WO2017041753A1

WO2017041753A1 - Continuous manufacturing method of rubber masterbatch, and rubber masterbatch manufactured by same

Info

Publication number: WO2017041753A1
Application number: PCT/CN2016/098635
Authority: WO
Inventors: 王梦蛟; 宋建军; 王正; 和富金; 贾维杰; 张红霞; 张秀彬
Original assignee: 怡维怡橡胶研究院有限公司
Priority date: 2015-09-11
Filing date: 2016-09-10
Publication date: 2017-03-16
Also published as: ZA201802326B; CN105131307A

Abstract

A continuous manufacturing method of a rubber masterbatch and rubber masterbatch manufactured by the same. The manufacturing method comprises the following steps: step A, adding a filler to a rubber solution, and forming a rubber/filler/solvent mixture via stirring; and step B, performing solvent separation and coagulation on the mixture obtained from step A, so as to obtain a rubber/filler masterbatch, wherein the solvent separation step is specifically separating the solvent from the mixture via evaporation, low-pressure vacuum drying, heating, spray drying, expansion drying, or flash evaporation.

Description

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

Technical field

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

Background technique

The common dry mixing method has a large difference between each batch of rubber compound, which has a great influence on the quality of the subsequent process. The rubber is repeatedly kneaded, the molecular weight of the rubber is decreased, and the dispersion of the filler in the rubber is uneven. The performance of the material is degraded, and a large amount of dust is also generated to cause environmental pollution. It is imperative to develop a more efficient and more uniform wet mixing method than the existing dry mixing process. The important step of the method is rubber/filler/additive. Coagulation and separation steps with solvent.

CN103113597A discloses a wet mixing method for efficient continuous coagulation using a specially designed agglomerator comprising nitrogen, water vapor, water, filler water slurry and oil, but the agglomerator has high requirements on equipment materials and high process cost. . CN103419291A discloses a method of using water as a heating medium, but the subsequent separation and removal of water by a separator causes breakage of the rubber particles and loss of the mother rubber. US 7,307,121 B2 discloses a steam stripping process for solvent removal by pumping a silica/rubber mixture into a stripping unit to coagulate and remove the solvent, but which requires dehydration drying. As can be seen from the published patent text, both of the wet mixing methods require agglomerating media, and some require a step of increasing the separation of the agglomerating media.

Summary of the invention

In order to solve the problem of coagulation medium in the prior art and the need to increase the separation step of the medium, it is a primary object of the present invention to provide a continuous manufacturing method of a rubber master batch. Another object of the present invention is to provide a rubber masterbatch prepared by the above method. It is still another object of the present invention to provide a rubber article prepared by using the above rubber master batch.

The manufacturing method of the present invention eliminates the coagulation of the medium by the rubber/filler/additive mixture, thereby eliminating the cost of the agglomerating medium. The manufacturing method of the invention simplifies the process, saves energy, improves the dispersion property of the filler and the vulcanization property of the rubber, and enhances the filler-polymer interaction, thereby improving the performance of the rubber product.

The invention discloses the following continuous manufacturing methods of rubber master batches, including:

A continuous manufacturing method of rubber masterbatch includes the following steps:

Step A): adding a filler to the rubber solution to form a rubber/filler/solvent mixture by stirring;

Step B): performing solvent separation and coagulation on the mixture obtained in the step A), the solvent separation step is specifically separating the mixture by evaporation, or separating the solvent by low-pressure vacuum drying, or separating the solvent by heating, or by spraying Dry way The solvent is separated from the solvent, either by expansion drying, or the solvent is separated by flashing to obtain a rubber/filler masterbatch.

Step B): performing solvent separation and coagulation on the mixture obtained in the step A), the solvent separation step is specifically separating the mixture by evaporation, or separating the solvent by low-pressure vacuum drying, or separating the solvent by heating, or by spraying The solvent is separated in a dry manner, or the solvent is separated by expansion drying, or the solvent is separated by flash evaporation;

Step C): drying the mixture obtained in the previous step to obtain a rubber/filler masterbatch; the drying is heat drying and/or mechanical drying.

Wherein the heating and drying in step C) is drying or air drying; the mechanical drying is drying using an open mill, a kneader, an internal mixer, a continuous internal mixer, a single screw extruder or a twin screw extruder. The working temperature of the mechanical drying is 10 ° C to 250 ° C; the step C) may be performed by heating and drying before mechanical drying, or may be mechanically dried and then dried by heating. Step C) selecting mechanical drying can be simultaneously heated and dried at a temperature of 10 ° C - 250 ° C; when heating and drying is selected, heating can be carried out in a gaseous medium comprising at least air, nitrogen, water vapor and CO ₂ One.

The rubber/filler/solvent mixture in step A) immediately enters step B), or is parked for a certain period of time before proceeding to step B), with or without heating during parking; when heated, the temperature is between 10 ° C and 200 ° C. Wherein step A) further comprises adding an additive to the rubber solution to form a rubber/filler/additive/solvent mixture by stirring. Step A) may directly add the filler and/or the additive to the rubber solution, or may first add the filler and/or the additive to the same or different solvent as the rubber solution to form the filler and/or the additive/solvent mixture. The filler and/or the additive/solvent mixture may be directly mixed with the rubber solution, or may be mixed with the rubber solution after being parked for a certain period of time, heated or not heated during parking, and when heated, the temperature is 10 ° C to 200 ° C, when the above heating When the temperature is higher than the boiling point of the solvent, the heating is carried out in a pressure vessel. The rubber/filler and/or additive/solvent mixture obtained in step A) can be immediately moved to the next step, or it can be parked for a certain period of time, heated or not heated during parking, and when heated, the temperature is 10 ° C to 200 ° C, When the above heating temperature is higher than the boiling point of the solvent, the heating is carried out in a pressure vessel. The additive may be selected from the group consisting of oils, antioxidants, coupling agents, active agents, antioxidants, heat stabilizers, light stabilizers, flame retardants, dyes, pigments, plasticizers, softeners, processing aids. One or more of additives to vulcanizing agents and accelerators. The amount of the additive used is a conventional amount or adjusted according to actual conditions.

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

The step A) may further comprise a fine dispersion step, which may be carried out by spraying the mixture obtained by the above agitation through a nozzle under high pressure and high shear to improve the filler and/or the additive. Dispersing; causing the above-mentioned ejected material to pass through a multi-bend tube to cause the mixed liquid to collide with the tube wall in the tube to increase the dispersibility of the filler and/or the additive; or to cause the ejected material to pass through the inner diameter of the tube for multiple times. To shift the shear stress to increase the dispersion of the filler and/or additive. The pressure used ranges from 0.1 MPa to 100 MPa. It is preferably 10 MPa to 80 MPa.

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

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

Ii. continuously adding the finely dispersed mixture to a mill for grinding to sufficiently disperse the filler and/or the additive in the rubber solution, the mill 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 100 MPa, preferably from 10 MPa to 80 MPa.

Iv. continuously adding the finely dispersed mixture to a multi-layer high-pressure slit disperser, and extruding the mixture from the slit between the two layers under high pressure, 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 100 MPa, preferably from 10 MPa to 80 MPa.

v. Dispersing the finely dispersed mixture continuously into a power disperser having a plurality of radially distributed slits or holes on the high speed rotating rotor, the mixture impinging on the stator surface at high speed The filler and/or the additive are uniformly dispersed in the rubber solution.

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 the solution rubber production line, and any type of dry glue can be prepared by dissolving in the 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 gum, gutta percha, silver inulin, etc.; the synthetic polymer includes, but is not limited to, a monomer obtained by polymerizing in a solution (ie, a solution rubber), and a monomer obtained by polymerization in an emulsion. (ie, latex rubber), the monomer body is obtained by polymerization. When the rubber solution is obtained directly from the preparation of a solution rubber production line, the solution rubber is diene or 6 using ethylene, propylene, butene, pentene, hexene, heptene, 4-7 carbon atoms. a homopolymer or copolymerized polymer of a triene of -7 carbon atoms or an ethylenic monomer having other atoms or functional groups, such as a silicon atom, a fluorine atom, a chlorine atom, a nitrogen atom, an oxygen atom, Sulfur atoms, ester groups, amino ester groups, cyano groups, also include 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, fluorine rubber, 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 and naphthene. a cycloalkane or n-alkane, the aromatic hydrocarbon solvent including but not limited to benzene, toluene, xylene, styrene, including but not limited to dichloromethane, chloroform, carbon tetrachloride, Ethyl chloride, 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 40% 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, calcium carbonate, 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 500m ² / g, more preferably 5 to 300m ² / g. For carbon black, silica (silica), the oil absorption value is 20 to 250 ml / 100 g, preferably 25 to 200 ml / 100 g, more preferably 30 to 150 ml / 100 g, wherein the filler comprises a mixture thereof and Multiphase fillers, including but not limited to carbon black, silica, alumina, magnesia, zinc oxide, calcium oxide, titanium oxide, boron oxide, etc., for biphasic or heterogeneous In the case of multiphase fillers, 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 described therein may be that a certain functional group is attached to the surface of the filler by a chemical reaction or the modifier is physically bonded to the surface of the filler by mixing or adsorption. In terms of the modification, the modification may be, but is not limited to, dissolving the modifier in a solvent and mixing with the filler for liquid phase modification, such as Wang W, Nanse G, Vidal A, et al. KGK [J], 1994, 47: 493. As described therein, it is also possible, but not limited to, to mix and modify the modifier with the filler 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 an organosilane coupling agent represented by the following formula:

(R _n -(RO) _3-n Si-(Alk) _m -(Ar) _p ) _q (A) (I)

R _n '(RO) _3-n Si-(Alk) (II)

Or R _n '(RO) _3-n Si-(Alk _eny l) (III)

Where, when q = 1, A is -SCN, -SH, -Cl, -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 6 carbon atoms;

Alk _eny l is a linear or branched alkenyl group having 1 to 6 carbon atoms;

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 ones are bis(triethoxypropylsilane) tetrasulfide and disulfide, 3-thiocyanopropyl-triethoxysilane, γ-mercaptopropyl-trimethoxysilane, zirconate An ester coupling agent, a titanate coupling agent, a nitro coupling agent, an alcohol compound, and the alcohol compound includes, but not limited to, a unit alcohol, a glycol, a polyol, and the alcohol compound includes but is not limited to Propanol, butanol, ethylene glycol, polyethylene glycol and derivatives thereof.

Wherein the evaporation in the step B) is carried out by using an oven or a drying plate; the atomization method of the spray drying is centrifugal atomization, pressure atomization or two-fluid atomization; the expansion and drying method is first heating and then suddenly The pressure is released; the flashing method is at least one of atmospheric flash distillation and vacuum flash evaporation, and the number of flashing stages is 1-3. The low pressure vacuum drying described in step B) is to volatize the solvent or suction filtration under vacuum to a pressure below one atmosphere, preferably at -0.1 MPa-0, more preferably -0.09 MPa-0, most preferably -0.08 MPa-0. The expansion and drying described in the step B) is to flash-vaporize the solvent by a screw expansion dryer, preferably in a screw expansion dryer at 0-20 MPa, more preferably 1-10 MPa, with a decreasing pitch, friction heat generation, and outlet. The pressure drops suddenly, the strip expands and relaxes, and the solvent in the strip flashes and vaporizes.

Wherein step B1) is further carried out before step B): the mixture obtained in the previous step is sent to the agglomerator and optionally in the agglomerator with one of nitrogen, water vapor, water, filler water slurry and oil or The plurality of fluids are contacted and mixed to form a mixture of the rubber/filler and or additive complex and solvent. Step B2) is further carried out before step B): the mixture obtained in the previous step is directly passed into a heating medium having a temperature higher than the boiling point of the solvent, the polarity of the heating medium is different from the polarity of the solvent used, and the mixture is agglomerated and desolvated. And the solvent evaporates rapidly to form a mixture of the rubber/filler and or additive complex and solvent containing the heating medium. The manufacturing method simultaneously includes the step B1), the step B2) and the step B), in particular, step B1) and step B2) are further sequentially performed before the step B), and the specific steps are: step B1): step A) is obtained The mixture is fed to the agglomerator and optionally contacted with one or more of the nitrogen, steam, water, filler slurry and oil in the agglomerator and agglomerated to obtain a rubber/filler and or additive a mixture of the complex and the solvent; Step B2): directly passing the mixture obtained in the step B1) to a heating medium having a temperature higher than the boiling point of the solvent, the polarity of the heating medium being different from the polarity of the solvent used, the mixture agglomerating and desolvating the solvent And the solvent evaporates rapidly to form a mixture of the rubber/filler and or additive complex and solvent containing the heating medium.

The agglomerator used in step B1) 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, and the outlet is 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 at an angle of 20-120°, more preferably at an angle of 70-100°, and most preferably at an angle of 85-95°. 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 other feed ports is opposite to the axial direction of the tube of the tube agglomerator 1-180° angle, preferably at an angle of 20-120°, more preferably at an angle of 70-100°, most preferably at an angle of 85-95°, the feed direction of each feed port being perpendicular to the axis of the tube axis The projection is in any direction between the radial direction of the cross section and the tangential direction of the cross section, It is preferably in the radial direction or in the tangential direction. The feed ports are all in the same plane perpendicular to the axial direction of the tube or the feed ports are on different planes.

The agglomerator used in step B1) may also be an agglomerator consisting of two or more mutually concentric tubes, wherein each tube has one or more feed ports, the feed of which is fed The direction is parallel to the axial direction of the tube or the tangential direction of the tube, and 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 the ends of the feed ports of each tube may be lengthened from the inside to the outside or the ends of the feed ports of each tube from the inside to the outside may be shortened.

The agglomerator used in step B1) may also be a cylindrical 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 it can be injected into the agglomerator in a tangential direction along the wall of the barrel.

The agglomerator used in the step B1) may also have a cylindrical shape with an upper portion and a conical tubular structure with a lower portion and one or more feed ports. The feed direction of the feed port may be the tangential direction of the tube wall; each feed port may be in the same plane or in different planes. 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 an angle of 20-110°, more preferably an angle of 70-100°, most preferably 85-95. °°, the projection 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, steam, water, filler slurry and oil described in step B1) and the rubber/filler/solvent mixture obtained in step A) 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, and the temperature of the filler water slurry is 20-100. °C. The oil is a commonly used oil for the manufacture of oil-filled rubber in the rubber field. The oil optionally used in step A) may be the same as or different from the oil used in step B1). The filler used in step A) may be the same as or different from the filler used in step B1).

In step B2), the mixture obtained in the previous step is passed directly into a heating medium having a temperature higher than the boiling point of the solvent. When the nature of the heating medium is different from the nature of the solvent used, especially the polarity, the mixture agglomerates and desorbs the solvent, and when the temperature of the heating medium is higher than the boiling point of the solvent, the solvent rapidly volatilizes to form a master batch containing a heating medium. The masterbatch is heated to remove the heating medium to form a masterbatch product. In the process, the solvent and the unreacted monomer in the rubber synthesis are recovered into the condenser and the fractionation column for recovery, and the obtained agglomerated mixture is obtained. The filter is separated from the heating medium and dried to form a masterbatch product. Such heating media include, but are not limited to, water. When water is used as the heating medium, the solvent is a solvent having a boiling point of less than 100 °C. The solvent and the unreacted monomer in the rubber synthesis and the water vapor are then introduced into the condenser and the fractionation column for recovery.

The agglomeration of step B2) can be carried out using any container; preferably, it is carried out without using any specially designed agglomerator; the agglomeration of step B2) can be carried out in a can container. Preferably, step B2) uses a can-shaped container of any shape, more preferably a cylindrical can-shaped container.

The solvent of step B) and step C) is recycled for recycling; the recovery is carried out by means of a condenser, a fractionation column and a spraying device. 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 the method of direct condensation contact is used, the coolant may be water or the same solvent. The invention also provides a rubber masterbatch prepared according to the above method. The present invention also provides a rubber article which is prepared using the rubber masterbatch described above.

The technical effect of the present invention is

i. Rubber/filler (or filler/additive)/solvent mixture agglomeration and solvent removal: rubber/filler (or filler/additive)/solvent mixture can be agglomerated without the need for media, reducing process costs.

Ii. Condensate In the heat medium, the separation from the solvent can be achieved without the need of a separator, and the physical properties of the masterbatch can be ensured to the greatest extent.

Iii. The solvent separation method disclosed in the present invention (the solvent is separated by evaporation, or the solvent is separated by low pressure vacuum drying, or the solvent is separated by heating, or the solvent is separated by spray drying, or the solvent is separated by expansion drying, Or the solvent can be separated by flashing), the complete separation of the solvent can be achieved, and the separation can be completed quickly, the oxidative aging phenomenon of the rubber molecules due to high temperature is avoided, and the reinforcing effect of the filler on the rubber is enhanced.

Iv. Strong process adaptability: It is possible to prepare rubber/filler/additive masterbatch by using rubber solution with simple process and poor product performance, filler and additive, and direct heating method. It can also use special designed dispersing device and mixed coagulation. Process and mechanical drying methods produce higher cost but better performance rubber/filler/additive masterbatch; masterbatch prepared by different processes can be reasonably adapted to the needs of different rubber products.

detailed description

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

序号Serial number	设备名称Device name	规格型号Specification model	生产厂家Manufacturer
11	密炼机Mixer	BR1600BR1600	美国法雷尔公司American Farrell Company
22	开炼机Open mill	Polymix 150LPolymix 150L	德国SERVITEC公司Germany SERVITEC
33	平板硫化机Flat vulcanizing machine	P-V-200-3RT-2-PCDP-V-200-3RT-2-PCD	磐石油压工业有限公司磐Petroleum Industry Co., Ltd.

Table 2 Test methods and instruments for physical properties of vulcanizates

(2) Examples and comparative examples

raw material:

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

White carbon black, Newsil HD165MP, confirmed into Silicon Chemical Co., Ltd.

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

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

Zinc oxide, Dalian zinc oxide plant;

Protective wax, Bairuimei Special Chemicals (Suzhou) Co., Ltd.;

Antioxidant RD, chemical plant of Sinopec Nanjing Chemical Industry Co., Ltd.;

Antioxidant 4020, Jiangsu Shengao Chemical Co., Ltd.;

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

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

Sulfur, Linyi Luozhuang Xin'an Chemical Plant.

Comparative example

Add 55 parts of silica, 5.5 parts of silane coupling agent Si69, 3.5 parts of zinc oxide to 100 parts of 12% cis-polyisoprene rubber in n-hexane solution, rubber / silica / Si69 / n-hexane After the 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. Thereafter, the mixture is continuously added to the mill for fine dispersion, that is, the mixture is refined, 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. Continuously injecting nitrogen gas at a temperature of about 180 ° C from the other two inlets, and then continuously spraying the resulting mixture In a desiccator filled with nitrogen gas at about 150 ° C, the solvent evaporates from the rubber/silica/Si69/n-hexane expanded droplets in 1-10 seconds to form a solvent-free colloidal particle containing powdery glue. The granular nitrogen and solvent mixture is separated from the colloidal particles by a cyclone to obtain a powder masterbatch 1.

Example 1

Add 55 parts of silica, 5.5 parts of silane coupling agent Si69, 3.5 parts of zinc oxide to 100 parts of 12% cis-polyisoprene rubber in n-hexane solution, rubber / silica / Si69 / n-hexane After the 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. Afterwards, the mixture is continuously added to the mill for fine dispersion, that is, the fine dispersion mixture is obtained, and then the rubber/filler/additive/solvent mixture is pushed along the shaft in a twin-screw dryer, heated and vacuumed, and the solvent is dried to obtain the masterbatch 2 .

Example 2

Add 55 parts of silica, 5.5 parts of silane coupling agent Si69, 3.5 parts of zinc oxide to 100 parts of 12% cis-polyisoprene rubber in n-hexane solution, rubber / silica / Si69 / n-hexane After the mixture is initially mixed with a paddle 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. After that, the mixture is continuously added to a homogenizer for fine dispersion, that is, the mixture is finely dispersed, and then the mixture is sprayed into a fineness at a normal pressure through a high-speed centrifugal atomizer at the top of a cone-shaped container having four inlets. The droplets are continuously sprayed from the other two inlets into a nitrogen gas having a temperature of about 180 ° C. The nitrogen gas is uniformly distributed in a spiral shape through the gas distributor, and the atomized droplets of the rubber/filler/additive/solvent mixture are uniformly distributed in a spiral shape. The nitrogen contact was atomized, the solvent was quickly evaporated, and the masterbatch 3 was dried in a vacuum oven.

Example 3

Add 55 parts of silica, 5.5 parts of silane coupling agent Si69, 3.5 parts of zinc oxide to 100 parts of 12% cis-polyisoprene rubber in n-hexane solution, rubber / silica / Si69 / n-hexane After the mixture is initially mixed with a ribbon 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. After that, the mixture is continuously added to the emulsification pump for fine dispersion, that is, the mixture is finely dispersed, and the obtained mixture is continuously sprayed directly from the outlet of the agglomerator into water of about 95 ° C, and then the mixture is flash-separated to separate the solvent, and dried in an oven. Masterbatch 4.

Example 4

Adding 55 parts of silica, 5.5 parts of silane coupling agent Si69, 3.5 parts of zinc oxide to 100 parts of 12% cis-polyisoprene in n-hexane solution, rubber/silica/Si69/n-hexane mixture After initial mixing 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 dispersion of the filler. Thereafter, the mixture is continuously added to a ball mill for fine dispersion, that is, the mixture is refined, and then the rubber/filler/solvent mixture is heated to remove the solvent to obtain a masterbatch 5.

The masterbatch 1 to 5 obtained above was added to the internal mixer by adding 2 parts of stearic acid, 1.0 part of protective wax, 1.5 parts of antioxidant RD and 2 parts of antioxidant 4020, and then kneading for 4 minutes to discharge from the internal mixer. The rubber material is passed over the roll on the open mill and the lower piece. After mixing for 8 hours, 2.3 parts of accelerator CZ, 1 part of accelerator DPG and 1.8 parts of sulfur were added to the internal mixer and then kneaded for 1.5 minutes to discharge from the internal mixer. Open mill After the film was left for 8 hours, it was vulcanized to a positive vulcanization in a 150 ° C plate vulcanizer to prepare wet vulcanizates 1 to 5, respectively.

Table 3 physical properties of wet vulcanizates

Table 3 shows the physical properties of the vulcanizates obtained in the examples of the wet masterbatch (wet gel 2-5) and the comparative example (wet gel 1) in the same formulation and different processes. It can be seen that, under the same formulation, the wet masterbatch of the present invention has higher dispersibility in the rubber than the wet masterbatch in the patent of CN103600434, and the hardness of the vulcanizate is higher. Low, tensile strength and elongation at break are slightly higher, elasticity is high, hysteresis loss is low, and wear resistance is good. The wet process glue 5 of the present invention has no drying step after solvent separation, and the method can greatly save energy consumption and reduce the process while maintaining the performance of the wet master batch in the patent of the publication No. CN103600434. Steps, the scope of application is broader.

Claims

A continuous manufacturing method of rubber masterbatch characterized by comprising the following steps:

Step A): adding a filler to the rubber solution to form a rubber/filler/solvent mixture by stirring;

Step B): performing solvent separation and coagulation on the mixture obtained in the step A), the solvent separation step is specifically separating the mixture by evaporation, or separating the solvent by low-pressure vacuum drying, or separating the solvent by heating, or by spraying The solvent is separated in a dry manner, or the solvent is separated by expansion drying, or the solvent is separated by flash evaporation to obtain a rubber/filler masterbatch.
A continuous manufacturing method of rubber masterbatch characterized by comprising the following steps:

Step A): adding a filler to the rubber solution to form a rubber/filler/solvent mixture by stirring;

Step B): performing solvent separation and coagulation on the mixture obtained in the step A), the solvent separation step is specifically separating the mixture by evaporation, or separating the solvent by low-pressure vacuum drying, or separating the solvent by heating, or by spraying The solvent is separated in a dry manner, or the solvent is separated by expansion drying, or the solvent is separated by flash evaporation;

Step C): drying the mixture obtained in the previous step to obtain a rubber/filler masterbatch; the drying is heat drying and/or mechanical drying.
The method according to claim 1 or 2, wherein the rubber/filler/solvent mixture in step A) immediately enters step B), or is parked for a certain period of time and then proceeds to step B), with or without heating during parking; When heated, the temperature is from 10 ° C to 200 ° C.
The method according to claim 2, wherein the step C) is heating and drying to dry or air dry; and the mechanical drying is using an open mill, a kneader, an internal mixer, a continuous internal mixer, and a single Drying by screw extruder or twin-screw extruder, the working temperature of mechanical drying is 10 ° C to 250 ° C; step C) drying is first performed by heating and drying, or mechanical drying is performed before heating. dry.
The method according to claim 2, wherein the step C) is drying while being mechanically dried, and the temperature is from 10 ° C to 250 ° C; and the drying is heating and drying, heating in a gaseous medium, the gaseous medium comprises at least one of the second air, nitrogen, water vapor and CO. the
The method according to claim 1 or 2, wherein the step A) further comprises adding an additive to the rubber solution to form a rubber/filler/additive/solvent mixture by stirring; the filler and the additive are directly added Into the rubber solution, or first add the filler and the additive to the same or different solvent as the rubber solution, and then directly added to the rubber solution or after being parked for a certain period of time, added to the rubber solution, heated or not heated during parking; When heated, the temperature is from 10 ° C to 200 ° C.
The method according to claim 6, wherein said additive is one or more selected from the group consisting of oils, antioxidants, coupling agents, active agents, antioxidants, flame retardants, heat stabilizers, and light stabilizers. Additives for dyes, dyes, pigments, plasticizers, softeners, processing aids, vulcanizing agents and accelerators.
The method according to claim 6 wherein said rubber/filler/additive/solvent mixture immediately enters step B), or is parked for a certain period of time and then proceeds to step B), with or without heating during parking; when heated The temperature is from 10 ° C to 200 ° C.
The method according to claim 1 or 2, wherein the evaporating in step B) is performed by using an oven or a drying plate; the atomizing method of the spray drying is centrifugal atomization, pressure atomization or two-fluid fog. The method of expanding and drying is to first perform heating and then suddenly release the pressure; the flashing method is at least one of normal pressure flashing and vacuum flashing, and the number of flashing stages is 1-3.
Process according to claim 1 or 2, characterized in that the low-pressure vacuum drying described in step B) is to volatilize the solvent or suction filtration under vacuum to a pressure below one atmosphere.
The method according to claim 1 or 2, wherein the expansion drying in the step B) is to flash-vaporize the solvent by means of a screw expansion dryer.
The method according to claim 1 or 2, wherein the step B1) is further carried out before the step B): the mixture obtained in the step A) is fed into the agglomerator, and optionally in the agglomerator with nitrogen and water. One or more of the vapor, water, filler slurry and oil are contacted and mixed and agglomerated to obtain a mixture of the rubber/filler composite and the solvent.
The method according to claim 1 or 2, wherein step B2) is further carried out before step B): the mixture obtained in step A) is directly passed into a heating medium having a temperature higher than the boiling point of the solvent, the heating medium The polarity is different from the polarity of the solvent used, the mixture agglomerates and the solvent is removed, and the solvent evaporates rapidly to form a mixture of the rubber/filler composite containing the heating medium and the solvent.
The method according to claim 1 or 2, wherein step B1) and step B2) are further carried out in sequence before step B), the specific steps are:

Step B1): feeding the mixture obtained in the step A) into the agglomerator and optionally contacting and mixing with one or more of the nitrogen, water vapor, water, the filler water slurry and the oil in the agglomerator Coagulating to obtain a mixture of a rubber/filler composite and a solvent;

Step B2): directly passing the mixture obtained in the step B1) into a heating medium having a temperature higher than the boiling point of the solvent, the polarity of the heating medium being different from the polarity of the solvent used, the mixture agglomerating and desolvating the solvent, and the solvent is rapidly volatilized, thereby A mixture of a rubber/filler composite containing the heating medium and a solvent is formed.
The process according to claim 1 wherein the solvent of step B) is recycled for recycling; said recovery is carried out by means of a condenser, a fractionation column and a spray apparatus.
The process according to claim 2, wherein the solvent of step B) and step C) is recycled for recycling; said recovery is carried out by means of a condenser, a fractionation column and a spraying device.
A rubber masterbatch prepared by the method of any of claims 1-16.
A rubber article characterized in that it is prepared using the rubber masterbatch according to claim 17.