CN104629110A - Masterbatch and preparation method thereof, vulcanized rubber and application thereof - Google Patents
Masterbatch and preparation method thereof, vulcanized rubber and application thereof Download PDFInfo
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- CN104629110A CN104629110A CN201310560510.XA CN201310560510A CN104629110A CN 104629110 A CN104629110 A CN 104629110A CN 201310560510 A CN201310560510 A CN 201310560510A CN 104629110 A CN104629110 A CN 104629110A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
- B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
- B29B7/12—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with single shaft
- B29B7/16—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with single shaft with paddles or arms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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Abstract
The invention discloses a masterbatch and a preparation method thereof, a vulcanized rubber and application thereof. The method includes: mixing a modified white carbon black-solvent dispersion solution with a rubber colloidal solution obtained by solution polymerization to obtain a modified white carbon black-rubber suspending solution. A mixing kettle used by the mixing process includes: a rotatable center shaft arranged in mixing kettle longitudinally, at least two radial flow type stirring paddles mounted on the center shaft and an annular disk arranged between two adjacent radial flow type stirring paddles, wherein the center shaft and the radial flow type stirring paddles pass through the inner circle of the annular disk, and the outer circle periphery of the annular disk is connected to the inner wall of the mixing kettle. The mixing temperature is 20-80DEG C, and the mixing time is 1-60min. With the preparation method of masterbatch provided by the invention, evenly mixed masterbatch can be obtained within a shorter period of time.
Description
Technical field
The present invention relates to a kind of master batch and preparation method thereof and vulcanized rubber and application thereof.
Background technology
In the preparation technology of rubber item, it is very important link that the filling of rubber coordinates, and decides the final performance of rubber item.Common rubber filling method is, carries out mixing, i.e. dry mixed by rubber and filler and chemical in Banbury mixer and mill.But solid rubber has very high toughness and elasticity, the rubber of solid form is thoroughly mixed not only consuming time but also consume energy with filler and chemical, also bring the pollution problem of rubber item enterprise.
The wet-mixed of filler and rubber glue is a kind of method of producing master batch.CN1900149A discloses the preparation method of a kind of organically-modified clay and butadiene styrene rubber nanometer composite material, the suspension of the clay and water with stratiform crystal layer overlay structure is mixed with styrene-butadiene latex, again through De-emulsification flocculent, drying, mixing, sulfuration, obtain clay and butadiene styrene rubber nanometer composite material.But this kind of method only limits to styrene-butadiene latex, the glue for solution polymerization styrene-butadiene rubber is then inapplicable.
CN101220177A discloses a kind of preparation method of white carbon black/solution polymerized butadiene styrene rubber nano-composite material, the method comprises and being mixed with solution polymerized butylbenzene glue by the white carbon black of modification, obtains white carbon black/solution polymerized butadiene styrene rubber nano-composite material after desolvation, oven dry.But this kind of method is white carbon black and the solution polymerized butylbenzene glue Homogeneous phase mixing of organifying modification.The method needs at 30-50 DEG C, be uniformly mixed 6-36 hour ability and obtains white carbon black/solution polymerized butadiene styrene rubber nano-composite material, is not suitable for suitability for industrialized production and is only suitable for solution polymerized butadiene styrene rubber.
Can provide containing Packed master batch by filler and rubber glue wet-mixed, although when can reduce existing rubber filling consumption energy consumption and pollute problem, but prior art still needs the mixing time grown very much, efficient technique means fast can't be provided to realize wet-mixed, be unsuitable for realizing white carbon black filler in the industrial production and be dispersed in rubber glue.And prior art only realizes preparing the master batch containing styrene-butadiene rubber(SBR).
As can be seen here, need a kind of applicable suitability for industrialized production to prepare the method for master batch, and more glue kind can be suitable for.
Summary of the invention
The object of the invention is the defect in order to overcome prior art, a kind of master batch and preparation method thereof and vulcanized rubber and application thereof are provided.
To achieve these goals, the invention provides a kind of preparation method of master batch, the method comprises: modified white carbon black-solvent dispersions mixes with the rubber glue obtained through solution polymerization by (1), obtains modified white carbon black-elastomeric suspension liquid; The mixing kettle that mixing process uses comprises: the annual disk being longitudinally arranged on the rotatable central shaft in mixing kettle, being arranged at least two radial-flow type stirring rakes on described central shaft and being arranged between adjacent two radial-flow type stirring rakes; Wherein said central shaft and radial-flow type stirring rake pass from the inner circle of described annual disk, and the cylindrical peripheral portion of described annual disk is connected on the inwall of mixing kettle; The temperature of described mixing is 20-80 DEG C, and the time of described mixing is 1-60min; (2) modified white carbon black-elastomeric suspension liquid that step (1) obtains is carried out condense and drying; Wherein, the modified white carbon black in described modified white carbon black-solvent dispersions for contacting white carbon black with silane coupler containing sulfur and obtaining under condensation condition.
Present invention also offers the master batch prepared by method provided by the invention.
Present invention also offers a kind of vulcanized rubber, this vulcanized rubber is obtained after mixing and sulfuration by the mixture containing master batch provided by the invention, vulcanizing agent, vulcanization activator, promotor and anti-aging agent, relative to polymkeric substance 100 weight part in described master batch, the consumption of described vulcanizing agent is 0.5-2.5 weight part, the consumption of described vulcanization activator is 3-10 weight part, the consumption of described promotor is 1-4 weight part, the consumption of described anti-aging agent is 1-3 weight part.
Present invention also offers vulcanized rubber provided by the invention and prepare the application in tire.
The preparation method of master batch provided by the invention can obtain the uniform master batch of modified white carbon black blending dispersion in a short period of time.The method is suitable for industrialization continuous seepage.Such as, in embodiment 1, method provided by the invention, can be 50-70 DEG C in the temperature of mixing, the time of mixing be under 5.0min, and obtain master batch M1, wherein relative to the polyisoprene rubber of 100 weight parts, modified white carbon black content is 20 weight parts.Through transmission electron microscope observing, the state of aggregation particle of not modified white carbon black in master batch M1.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of master batch, the method comprises: modified white carbon black-solvent dispersions mixes with the rubber glue obtained through solution polymerization by (1), obtains modified white carbon black-elastomeric suspension liquid; The mixing kettle that mixing process uses comprises: the annual disk being longitudinally arranged on the rotatable central shaft in mixing kettle, being arranged at least two radial-flow type stirring rakes on described central shaft and being arranged between adjacent two radial-flow type stirring rakes, wherein said central shaft and radial-flow type stirring rake pass from the inner circle of described annual disk, and the cylindrical peripheral portion of described annual disk is connected on the inwall of mixing kettle; The temperature of described mixing is 20-80 DEG C, and the time of described mixing is 1-60min; (2) modified white carbon black-elastomeric suspension liquid that step (1) obtains is carried out condense and drying; Wherein, the modified white carbon black in described modified white carbon black-solvent dispersions for contacting white carbon black with silane coupler containing sulfur and obtaining under condensation condition.
In the present invention, described mixing kettle is one of applicant can be specifically the Chinese patent application of CN102600749A see application publication number in first patent application, and this patent application is introduced by reference to full text at this.
In the present invention, the outside diameter of described annual disk mates with the internal diameter of described mixing kettle, to make described annual disk circumferentially be connected on described mixing kettle inwall by symmetric mode, the interior circular diameter of described annual disk is 1-1.5 times of the diameter of radial-flow type stirring rake.
In the present invention, the ring part of described annual disk circumferentially symmetric mode between every two tie points radially ecto-entad dig fluted, like this, the center hole of described annual disk and peripheral groove form the flow passage of polyreaction material in described mixing kettle jointly.More specifically, determining in described annual disk after circular diameter and outer original diameter, circumferentially symmetric mode determines that described annual disk is connected to the tie point on still inwall, namely described tie point circumferentially symmetric mode described annual disk is divided into several Shan Huan districts, then, between every two tie points, in Ji Ge eccentric circular ring district, radially ecto-entad digs fluted.Ensureing connective stability and intensity and under considering the prerequisite of processing mounting complexity, circumferentially 2-8 tie point can be set on described annual disk symmetric mode, be preferably 3-6, most preferably be 4, correspondingly, described annual disk circumferentially will dig 2-8 groove by symmetric mode.Under preferable case, described annual disk is provided with 3-6 the groove radially caved in from cylindrical to inner circle, most preferably is 4.
In the present invention, the area (i.e. the Shan Huan district area of cutouts) of described groove should ensure the circulation area of polyreaction material as far as possible under the prerequisite of intensity not destroying whole annual disk, be preferably the 1/4-1/2 of the Shan Huan district area between two tie points corresponding on described annual disk, be preferably 1/3.
In the present invention, the mode of connection of described annual disk and still inwall can be the conventional suitable mode of connection in this area, such as, can arrange support to support described annual disk on still inwall.
In the present invention, described annual disk is arranged on the axial midpoint position between adjacent two radial-flow type stirring rakes.
In the present invention, the radial-flow type stirring rake on described central shaft can be 2-10 layer.Described mixing kettle, it utilizes the high-shear dissemination of the multilayer radial-flow type stirring rake in still, central shaft arranged to be smashed material to be mixed, then utilize the annual disk between described stirring rake to impel throughout its mass systemic circulation in still, thus make material reach the mixing of height microcosmic at short notice.
In the present invention, the aspect ratio of described mixing kettle can be 1-4, is preferably 2-3.The number of plies of radial-flow type stirring rake is 1-3 times of the aspect ratio of described mixing kettle, is preferably 1.5-2 doubly, like this, after the aspect ratio determining described mixing kettle, just correspondingly can determines the number of plies of the radial-flow type stirring rake wherein arranged.Described aspect ratio refers to the ratio of the height of mixing kettle and the diameter of mixing kettle.
In the present invention, the diameter of described radial-flow type stirring rake can be the 1/4-2/3 of the diameter of described mixing kettle, is preferably 1/3-1/2.Spacing between adjacent two radial-flow type stirring rakes can be 0.5-2 times of the diameter of radial-flow type stirring rake.Described interlamellar spacing increases from bottom to top gradually along central shaft in still, like this, after according to industrial scale determination mixing kettle diameter, just correspondingly can determine diameter and the interlamellar spacing of stirring rake, then to dredging, successively stirring rake is set from close from bottom to top according to the relation of interlamellar spacing and diameter of stirring paddle, thus plays the shearing dissemination of stirring rake better.
In the present invention, describedly be mixed into the different import that modified white carbon black-solvent dispersions and rubber glue be provided with respectively bottom described mixing kettle and enter described mixing kettle, the outlet that the modified white carbon black obtained-elastomeric suspension liquid is provided with from described mixing kettle top is discharged.
In the present invention, described radial-flow type stirring rake is the radial-flow type stirring rake that this area is commonly used, and this stirring rake is high speed rotating under driven by motor, and its rotating speed can be 200-800rpm, is preferably 300-700rpm, is more preferably 350-600rpm.
According to the present invention, adopt described mixing kettle can shorten the time of modified white carbon black-solvent dispersions and the mixing of rubber glue, and mix.Method provided by the invention can carry out continuous prodution, is suitable for industrial application.The temperature of preferred described mixing is 40-70 DEG C, and the time of described mixing is 5-20min.
Described modified white carbon black be another of applicant in first patent application, can be specifically the Chinese patent application of CN103159994A see application publication number, this patent application at this by reference to introducing in full.
More specifically, in the preparation method of obtained described modified white carbon black, the mass ratio of described white carbon black and silane coupler containing sulfur is 1:0.03-0.15, is preferably 1:0.05-0.12; The specific surface area of described white carbon black is 100-175m
2/ g; Described silane coupler containing sulfur is selected from two-(γ-triethoxysilylpropyl)-tetrasulfide and/or two-(3-triethoxysilylpropyl)-disulphide; The temperature of described contact is 80-120 DEG C, and preferably, the temperature of described contact is 90-100 DEG C; The time of described contact is 1-5 hour, and preferably, the time of described contact is 2.5-4 hour.
According to the present invention, under preferable case, described modified white carbon black-solvent dispersions is also containing the first organic solvent; Described first organic solvent is at least one in benzene, toluene, hexane, Skellysolve A and normal heptane, and preferably, described first organic solvent is hexane.It is at least one in the hexane fraction of more than 60 % by weight that described hexane can be selected from normal hexane, hexanaphthene and normal hexane content.
According to the present invention, under preferable case, in described modified white carbon black-solvent dispersions, the content of modified white carbon black is 100-700g/L; Preferably, the content of modified white carbon black is 200-500g/L.
According to the present invention, under preferable case, described rubber glue contains polymkeric substance and the second organic solvent; Described second organic solvent is at least one in benzene, toluene, hexane, Skellysolve A and normal heptane, and preferably, described second organic solvent is hexane.It is at least one in the hexane fraction of more than 60 % by weight that described hexane can be selected from normal hexane, hexanaphthene and normal hexane content.
According to the present invention, under preferable case, polymkeric substance is selected from least one in polyhutadiene, polyisoprene, butadiene-styrene copolymer, ethylene-propylene copolymer, ethylene-propylene-Isosorbide-5-Nitrae-hexadiene multipolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-5-ethylidene-2-norbornene multipolymer; The weight-average molecular weight of described polymkeric substance is 200,000-200 ten thousand.
According to the present invention, under preferable case, in described rubber glue, the content of polymkeric substance is 70-200g/L; Preferably, the content of polymkeric substance is 80-150g/L.
According to the present invention, under preferable case, relative to polymkeric substance 100 weight part that described rubber glue contains, the consumption of the modified white carbon black that described modified white carbon black-solvent dispersions contains is 10-100 weight part; Preferably, relative to polymkeric substance 100 weight part that described rubber glue contains, the consumption of the modified white carbon black that described modified white carbon black-solvent dispersions contains is 20-70 weight part.
In the present invention, step (1) modified white carbon black-solvent dispersions is with the rubber glue mixing process obtained through solution polymerization, and described modified white carbon black-solvent dispersions is charging under room temperature; The feeding temperature of described rubber glue is determined according to the polymerization temperature that rubber glue is final.Generally, described modified white carbon black-solvent dispersions is 0-100 DEG C with the temperature mixed of rubber glue, and preferably, the temperature of described mixing is 20-80 DEG C, and the temperature of described mixing is more electedly 20-60 DEG C.
In the present invention, the cohesion of step (2) and drying can be that this area routine uses cohesion and dry method and condition, such as, the method of described cohesion can be two stills or three stills series connection hot water coacervation, the condition of described cohesion can comprise condensation temperature 85-105 DEG C, and cohesion pressure is less than 0.1MPa; The method of described drying can be extrusion dehydration-expansion drying method, and be specifically as follows and the micelle of water-content about 50 % by weight is sent into screw extrusion press dehydration, the micelle water-content after dehydration is 8-15 % by weight.Dehydration micelle is dry in die swell drying machine, and micelle water-content is down to 0.3-0.5 % by weight, dried micelle through briquetting, shaping, be packaged to be finished product.
According to the preparation method of master batch provided by the invention, white carbon black and silane coupler containing sulfur are prepared into modified white carbon black, modified white carbon black-the solvent dispersions again this modified white carbon black made, then this modified white carbon black-solvent dispersions is mixed with rubber glue in described mixing kettle, thus dispersed in rubber glue of modified white carbon black can be realized at faster speed.The state of aggregation particle of modified white carbon black in master batch is not observed by transmission electron microscope detection method.
Present invention also offers the master batch prepared by method provided by the invention.
Present invention also offers a kind of vulcanized rubber, this vulcanized rubber is obtained after mixing and sulfuration by the mixture containing master batch provided by the invention, vulcanizing agent, vulcanization activator, promotor and anti-aging agent, relative to polymkeric substance 100 weight part in described master batch, the consumption of described vulcanizing agent is 0.5-2.5 weight part, the consumption of described vulcanization activator is 3-10 weight part, the consumption of described promotor is 1-4 weight part, the consumption of described anti-aging agent is 1-3 weight part.
According to vulcanized rubber provided by the invention, described vulcanizing agent, vulcanization activator, promotor and anti-aging agent all can adopt known various for rubber compounding, mixing vulcanizing agent, vulcanization activator, promotor and anti-aging agent.Such as, described vulcanizing agent is selected from one or more in sulphur, selenium, tellurium, benzoyl peroxide, urethanum and 2,5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane; Described vulcanization activator be selected from zinc oxide, magnesium oxide, stearic acid one or more; Described promotor be selected from vulkacit D (vulkacit D), tetramethyl-thiuram disulfide (promotor TT), 2-thiol benzothiazole (captax), ethylene thiourea (accelerant N A-22) and N-cyclohexyl-2-benzothiazole sulfonamide (accelerant CZ) one or more; Described anti-aging agent is selected from 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer (anti-aging agent RD), 6-oxyethyl group-2,2, one or more in 4-trimethylammonium-1,2-dihyaroquinoline (antioxidant A W), N-phenyl-α-aniline (antioxidant A), N-Phenyl beta naphthylamine (antioxidant D), N-phenyl-N '-cyclohexyl Ursol D (antioxidant 4010) and N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine (antioxidant 4020).
According to vulcanized rubber provided by the invention, the preparation of this vulcanized rubber can adopt various known method to carry out.Such as, by mixing in mill for the mixture containing rubber ingredients such as above-mentioned master batch and vulcanizing agent, vulcanization activator, promotor and anti-aging agent, the rubber unvulcanizate obtained vulcanization crosslinking in vulcanizing press, obtains vulcanized rubber.For the vulcanized rubber of preparation butadiene-styrene copolymer, mixing condition can comprise roller speed for 15-30 rev/min, mixing time is 10-30 minute, and cure conditions comprises that curing temperature is 140-180 DEG C, pressure is 10-20MPa, the time is 10-40 minute.As required vulcanized rubber can be cut to the dimensions that various rubber testing standard specifies to test, to determine the performance of this vulcanized rubber, and determine the purposes of this vulcanized rubber according to performance.Vulcanized rubber of the present invention can use like the prior art, as the preparation of various tire.
Present invention also offers vulcanized rubber provided by the invention and prepare the application in tire.
In the present invention, the pressure related to all is expressed as gauge pressure.
The present invention is described in detail by the following examples.In following examples, the dispersing uniformity of modified white carbon black in master batch is by transmission electron microscope (model: JEOL JEM2010 type, acceleration voltage is 200kV).Sample processing conditions: adopt Leica Ultracut-R type ultramicrotome to cut into slices at-100 DEG C, the thin slice cut is placed on carbon support membrane copper mesh, carries out electron microscopic observation.
Unless stated otherwise, raw materials usedly in embodiments of the invention, comparative example and preparation example all can be commercially available.
Embodiment 1
The present embodiment is for illustration of the preparation method of master batch of the present invention.
(1) mix.By the modified white carbon black of normal temperature-normal hexane dispersion liquid, (modified white carbon black content is 200g/L, and the specific surface area of white carbon black is 115m
2/ g, silane coupler containing sulfur is two-(γ-triethoxysilylpropyl)-tetrasulfide, the mass ratio of white carbon black and silane coupler containing sulfur is 1:0.07, it is 1L/min that modified white carbon black-normal hexane dispersion liquid adds speed) and (polyisoprene rubber content is 100g/L, and adding speed is 10L/min to be preheated to the polyisoprene rubber glue of 60 DEG C; Polyisoprene rubber weight-average molecular weight 720,000, solvent is normal hexane) introduce 5L mixing kettle from respective two opening for feeds below mixing kettle respectively simultaneously.
The height of mixing kettle is 300mm, and diameter is 150mm, is provided with 4 layers of radial-flow type stirring arm, and the diameter of stirring rake is 1/2 of mixing kettle diameter, and the axial spacing between each stirring rake is followed successively by 56mm, 70mm, 98mm from bottom to top.Axial mid-way between every two-layer stirring arm is provided with an annual disk, and the center-hole diameter of annual disk is 1.15 times of diameter of stirring paddle.Axially symmetrical 4 the connecting portion places of annual disk on its outer peripheral portion are connected with the inwall of mixing kettle, and include 4 grooves, the area of each groove be corresponding fan anchor ring amass 1/3.Under the effect of stirring rake and annual disk, material fully mixes in mixing kettle, the rotating speed of stirring rake is 350rpm, the mixing temperature of material in mixing kettle is 60 DEG C, the time (mean residence time) of mixing is 5.0min, thus obtains the modified white carbon black-polyisoprene rubber normal hexane suspension mixed.
(2) cohesion and drying.Three still series connection hot-water process cohesion process, remove the normal hexane solvent in white carbon black-polyisoprene rubber hexane suspension, obtain the micelle that water ratio is about 50 % by weight; This micelle removes water and other volatile matter through extruding-desiccation machine and expansion-exsiccation machine, and obtain the polyisoprene rubber relative to 100 weight parts, modified white carbon black content is the master batch M1 of 20 weight parts.
Through transmission electron microscope observing, the state of aggregation particle of not modified white carbon black in master batch M1.Illustrate that modified white carbon black is uniformly dispersed in master batch.
Embodiment 2
The present embodiment is for illustration of the preparation method of master batch of the present invention.
According to the method for embodiment 1, unlike, with " it is 0.5L/min that modified white carbon black-normal hexane dispersion liquid adds speed " and " it is 5L/min that polyisoprene rubber glue adds speed ", substitute " it is 1L/min that modified white carbon black-normal hexane dispersion liquid adds speed " and " it is 10L/min that polyisoprene rubber glue adds speed ".
Unlike, in mixing kettle, the center-hole diameter of annual disk is 1.3 times of diameter of stirring paddle.The mean residence time of material in mixing kettle is 10min.
Finally obtain the polyisoprene rubber relative to 100 weight parts, modified white carbon black content is the master batch M2 of 20 weight parts.
Through transmission electron microscope observing, the state of aggregation particle of not modified white carbon black in master batch M2.
Embodiment 3
The present embodiment is for illustration of the preparation method of master batch of the present invention.
According to the method for embodiment 1, unlike, with " it is 0.25L/min that modified white carbon black-normal hexane dispersion liquid adds speed " and " it is 2.5L/min that polyisoprene rubber glue adds speed ", substitute " it is 1L/min that modified white carbon black-normal hexane dispersion liquid adds speed " and " it is 10L/min that polyisoprene rubber glue adds speed ".
Unlike, in mixing kettle, the diameter of stirring rake is 2/3 of the diameter of mixing kettle.The mean residence time of material in mixing kettle is 20min.
Finally obtain the polyisoprene rubber relative to 100 weight parts, modified white carbon black content is the master batch M3 of 20 weight parts.
Through transmission electron microscope observing, the state of aggregation particle of not modified white carbon black in master batch M3.
Embodiment 4
The present embodiment is for illustration of the preparation method of master batch of the present invention.
According to the method for embodiment 3, unlike, with " modified white carbon black content is 400g/L ", substitute " modified white carbon black content is 200g/L ".
The mean residence time of material in mixing kettle is 20min.
Finally obtain the polyisoprene rubber relative to 100 weight parts, modified white carbon black content is the master batch M4 of 40 weight parts.
Through transmission electron microscope observing, the state of aggregation particle of not modified white carbon black in master batch M4.
Embodiment 5
The present embodiment is for illustration of the preparation method of master batch of the present invention.
According to the method for embodiment 3, unlike, substitute " modified white carbon black content is 200g/L " with " modified white carbon black content is 700g/L ".The mean residence time of material in mixing kettle is 20min.
Finally obtain the polyisoprene rubber relative to 100 weight parts, modified white carbon black content is the master batch M5 of 70 weight parts.
Through transmission electron microscope observing, the state of aggregation particle of not modified white carbon black in master batch M5.
Embodiment 6
The present embodiment is for illustration of the preparation method of master batch of the present invention.
According to the method for embodiment 4, unlike, with " cis-1,4-polybutadiene rubber glue (cis-1,4-polybutadiene rubber content 100g/L, adding speed is 2.5L/min; Cis-1,4-polybutadiene rubber weight-average molecular weight 230,000, solvent is normal hexane) ", substitute " polyisoprene rubber glue ".
The mean residence time of material in mixing kettle is 20min.
Finally obtain the cis-1,4-polybutadiene rubber relative to 100 weight parts, modified white carbon black content is the master batch M6 of 40 weight parts.
Through transmission electron microscope observing, the state of aggregation particle of not modified white carbon black in master batch M6.
Embodiment 7
The present embodiment is for illustration of the preparation method of master batch of the present invention.
According to the method for embodiment 4, unlike, with " solution polymerized butadiene styrene rubber glue (solution polymerized butadiene styrene rubber content 100g/L, adding speed is 2.5L/min, solution polymerized butadiene styrene rubber weight-average molecular weight 230,000, and solvent is hexanaphthene) ", substitute " polyisoprene rubber glue ".
The mean residence time of material in mixing kettle is 20min.
Finally obtain the solution polymerized butadiene styrene rubber relative to 100 weight parts, modified white carbon black content is the master batch M7 of 40 weight parts.
Through transmission electron microscope observing, the state of aggregation particle of not modified white carbon black in master batch M7.
Comparative example 1
According to the method for embodiment 1, unlike, only retain in mixing kettle from lower several second layer stirring rake, remove other stirring rake and all annual disks.
Obtain master batch DM1.Through transmission electron microscope observing, in master batch DM1, there is the state of aggregation particle of modified white carbon black, illustrate that modified white carbon black dispersion is uneven.
Comparative example 2
According to the method for comparative example 1, unlike, in step (1), substitute " time (mean residence time) of mixing is 5.0min " with " time (mean residence time) of mixing is 10 hours ".
Obtain master batch DM2.Through transmission electron microscope observing, the state of aggregation particle of not modified white carbon black in master batch DM2.
Preparation example 1
By master batch M1 and 1.4g sulphur, 2g vulkacit D, 1g N-cyclohexyl-2-benzothiazole sulfonamide, 2g N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine, 1g stearic acid, 2g zinc oxide in mill with roller speed 18-24 rev/min mixing 20 minutes, the rubber unvulcanizate obtained with 150 DEG C, 15MPa sulfuration 40 minutes, finally obtains vulcanized rubber S1 in vulcanizing press.
Preparation example 2-7
Prepare vulcanized rubber according to the method for preparation example 1, separately replace M1 unlike with M2-M7, obtain vulcanized rubber S2-S7.
Test case
By the following method vulcanized rubber S1-S7 is tested:
(1) wear resisting property: 23 ± 2 DEG C, relative humidity is 50 ± 5% use DIN abrasion instruments, test according to GB9867-2008;
(2) dynamic property: use Dynamic Mechanical Analyzer (DMA2980) with stretch mode (pre-tension is 0.05 newton), frequency be 2Hz, heat-up rate 3 DEG C/min, range of temperature-100 DEG C test to 100 DEG C;
(3) mechanical property: fracture tensile strength, tensile yield and 300% stress at definite elongation are tested according to GB/T528-1998; Tear strength test is tested according to GB/T529-2008; Hardness (shore hardness A) is tested according to GB/T23651-2009;
(4) dynamic compression heat build-up: use rubber compression heat generation trier (RH-2000, Taiwan High Speed Rail Testing Instruments company limited) with stroke 4.45 millimeters, load 1MPa, test 25 minutes at 55 DEG C;
All test results are as shown in table 1.
Table 1
As can be seen from the result of embodiment 1-7, method provided by the invention can obtain the uniform master batch of blending dispersion within the shorter time.And the method can be suitable for more glue kind, as polyisoprene rubber, cis-1,4-polybutadiene rubber, solution polymerized butadiene styrene rubber.
In comparative example 1, the mixing kettle used is not the mixing kettle used in method provided by the invention, and the actual mixing kettle for prior art use, result can not realize the dispersed of modified white carbon black at short notice.In comparative example 2, when the time to 10 extending mixing little constantly (mixing time that prior art routine uses), use the mixing kettle of prior art could obtain the homodisperse effect of modified white carbon black.As can be seen here, method provided by the invention, relative to prior art, can improve the production efficiency of the homodisperse master batch of modified white carbon black effectively.
In table 1, the data of S1-S7 can be found out, vulcanized rubber S1-S7 has the wear resisting property of good mechanical property, lower rolling resistance, preferably wet-sliding resistant performance and excellence.
Claims (18)
1. a preparation method for master batch, the method comprises:
(1) modified white carbon black-solvent dispersions is mixed with the rubber glue obtained through solution polymerization, obtain modified white carbon black-elastomeric suspension liquid; The mixing kettle that mixing process uses comprises: the annual disk being longitudinally arranged on the rotatable central shaft in mixing kettle, being arranged at least two radial-flow type stirring rakes on described central shaft and being arranged between adjacent two radial-flow type stirring rakes; Wherein said central shaft and radial-flow type stirring rake pass from the inner circle of described annual disk, and the cylindrical peripheral portion of described annual disk is connected on the inwall of mixing kettle; The temperature of described mixing is 20-80 DEG C, and the time of described mixing is 1-60min;
(2) modified white carbon black-elastomeric suspension liquid that step (1) obtains is carried out condense and drying;
Wherein, the modified white carbon black in described modified white carbon black-solvent dispersions for contacting white carbon black with silane coupler containing sulfur and obtaining under condensation condition.
2. method according to claim 1, wherein, described annual disk is provided with 3-6 the groove radially caved in from cylindrical to inner circle, the interior circular diameter of described annual disk is 1-1.5 times of the diameter of radial-flow type stirring rake, and described annual disk is arranged on the axial midpoint position between adjacent two radial-flow type stirring rakes.
3. method according to claim 1, wherein, the aspect ratio of described mixing kettle is 2-3:1, the diameter of described radial-flow type stirring rake is the 1/3-1/2 of the diameter of described mixing kettle, spacing between adjacent two radial-flow type stirring rakes is 0.5-2 times of the diameter of radial-flow type stirring rake, and the number of plies of described radial-flow type stirring rake is 1.5-2 times of the aspect ratio of described mixing kettle.
4. method according to claim 1, wherein, describedly be mixed into the different import that modified white carbon black-solvent dispersions and rubber glue be provided with respectively bottom described mixing kettle and enter described mixing kettle, the outlet that the modified white carbon black obtained-elastomeric suspension liquid is provided with from described mixing kettle top is discharged.
5. method according to claim 1, wherein, described in step (1), the temperature of mixing is 40-70 DEG C, and the time of described mixing is 5-20min.
6. method according to claim 1, wherein, the condition that white carbon black and silane coupler containing sulfur contact under condensation condition comprised: temperature is 80-120 DEG C, the time is 1-5 hour.
7. method according to claim 1, wherein, the specific surface area of described white carbon black is 100-175m
2/ g; Described silane coupler containing sulfur is selected from two-(γ-triethoxysilylpropyl)-tetrasulfide and/or two-(3-triethoxysilylpropyl)-disulphide.
8. method according to claim 1, wherein, the mass ratio of described white carbon black and silane coupler containing sulfur is 1:0.03-0.15; Be preferably 1:0.05-0.12.
9. method according to claim 1, wherein, described modified white carbon black-solvent dispersions is also containing the first organic solvent; Described first organic solvent is at least one in benzene, toluene, hexane, Skellysolve A and normal heptane, and preferably, described first organic solvent is hexane.
10. method according to claim 9, wherein, in described modified white carbon black-solvent dispersions, the content of modified white carbon black is 100-700g/L; Preferably, the content of modified white carbon black is 200-500g/L.
11. methods according to claim 1, wherein, described rubber glue contains polymkeric substance and the second organic solvent; Described second organic solvent is at least one in benzene, toluene, hexane, Skellysolve A and normal heptane, and preferably, described second organic solvent is hexane.
12. methods according to claim 11, wherein, described polymkeric substance is selected from least one in polyhutadiene, polyisoprene, butadiene-styrene copolymer, ethylene-propylene copolymer, ethylene-propylene-Isosorbide-5-Nitrae-hexadiene multipolymer, ethylene-propylene-dicyclopentadiene copolymer and ethylene-propylene-5-ethylidene-2-norbornene multipolymer; The weight-average molecular weight of described polymkeric substance is 200,000-200 ten thousand.
13. methods according to claim 11 or 12, wherein, in described rubber glue, the content of polymkeric substance is 70-200g/L; Preferably, the content of polymkeric substance is 80-150g/L.
14. methods according to claim 1, wherein, in step (1), relative to polymkeric substance 100 weight part that described rubber glue contains, the consumption of the modified white carbon black that described modified white carbon black-solvent dispersions contains is 10-100 weight part; Preferably, relative to polymkeric substance 100 weight part that described rubber glue contains, the consumption of the modified white carbon black that described modified white carbon black-solvent dispersions contains is 20-70 weight part.
15. master batchs prepared by the method in claim 1-14 described in any one.
16. 1 kinds of vulcanized rubbers, this vulcanized rubber is obtained after mixing and sulfuration by the mixture containing master batch according to claim 15, vulcanizing agent, vulcanization activator, promotor and anti-aging agent, relative to polymkeric substance 100 weight part in described master batch, the consumption of described vulcanizing agent is 0.5-2.5 weight part, the consumption of described vulcanization activator is 3-10 weight part, the consumption of described promotor is 1-4 weight part, the consumption of described anti-aging agent is 1-3 weight part.
17. vulcanized rubbers according to claim 16, wherein, described vulcanizing agent is selected from sulphur, selenium, tellurium, benzoyl peroxide, urethanum and 2, at least one in 5 2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane; Described vulcanization activator is selected from least one in zinc oxide, magnesium oxide and stearic acid; Described promotor is selected from least one in vulkacit D, tetramethyl-thiuram disulfide, 2-thiol benzothiazole, ethylene thiourea and N-cyclohexyl-2-benzothiazole sulfonamide; Described anti-aging agent is selected from 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer, 6-oxyethyl group-2,2, at least one in 4-trimethylammonium-1,2-dihyaroquinoline, N-phenyl-α-aniline, N-Phenyl beta naphthylamine, N-phenyl-N '-cyclohexyl Ursol D and N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine.
The application in tire prepared by vulcanized rubber described in 18. claims 16 or 17.
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