layers, and the strong shear force generated at this time can increase the filler and / or the degree of dispersion of the additive in the rubber solution. The pressure used ranges from 0.1 MPa to 60 MPa, preferably 10 MPa to 0 MPa.

v. The household; M finely dispersed mixture is continuously added to the power disperser for dispersion, the high speed rotating rotor of the power disperser has a plurality of radially distributed slits or holes, and the mixture impinges on the stator at high speed On the surface Two or more of the above five fine dispersion methods may be used in series with each other.

The rubber solution can be directly obtained from the preparation of a solution rubber production line, and any type of dry glue can be dissolved in a solvent of the glue. When the rubber solution is prepared from dry glue, the dry glue may be any kind of rubber used in the art, such as a natural polymer or a synthetic polymer. The natural polymer includes, but is not limited to, natural rubber, gutta percha, silver chrysanthemum, etc.; synthetic polymers including, but not limited to, monomers obtained by polymerization in a solution (ie, a solution rubber), and polymerization of monomers in an emulsion ( That is, the latex rubber) and the monomer body are obtained by polymerization. When the M rubber solution is obtained directly from the preparation of the solution rubber production line, the solution rubber is a diene using ethylene, propylene, butene, pentene, hexene, heptene, 4-7 carbon atoms or a homo- or copolymer of a triene of 6 to 7 carbon atoms or an ethylenic monomer having other atoms or functional groups, the other atom or functional group being a silicon atom, a fluorine atom, a chlorine atom, a nitrogen atom, an oxygen atom , sulfur atom, ester group, amino ester group, cyano group, also includes homopolymers and copolymers containing the above monomers, including but not limited to polybutadiene, polyisoprene, styrene-butadiene rubber Ethylene-propylene rubber, butyl rubber, nitrile rubber, neoprene, silicone rubber, fluororubber, urethane rubber, chlorosulfonated polyethylene rubber, acrylate rubber, etc. The rubber has a molecular weight of from 1,000,000 to 40,000,000, preferably from 5,000 to 30,000,000, more preferably from 10,000 to 8,000,000.

The solvent in the rubber solution is a good solvent for various rubbers. The solvent may specifically be an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a chlorinated hydrocarbon solvent, a ketone solvent, an ether solvent, and an ester solvent, and the aliphatic hydrocarbon solvent includes, but is not limited to, various solvents such as gasoline, naphthene, and substituted cycloalkane. , n-alkane, the aromatic hydrocarbon solvent, including but not limited to benzene, toluene, xylene, styrene, household; M chlorinated hydrocarbon solvent including but not limited to dichloromethane, chloroform, carbon tetrachloride, dichloroethane Alkane, chlorobenzene, tetrachloroethylene, chlorotoluene. The concentration of the rubber in the solution ranges from 1% by weight to 60% by weight, preferably from 5% by weight to 0% by weight, more preferably from 10% by weight to 30% by weight.

The fillers include, but are not limited to, various solid powdered reinforcing agents and fillers used in rubber, such as various types of carbon black, silica, metal oxides, salts, different resins, and nanoscale materials of the above fillers. The metal oxides include, but are not limited to, alumina, magnesia, zinc oxide, etc., and the salts include, but are not limited to, carbonic acid, clay, and nanoscale materials of the above fillers. The specific surface area of the filler is 0.1 to 800m ² / g, preferably from 1 to 500 m ² / g, more preferably 5 to 300 m ² / g. For carbon black, silica (silica), the oil absorption value is from 20 to 250 ml / 100 g, preferably from 25 to 200 ml / 100 g, more preferably from 30 to 150 ml / 100 g, wherein the filler comprises a mixture thereof, Such as multiphase fillers, including but not limited to carbon black, silica, alumina, magnesia, zinc oxide, oxidized titanium oxide, boron oxide, etc., for two-phase or multi-phase fillers, for two-phase or multi-phase In terms of filler, the oil absorption value is from 20 to 250 ml/100 g, preferably from 25 to 200 ml/100 g, more preferably from 30 to 150 ml/100 g. The filler is used in an amount of 5 to 300 parts by weight (based on 100 parts by weight of the rubber), preferably 10 to 200 parts by weight, more preferably 30 to 150 parts by weight. The filler also includes a combination of two or more of the above fillers.

The fillers also include their surface modifying fillers. The surface modification may be carried out by chemically reacting a certain functional group on the surface of the filler or by mixing or adsorbing the modifier in a physical manner. On the surface of the material. In terms of modification, the modifier may be dissolved in a solvent and mixed with a filler, such as Wang W, Nanse G, Vidal A, et al. K. GK [J], 1994, 47:493. As described, the modifier may be mixed with a filler and heated for solid phase modification, as described in Wang MJ, Wolff. SRCT [J], 1992, 65:715. The surface modification may also be carried out before the filler is added to the rubber solution, or the modifier may be added to the mixture of the rubber solution and the filler for surface modification. The modifier is a conventional modifier in the art, such as the silane coupling agent indicated below:

( _n - ( O ) _3- „Si- (Alk) _m - ( Ar) _p ) _q (A) (I )

R _n '( O) _3-n Si- (Alk) (Π)

or! ^ ! ^^-^ ^ ) (m)

Where, when q = 1, A is -SCN, -SH, -CI, -NH ₂ ;

When q=2, A is -S _x -;

R and R' are a branched or linear alkyl or phenol group having from 1 to 4 carbon atoms, and R and R' may be the same or different;

n is 0, 1 or 2;

Alk is a linear or branched hydrocarbon group having 1 to 1 carbon atom;

Alkenyl is a linear or branched alkenyl group containing from 1 to 1 carbon atom;

m is 0 or 1;

Ar is an aryl group having 6 to 12 carbon atoms;

p is 0 or 1, p and n cannot be 0 at the same time;

X is 2 to 8;

The most commonly used are bis(triethoxypropylsilane) tetrasulfide and disulfide, 3-thiocyanopropyl-triethoxysilane, γ-mercapto-trimethoxysilane, zirconate couple a coupling agent, a phthalate coupling agent, a nitro coupling agent, an alcohol compound, a compound; the alcohol compound includes, but not limited to, a unit alcohol, a glycol, a polyol, and the alcohol compound includes, but not limited to, C. Alcohol, butanol, ethylene glycol, polyethylene glycol and derivatives thereof.

Step 1) of the present invention may directly add the filler and/or the additive to the rubber solution, or may add the filler and/or the additive to the same or different solvent as the rubber solution to form a uniform suspension, and then add and pass through. Stir in the rubber solution. The additive may optionally include one or more of an oil, an antioxidant, a coupling agent, an active agent, an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a dye, a pigment, a vulcanizing agent, or an additive for an accelerator. . The amount of the additive used is a conventional amount or adjusted according to actual conditions.

The agglomeration described in the step 2) may be one, a plurality, or a combination of a flocculant flocculation method, a heating method, and a solvent removal method.

Preferably, the rubber/filler/solvent mixture in step 1) is fed to the agglomerator in step 2) and is condensed The polymerizer is contacted with one or more of nitrogen, water vapor, water, a filler slurry and an oil to form a mixture of the rubber/filler composite and the solvent.

The agglomerator used in step 2) may be a tubular agglomerator having one or more feed ports, wherein the feed port may be fed in a direction parallel to the axial direction of the tubular agglomerator tube, the outlet being at The end of the tube may also be at an angle of 1-180° to the axial direction of the tubular agglomerator tube, preferably; 20-120° angle, more preferably 70-100° angle, most preferably 85-95° angle. When there are a plurality of feed ports, the feed direction of the partial feed port is parallel to the axial direction of the tube agglomerator tube; the feed direction of the remaining feed ports is opposite to the axial direction of the tube of the tube agglomerator An angle of 1-180°, preferably an angle of 20-120°, more preferably 70-100. The angle is most preferably 85-95. Angle, the projection of the feed direction of each feed port on a cross section perpendicular to the tube axis is any direction between the radial direction of the cross section to the tangential direction of the cross section, preferably a radial direction, or a tangent direction. The feed ports are all on the same plane perpendicular to the axial direction of the tube or the household; the feed ports of the 3⁄4 are on different planes.

The agglomerator used in step 2) may also be an agglomerator consisting of two or more mutually concentric tubes, wherein each tube has one or more feed ports, and the feed direction of the feed port is Parallel to the axial direction of the tube or the tangential direction of the tube, the outlet is at the end of the tube. The fluid can be passed directly or through the tangential direction of the tube wall. The ends of the feed ports of each tube may be in the same plane, or may be lengthened from the ends of the feed ports of the inner and outer tubes or sequentially shortened from the inner and outer ends of the feed ports of each tube.

The agglomerator used in step 2) may also be a barrel agglomerator having only one feed port located at the upper end of the barrel agglomerator or on the wall of the barrel, the outlet being at the lower end of the barrel. The fluid can be injected directly into the agglomerator through the feed port or injected into the agglomerator in a tangential direction along the wall of the vessel.

The agglomerator used in the step 2) may also have a cylindrical shape at the upper portion and a conical tubular structure at the lower portion, and have one or more feed ports. The feed direction of the feed port may be the tangential direction of the barrel wall; each feed port may be in the same plane or in a different plane. The feed direction of the feed port may also be perpendicular to the axial direction of the barrel or at an angle of 1-180° to the axial direction of the barrel, preferably 20-110°, more preferably 70-100°, most preferably 85-95. ° angle, the projection direction of the feed direction of each feed port in a cross section perpendicular to the axis of the cylinder is any direction between the radial direction of the cross section to the tangential direction of the cross section, preferably the tangential direction of the cross section .

One or more of the nitrogen, water vapor, water, filler slurry and oil described in step 2) and the rubber/filler/solvent mixture obtained in step 1) are condensed through one or more feed ports The temperature of the nitrogen gas is 20-300 ° C, the temperature of the water vapor is 100-300 ° C, the temperature of the liquid water is 20-100 ° C, the temperature of the oil is 20-300 ° C, the temperature of the filler water slurry. For 2o-iorc. Household oil; M oil is a commonly used oil for the production of oil-filled rubber in the rubber field. The oil optionally used in step 1) may be the same as or different from the oil used in step 2). The filler used in step 1) may be the same as or different from the filler used in step 2).

Drying in step 3) means transferring the mixture obtained in step 2) into a heated conveyor belt dryer, Drying under vacuum or an inert gas (such as nitrogen), the solvent and the unreacted monomer in the rubber synthesis enter the condenser and the t-retaining column for recovery; or spray-dry the mixture obtained in step 2) Or flash,

195 The heating medium used is an inert gas (such as nitrogen) or water vapor, and the solvent and the unreacted monomer in the rubber synthesis enter the condenser and the column for recovery.

When water vapor is used as the heating medium, the dried solid mixture may contain water, and then dried by vacuum drying, heat drying or extrusion heating to obtain a rubber/filler masterbatch. The vacuum drying includes vacuum drying at room temperature, freeze vacuum drying, and heating under vacuum. Household; 3⁄4 heating and drying can be a general drying method, such as drying

200 or air dried. The extrusion heating and drying is performed by first removing and removing the heating medium and then further drying, wherein the drying in one step is air drying, drying or mechanical drying, and the mechanical drying is using an open mill, a kneader, an internal mixer, and a continuous density. Drying is carried out in a mixer, a single screw extruder, and a twin screw extruder.

The method of recovering the solvent can be recovered by any method known in the art, such as by vaporizing the solvent by surface condensation or direct contact condensation. When using the method of direct condensation contact, the coolant can be used.

205 Water.

The technical features of the present invention are as follows:

i. The technical feature of the invention is that the process adaptability is strong: the rubber/filler/additive masterbatch can be prepared by using the rubber solution with the simple process, the filler dispersibility and the slightly poor product performance, the filler and the additive, and the direct heating method. It can be used to make the cost of the fc3⁄4, mixed agglomerator and mechanical drying method.

210 Good rubber / filler / additive masterbatch; masterbatch prepared by different processes can be reasonably adapted to the needs of different rubber products.

技术. The technical feature of the present invention is the use of a specially designed agglomerator, which is a 3⁄4 consisting of one or more inlets and an outlet. When the finely dispersed rubber/filler/addition solvent mixture is injected into the agglomerator at high speed and high turbulent flow, the internal pressure of the mixture is very high according to the principles of fluid mechanics and turbulent fluid mechanics due to the high speed.

215 The force has dropped sharply. The mixture flow will form fine droplets under high shear, and the low boiling solvent in the liquid mixture at low pressure may reach its boiling point, the solvent accelerates volatilization, and the solvent is separated from the mixture. This separation process can also be carried out by ejecting a droplet containing a large amount of solvent vapor through a narrow outlet from the agglomerator, and the pressure is greatly lowered due to an increase in the flow rate, so that the vaporization rate and degree of the solvent are greatly enhanced. When this mixed fluid is sprayed into a dry gas with a high temperature gas such as nitrogen, the temperature rise causes the solvent to rapidly diffuse from the mixture to the heat.

220 The atmosphere is greatly improved in drying efficiency.

Iii. The above-described method of agglomerating and desolventizing the present invention is such that one or both of the plurality of inlets of the agglomerator are injected with a t-gel/filler/additive/solvent mixture, and nitrogen is introduced from the other one or more inlets. When both the incoming mixture and the gas are in a high energy, high velocity turbulent state, the mixing of the two can be completed in a few milliseconds to tens of milliseconds and the mixture becomes a droplet during this time. The solvent in the droplet rapidly expands and vaporizes under the low pressure of turbulent flow, and makes the mixture 225 The rubber/filler/additive component is rapidly agglomerated to form a dispersed solid/slave three-phase mixture. During this process, when the nitrogen gas injected into the agglomerator is higher, the expansion rate of the solvent, the gasification and the solidification rate of the solid are greatly increased, and the liquid phase composition is greatly lowered. In extreme cases, it becomes only solid agglomerates and solid and gas phases formed by nitrogen and solvent vapors. When the three-phase or two-phase mixture ship agglomerator has a narrow outlet, the fluid pressure is further lowered due to an increase in the flow rate, so that the degree and speed of vaporization of the solvent are greatly increased, and the liquid phase is rapidly decreased. When the mixed fluid is sprayed with high temperature gas

After the drying apparatus of the body such as a nitrogen atmosphere, the solvent remaining in the rubber/filler/additive condensate is further expanded in the light hot gas phase due to the increase in temperature, so that the drying efficiency is greatly improved.

Iv. One way of the above-described coagulation and desolvation of the present invention is that if oil is included in the additive, one or both of the plurality of inlets of the agglomerator are injected with rubber/filler/additive at high pressure and high speed (without or Contains only the oil/solvent mixture required in the portion of the compound, and the oil is injected from one or more other inlets. The amount of oil is the masterbatch

235 The amount of formula required is the difference between the amount of oil used in the t-gel/filler/additional solvent mixture. The mixture and oil are mixed and agglomerated in the presence of high energy turbulence, and the low pressure of the high velocity turbulent fluid will rapidly vaporize the solvent to separate from the rubber/filler suspension compound. If the temperature of the oil is increased, the gasification process of the solvent will be accelerated due to the large heat capacity of the oil. When the formed solid, liquid, and gas mist mixture is sprayed into the dry gas containing high temperature gas through a small outlet at a high speed, the vaporous solid-liquid phase dispersion state further increases the contact with the gas phase due to the decrease of the fluid pressure at the time of discharge. Area, from

The vaporization rate of the solvent is accelerated by 240, and the high temperature atmosphere also greatly improves the efficiency of solvent removal.

V. The above method of the present invention for suspected polymerization and solvent removal is by injecting a rubber/filler/addition solvent mixture at a high pressure and high speed through one or two inlets of a plurality of inlets of the suspected polymer, and by one or more The inlet is filled with high pressure water vapor. Under the action of water desolvation and high temperature, the rubber/filler/additive is agglomerated in a solvent in a few milliseconds to several tens of milliseconds, and is aerosolized at a low pressure, and the solvent is largely volatilized. Due to the latent heat of steam liquefaction, dissolve

The 245 agent is vaporized much faster than hot nitrogen. However, the formation of a smoke-like solid, liquid, and gas three-phase mixture also increases moisture.

When the mixture is sprayed into the high-temperature gas at a high speed through a narrow outlet of the agglomerator under high pressure, the water and the solvent are vaporized to separate from the solid phase rubber/filler/additive complex and enter the gas phase due to the pressure drop and the further increase in temperature. The drying efficiency of the composite is improved.

Vi. One way of the above coagulation and desolvation of the present invention is to make the leaking shed blister 'J mixture at high pressure

At high speed, one or two of the multiple inlets of the agglomerator are injected into the mixing/aggregator, and water, especially high temperature water, is simultaneously injected into the agglomerator from its mouth at high pressure and high speed. In the state of high energy turbulence, combined with the desolvation effect of water on the rubber solution, the rubber/filler/additive completes agglomeration in a period of several milliseconds to tens of milliseconds. Due to the low pressure characteristics of high energy turbulent liquids, especially when high temperature water is used, the solvent rapidly evaporates to its boiling point and the water is partially vaporized. When the solid, liquid, and gas three-phase mixture in the agglomerator is discharged under high pressure, the narrow outlet of the ship is sprayed to

255 After drying with high temperature air or nitrogen, the low pressure flow formed by high speed is dispersed in high temperature hot air or hot nitrogen in a mist. The large specific surface area and low pressure of the rubber/filler/additive solid/liquid phase condensed in the smoke will make The water and solvent are volatilized in one step, which increases the moisture and solvent drying effect of the solid composite. If too much water is injected into the agglomerator, the rubber/filler/additive coagulated complex may be mixed in water. At this time, a general separation method such as filtration, centrifugation or the like separates the moisture-containing composite from water and then performs drying.

260 Vii. One way of the above-mentioned agglomeration and desolvation of the present invention is to inject a mixture of the leaking sheds into the agglomerator through one or more of the plurality of inlets of the agglomerator at high pressure and high speed. The filler water slurry, preferably a high temperature filler water slurry, is simultaneously injected into the agglomerator from other inlets under high pressure and high speed conditions. In the state of high energy turbulent flow, combined with the desolvation effect of water on the t-glue solution, the t-gel/filler/addition-disposing i solvent is uniformly mixed with the filler water slurry, and the aggregation of the rubber/filler/additive is completed in several milliseconds to several tens of milliseconds. . Due to the low pressure characteristics of high energy turbulence, especially

265 is a high-temperature filler water slurry, the solvent quickly reaches its boiling point and volatilizes, and the water is partially vaporized. When the solid, liquid, and gas three-phase mixture in the mixing/aggregator enters the collection stage through its narrow outlet under high pressure, the low-pressure flow formed by the high-speed is dispersed in the high-temperature air or nitrogen in a mist. On the one hand, the pressure is very low, and on the other hand, since the contact surfaces of the solid, liquid phase and gas are greatly increased, the solvent and the water therein are diffused into the gas phase. If the water in the slurry of the filler injected into the condenser is too much, the water after the spray is not completely volatilized, and the rubber/filler/additive is agglomerated.

The complex of 270 may be mixed in water, at which time the separation of the aqueous component is separated from the water by a general separation method such as filtration, centrifugation, and the like, followed by drying.

Vii i. The technical feature of the present invention is that when a high-temperature inert gas is introduced into the agglomerator, the solid mother-side separator which is agglomerated and desolvated in the agglomerator can be separated from the solvent gas to obtain a master batch. Separators include, but are not limited to, cyclone separators. This technique allows the needle-bonded rubber to be in contact with water.

275 IX. The technical feature of the present invention is that when any of the rubber/filler/additive aggregated water contains water, it can be dehydrated by filtration and extrusion, and dried at a high temperature. The drying machine used is an open mill, a kneader, an internal mixer, a continuous internal mixer, a single screw extruder, and a twin screw extruder. This method further improves the dispersion of fillers and additives.

Forced

The invention is further described by the following examples, but the scope of the invention is not limited by the examples.

(1) The experimental data in the examples were determined by the following instruments and equipment:

Table 1 Equipment for the preparation of rubber samples

sequence

Test item Test standard Equipment name Specification model Manufacturer No.

In the rubber compound

1 - Carbon black disperser GT-505-CBD High-speed rail testing equipment company

2 Hardness GB T 531.1-2008 Hardness Tester (Shao A) LX-A Shanghai Liuling Instrument Factory

Waiting for the moon

3 Stretch bow ship (MPa) GB T 528-2009 A1-3000 High-speed rail testing equipment company

Waiting for the moon

4 elongation at break (%) GB T 528-2009 A1-3000 High-speed rail testing equipment company

5 Resilience (%) GB T 1681-2009 Resilience Tester GT-7042-RE High-speed Rail Testing Equipment Company

6 Fatigue heat generation GB T 1687-1993 Compressed heat generation Several RH-2000N High-speed rail testing equipment company

7 Wear A few GB T1689-1998 DIN wear 佥 GT7012-A High-speed rail testing equipment company

(2) Example ratio of pigment

Raw materials:

Synthetic polyisoprene rubber, IR-70, Qingdao Ikesi New Materials Co., Ltd.;

White carbon black, NEWSIL1165-MP, Wuxi Chengcheng Silicon Industry Co., Ltd.;

Mm, Dalian Zinc Oxide Plant;

Stearic acid, PF1808, Malaysia Licheng Co., Ltd.;

Antioxidant 020, Jiangsu Shengao Chemical Co., Ltd.;

Silane coupling agent Si69, Nanjing Shuguang Chemical Group Co., Ltd.;

Accelerator CZ, Shandong Shanghao Chemical Co., Ltd.;

Promoter DPG, Shandong Danxian Chemical Co., Ltd.;

Sulphur Yellow gold 盛 :: ::::: Ltd.

Comparative example 1

In the internal mixer, 56 parts of white carbon black and 5.6 parts of silane coupling agent Si69 were added to 100 parts of synthetic cis-polyisoprene for kneading. When the filler was mixed into the rubber, 3.5 parts of zinc oxide was added. 2 parts of stearic acid, 2 parts of anti-aging agent 4020, and then kneaded for 4 minutes, discharged from the internal mixer, and then pre-mixed on the open mill through the roll. After 8 hours of parking, 2 parts of CZ, 1 part of DPG and 1.8 parts of sulfur were added to the premixed rubber to prepare a compound. After being placed in the open mill for 8 hours, it was vulcanized to a positive vulcanization in a 15 CTC flat vulcanizer to obtain a dry vulcanizate 1.

Example 1

Add 56 parts of silica, 5.6 parts of silane coupling agent Si69, 3.5 parts of zinc oxide to 100 parts of 12% cis-polyisoprene in n-hexane solution, rubber / white carbon / After the Si69/n-hexane mixture is initially mixed with a vane mixer, Spraying the mixture through a nozzle into a multi-bend tube causes the mixture to collide with the tube wall in the tube to increase dispersion of the filler. Afterwards, the mixture is continuously added to the mill for fine dispersion, that is, the mixture is refined, and then the mixture is connected to the agglomerator through two inlets of a four-inlet cone-type agglomerator under a pressure of 30 MPa. At the same time, nitrogen gas was continuously injected from another 310 inlets at a temperature of about 180 ° C, and then the resulting mixture was continuously sprayed into a desiccator filled with nitrogen at about 150 ° C. The solvent was from rubber/silica in 10 seconds. The /Si69/n-hexane expanded droplets are volatilized to form desolvated colloidal particles, and the nitrogen-containing and solvent mixture containing the powder leakage is separated from the colloidal particles by a cyclone to obtain a powder masterbatch 1.

Example 2

315 56 parts of white carbon black, 5.6 parts of silane coupling agent Si69, 3.5 parts of zinc oxide were added to 100 parts of 12% cis-polyisoprene in n-hexane solution, rubber / white carbon black After the /Si69/n-hexane mixture is initially mixed with a vane mixer, the mixture is sprayed through a nozzle into a multi-bend tube to cause the mixture to collide with the tube wall in the tube to increase the dispersion of the filler. The mixture is then continuously added to the mill for fine dispersion, i.e., the finely dispersed mixture is obtained, and then the mixture is continuously injected into the agglomerator through two inlets in a cone-type agglomerator having four inlets under a pressure of 30 MPa.

320 The mixture was continuously injected with water at a temperature of about 95 ° C from the other two inlets to coagulate the mixture. The colloidal particles obtained by the polymerization and desolvation were filtered and dried in a vacuum dryer at a vacuum of -0.08 MPa for 20 min to obtain a masterbatch 2.

Example 3

Add 56 parts of silica, 5.6 parts of silane coupling agent Si69, 3.5 parts of zinc oxide to 100 parts of 12% cis-polyisoprene in n-hexane solution, rubber / white carbon / After the Si69/n-hexane mixture is initially mixed with a vane mixer,

325 Spraying the mixture into a multi-bend tube causes the mixture to collide with the tube wall in the tube to increase the dispersion of the filler.

After that, the mixture is continuously added to the mill for fine dispersion, that is, the mixture is refined, and then the mixture is passed through the two inlets of the four-inlet cone-type agglomerator at a pressure of 30 MPa into the agglomerator. At the same time, the water was condensed at a temperature of about 95 ° C from the other two inlets. The coagulated and desolvated colloidal particles were filtered and dried in a single screw extruder for 3 minutes to obtain a masterbatch 3.

330. The masterbatch 1-3 obtained above is added to 2 parts of stearic acid and 2 parts of anti-aging agent 4020 in an internal mixer, and then kneaded for 4 minutes, and discharged from the internal mixer. , the next piece. After 8 hours of mixing and parking, add 2 parts of CZ, 1 part of accelerator D and 1. 8 parts of sulfur and then mix it in the mixer. 1. Remove the material from the mixer. After being placed in the opener for 8 hours, it was vulcanized to a positive vulcanization in a 150 ° C flat vulcanizing machine to separately cure the vulcanizate 3 .

335 Table ³ physical properties of vulcanizate

It can be seen from Table 3 that under the same formulation, the properties of the rubber prepared by the wet mixing method are different. Compared with the dry masterbatch, the filler in the wet masterbatch is rubber. The degree of dispersion in the rubber is greatly improved, and the tensile strength, resilience and wear resistance of the vulcanized rubber are remarkably improved, and the compression fatigue heat generation is lowered.

Claims

1. A continuous manufacturing method of rubber masterbatch, including the following steps:

Step 1): Add the filler to the rubber solution and stir to form a smooth mixture;

The rubber/filler/solvent mixture in step 1) is condensed to obtain a mixture of rubber/filler composite and solvent;

Step 3): Remove the solvent and dry the mixture to obtain tJt/filler masterbatch; wherein, the drying in step 3) means transferring the mixture obtained in step 2) to a heated conveyor belt for drying In the machine, it is heated and dried under vacuum or inert gas, and the volatilized solvent and unreacted monomers in the rubber synthesis enter the condenser and fractionation tower for recovery; or the drying in step 3) refers to the step 2) The mixture obtained is spray dried or flash evaporated, and the heating medium used is inert gas or water vapor. The volatilized solvent and unreacted monomers in the rubber synthesis enter the condenser and fractionation tower for recovery.

2. The method according to claim 1, wherein the coagulation in step 2) can be one, more or a combination of flocculant flocculation method, heating method, desolvation method.

3. The method according to claim 1, wherein the solvent removed in step 3) is optionally recovered and recycled.

4. The method according to claim 1, wherein in step 1) and/or step 2), one or more agents selected from the group consisting of oil, antioxidant, coupling agent, active agent, antioxidant, flame retardant are optionally added Agents, heat stabilizers, light stabilizers, dyes

, pigments, vulcanizing agents and adhesive additives.

5. The method according to any one of claims 1 to 4, wherein water vapor is used as the heating medium, the dried solid mixture will contain water, and the rubber/filler is obtained after vacuum drying, heating drying or extrusion heating drying. Masterbatch.

6. The method according to any one of claims 1 to 4, wherein the inert gas is a gas.

7. According to the method of claim 5, the heating and drying is oven drying or air drying.

8. The method according to claim 5, wherein the extrusion and heating drying involves first extruding to remove water and then further drying.

9. The method of claim 8, wherein the step of drying is air drying, oven drying or mechanical drying.

10. The method according to claim 9, wherein the mechanical drying uses an open mill, a kneader, an internal mixer, a continuous internal mixer, a single-screw extruder, or a twin-screw extruder for drying.

11. A rubber masterbatch prepared according to the method of claims 1-10.

12. A rubber product prepared using the rubber masterbatch according to claim 11.