CN106479006A - Elastic composites - Google Patents
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- CN106479006A CN106479006A CN201510527292.9A CN201510527292A CN106479006A CN 106479006 A CN106479006 A CN 106479006A CN 201510527292 A CN201510527292 A CN 201510527292A CN 106479006 A CN106479006 A CN 106479006A
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Abstract
A kind of elastic composites, including following components：Polymerisation in solution synthetic rubber and filler, described filler is modified white carbon black or white carbon black；The ratio of rubber and filler is 100:30～110；Filler aggregate particle size is 100nm-10 μm；Comprise the steps：(1) in non-polar organic solvent, make modified white carbon black grinding milk or white carbon black grinding milk, modified white carbon black grinding milk or white carbon black grinding milk are denoted as filler serosity, modified white carbon black or white carbon black are denoted as filler；(2) above-mentioned filler serosity or filler carry out dispersion mixing in proportion with rubber glue under high energy shear, form compound somaplasm glue；(3) above-mentioned dispersion mixing is uniformly combined somaplasm glue dry removal solvent in a dynamic state；(4) complex of above-mentioned desolvation is carried out shearing kneading drying, obtain product.
Description
Technical field
The present invention relates to a kind of elastic composites, particularly a kind of elastic composite material for high-performance tire
Material.
Background technology
Since nearly half a century, polymerisation in solution synthetic rubber has evolved into the important former material that tire is not replaced
Material.Particularly solution polymerized butadiene styrene rubber, provides the various viscoelastics of tire needs with the new construction that it is continually changing
Performance, and make white carbon become the important reinforced filling of reinforced rubber.Make of white carbon and solution polymerized rubber
Tire has the anti-slippery of lower rolling resistance and Geng Gao than with the tire that white carbon black and emulsion polymerized rubber make
Energy.Therefore, polymerisation in solution synthetic rubber and white carbon, it has also become the important foundation material of high-performance tire.
Braking quality on wet road for the tire, on the one hand comes from the gripping power to wet road surface for the tire, the opposing party
Face comes from the absorption to kinetic energy for the tire.The key component of tire tread glue is rubber and filler, wherein Linesless charcoal
Black is hydrophilic, can penetrate the moisture film being present between tyre surface and road surface, catch road surface beneficial to tire；And
The kinetic energy absorption of tire can be converted by viscoelastic property that rubber molecule has under certain condition.However,
It is known that the tire being made using same raw materials, its to the penetrance of moisture film with the viscoelasticity that has,
Not necessarily identical.In fact, difference can be very big, the dispersion that this is main and white carbon is in rubber and with
The interaction of rubber molecule is closely related.
The rolling resistance of tire refers to the part kinetic energy that in traveling, tire consumes.Research is it was demonstrated that in energy consumption
The overwhelming majority, for destroying network structure present in tire tread glue.In the manufacturing process of tire, mend
Strong filler (white carbon black or white carbon) forms network in rubber, during the cyclic deformation of tire running,
Filler network is subject to reciprocating destruction with deformation, so that kinetic energy is consumed in material, the network in material is more,
Bigger to the energy consumption of kinetic energy, that is, kinetic energy be converted into idle work ratio higher.Using same raw materials
The tire making, rolling resistance can differ greatly, and this depends entirely on the knot of filler network present in material
Structure number, and determine to be formed the how many key factor of filler network be dispersion in rubber for the reinforced filling and
Its interaction with rubber.
The mechanism of abrasion of tire is more complicated than the above two, but has any to be clearly, i.e. wear hardness and filler
Form and its dispersion in rubber and interacting closely be connected.
One common ground of these three mechanism is it is simply that be directed to dispersion and its phase with rubber of reinforced filling
Interaction.Therefore, improve the tackling key problem of the big performance of tire three also just round how improving reinforced filling, especially
It is white carbon, the dispersion in rubber and launching with the interaction of rubber.
White carbon field, for improving its dispersive property, has taken its surface hydroxyl quantity of abatement, has reduced basis
Interparticle cohesiveness, makes to be easily dispersed in compounding rubber；Also have in white carbon surface grafting coupling agent,
Increase the interaction of itself and rubber.White carbon black field, for increasing the hydrophilic of filler, in carbon blacksurface " edge
Embedding " or " cladding " white carbon, but the thing followed is dispersibility decline in rubber for the filler；For improving
Interaction between white carbon black and rubber, has in carbon blacksurface graft compound so as to produce and rubber between
The chemical bonding occurring when similar white carbon is using coupling agent.Rubber materials, for the phase between raising and filler
Interaction, promotes filler dispersion, grafted polar functional group on rubber molecular chain.But the viscoelastic property of rubber
Also can change therewith.
No matter how rubber and filler are mutually transformed each other each other, they are fabricated to composite, are all now
The production line of tire plant completes, mainly completes in mixing workshop, equipment is many decades, up to a hundred
Year constant mill and banbury.In manufacturing process, rotor passes through rubber, and shear action is being filled out
On material granule, filler is pulverized in rubber by filler absorption rubber, is uniformly dispersed.Here have one from
Start to be known that but the difficult problem that cannot change is not it is simply that rubber is shearing force " optimum " transmitter.Do not say
Itself can occur mechanical chain rupture and oxidation under shearing force, and its viscosity with temperature raises and declines, just foot
To weaken its transitivity to shearing force.Therefore, the dispersion in rubber of white carbon and white carbon black, becomes weighing apparatus
One important indicator of amount tyre company Technology ability.Each company has paid unremitting effort for this, but
Because technique does not have the change of essence, the performance of material there will not be breakthrough raising.
Revolutionary change is carried out to calendering process, is that eighties of last century rubber field is constantly pursued always
Cause.Liquid phase mixing early at the beginning of eighties of last century just it has been proposed that a lot of research institution invests exploration for it, but,
Industrialization is not as the so easy of the imagination, is formed with the production technology of economic worth, up to the present, only
Have aqueous phase hybrid technique (US19970823411, CN97195156, CN98811684, CN00808002,
CN02825969).It is a revolutionary reform, with a kind of method different from traditional handicraft, incites somebody to action
Traditional handicraft pursue less than performance be changed into true.But, the glue that it uses is Heveatex, and filler is
White carbon black, makes serosity in water.And most of synthetic rubber, particularly tackle the SSBR of tire tag method
And NdBR, it is to synthesize in organic solvent, be organic faciess latex, filler is based on white carbon.This
In system with organic solvent and white carbon as feature, realize solution dispersion mixing, make complex, will have
There is more, bigger challenge.In recent decades, many companies develop this as research topic.
White carbon black slurry is mixed directly into polymer by U.S.Pat.No.3055956 and U.S.Pat.No.3767605
In latex, flocculation, dry, prepared white carbon black/rubber mixed after mixing.Here rubber is emulsion polymerization rubber
Glue, its glue is aqueous phase, using a large amount of emulsions during rubber polymerization, is unfavorable for white carbon and rubber molecule
Interact.
CN201310027024.1, CN201310037190.X, CN201310095415.7 and
Not ground modified filler is added directly in solution polymerized rubber glue CN201310027002.5, passes through
Stirring forms mixture；This mixture is carried out with refinement dispersion and essence dispersion, to improve filler in rubber solutions
In degree of scatter；Again the mixture after essence dispersion is passed through or flocculence or heating or move back solvent method,
Desolvation；And the mixture after desolventizing is dried, obtain rubber/filler masterbatch.Here,
The modification of white carbon is not before mixing with rubber glue, in desolvation, or employs water, or
Person is not carried out under the conditions of dynamic shearing.
CN200810056820.7 reports wet processing and prepares white carbon black/solution polymerized butylbenzene elastomeric compound.It uses
Amino silane coupler (ethanol) in polar solvent carries out surface modification to the white carbon not ground；So
Afterwards this modified white carbon and hexamethylene are configured to serosity, mix with solution polymerized butylbenzene glue；Finally remove
Solvent, obtains white carbon black/solution polymerized butylbenzene elastomeric compound.
US7790798 reports a kind of wet processing and prepares elastomeric compound.It is by unmodified white carbon and non-pole
Property solvent mixing, then grind slurrying, the particle diameter of white carbon reaches 6-20 micron after grinding；To fill out again
Slip and rubber glue are blended under non-shear conditions；Remove solvent finally by cylinder dry, mixed
Refining glue.
Content of the invention
It is an object of the invention to provide a kind of high-performance elastic complex, particularly one kind are used for tire tread rubber
Glue/filler complex.This complex adopts solution dispersion hybrid technique to prepare, and filler is modified through grinding,
Aggregate particle size can reach nanoscale, and filler is uniformly dispersed in rubber, forms good phase with rubber molecule
Interaction.Vulcanizate and the vulcanizate phase with traditional calendering process preparation using the preparation of this elastic composites
Dynamic mechanical significantly improves ratio, and strength and extension property is good, and hardness is low.
The present invention provides a kind of elastic composites, including following components：Polymerisation in solution synthetic rubber and filler,
Described filler is modified white carbon black or white carbon black；The ratio of rubber and filler is 100:30～110；Filler aggregation
Particle diameter is 100nm-10 μm.Described modified white carbon black adopts in number of patent application 201410724713.2
Disclosed modified white carbon black.
Elastic composites of the present invention, wherein, the ratio of rubber and filler is preferably 100:40-80.
Elastic composites of the present invention, wherein, modified white carbon black aggregate particle size is preferably 100nm-5
μm.
Elastic composites of the present invention, wherein, carbon black aggregate particle diameter is preferably 1 μm -8 μm.
Elastic composites of the present invention, wherein, polymerisation in solution synthetic rubber be preferably Butadiene-Styrene Rubber,
Rare earth cis-butadiene cement, cis-butadiene cement, rare-earth isoprene rubber or isoprene rubber.
Present invention simultaneously provides a kind of preparation method of elastic composites, comprise the steps：
(1) in non-polar organic solvent, modified white carbon black grinding milk or white carbon black grinding milk are made,
Modified white carbon black grinding milk or white carbon black grinding milk are denoted as filler serosity, modified white carbon black or white carbon black are denoted as
Filler；
(2) above-mentioned filler serosity or filler carry out dispersion mixing in proportion with rubber glue under high energy shear,
Form compound somaplasm glue；
(3) above-mentioned dispersion mixing is uniformly combined somaplasm glue dry removal solvent in a dynamic state；
(4) complex of above-mentioned desolvation is carried out shearing kneading drying, obtain product；
Wherein, non-polar organic solvent described in step (1), rubber glue solvent for use in step (2)
It is fat hydrocarbon, alicyclic hydrocarbon type or arene non-polar organic solvent.
The preparation method of elastic composites of the present invention, these, it is preferred to described in step (1)
In non-polar organic solvent, step (2) rubber glue solvent for use be respectively pentane, Pentamethylene., hexane,
Hexamethylene, heptane, toluene or petroleum ether.
The preparation method of elastic composites of the present invention, wherein, described carbon black aggregate particle diameter is preferably
1 μm -10 μm, more preferably 1 μm -8 μm.
The preparation method of elastic composites of the present invention, wherein, modified white carbon black aggregate particle size is preferred
For 100nm-5 μm.
The preparation method of elastic composites of the present invention, wherein, rubber is preferably Butadiene-Styrene Rubber, dilute
Native cis-butadiene cement, cis-butadiene cement, rare-earth isoprene rubber or isoprene rubber.
The preparation method of elastic composites of the present invention, wherein, in modified white carbon black serosity, modified white
The solid content of white carbon black is preferably 5%～20%, and the solid content of modified white carbon black is more preferably 10-15%；White carbon black
In serosity, the solid content of white carbon black is preferably 5%～15%, and the solid content of white carbon black is more preferably 5-10%.
The preparation method of elastic composites of the present invention, wherein, in step (2), rubber glue is dense
Degree is preferably 5%～30%, and the concentration of rubber glue is more preferably 15-20%.
The preparation method of elastic composites of the present invention, wherein, is combined somaplasm described in step (2)
Glue, ratio in rubber for the filler is preferably 30-110phr.
The preparation method of elastic composites of the present invention, wherein, ratio in rubber for the filler is preferably
40-80phr.
The preparation method of elastic composites of the present invention, wherein, preferred scheme is in step (3)
The equipment dynamically descending dry removal solvent has multistage and reduces pressure the screw extruder of devolatilization mouth, and temperature control exists
40-100 DEG C, the complex volatile matters at 100-250 rev/min, after devolatilization for the screw speed<1%.
The technical characterstic of the present invention is：
Using liquid-phase mixing dispersing technology, difficult scattered nano-sized filler is evenly dispersed in polymerisation in solution
In synthetic rubber；In complex, packing material size is little, combines closely with rubber.The sulfur being obtained by this compound adhesive
Change glue, dynamic mechanical is superior, and strength and extension property is good, and hardness is low；It is particularly well-suited to make the tyre surface of tire,
Advantageously reduce tire drag, improve wet-sliding resistant performance and abrasion resistance properties.
Brief description
Fig. 1：White carbon after the grinding tested with laser particle analyzer (Malvern 3000) and carbon black aggregate
Particle diameter.
Specific embodiment
Hereinafter embodiments of the invention are elaborated：The present embodiment is premised on technical solution of the present invention
Under implemented, give detailed embodiment and process, but protection scope of the present invention be not limited to following
Embodiment, the experimental technique of unreceipted actual conditions in the following example, generally according to normal condition.
High-performance elastic complex according to the present invention, mainly contains polymerisation in solution rubber in composition and silane is even
The modified white carbon of connection agent or white carbon black.The ratio of rubber and filler is 100:30～110.Wherein silane coupler
The white carbon of graft modification refers to that there are the silane coupler of the sulfur-bearing being grafted therewith, aggregation in the surface of white carbon
Preferably at 100nm-5 μm, the detailed description with regard to all technical characteristics of modified white carbon black is shown in patent to particle diameter
Technology contents disclosed in Application No. 201410724713.2.
Filler in the elastic composites of the present invention, can be to grind modified white carbon, its aggregation grain
Footpath D50≤300nm, D90≤5um, silane coupler grafts on its surface, because modification is in fat
Carry out in the non-Aqueous organic solvent such as hydro carbons, alicyclic hydrocarbon type, arene, surface cleaning, do not have solvent to divide
The graft product of son.
Filler in the elastic composites of the present invention or the white carbon black after grinding, its aggregate particle size
D50≤4um, D90≤8um.
The rubber size that the present invention uses is polymerisation in solution synthetic rubber, can be Butadiene-Styrene Rubber, Rare-earth Cis
Fourth glue, cis-butadiene cement, rare-earth isoprene rubber, isoprene rubber etc..
It has following features：A) its filler is the white carbon of silane coupler graft modification, aggregation
Preferably at 100nm-5 μm, surface does not have the key compound of polarity organic molecule to particle diameter；Can also be to assemble
Body particle diameter is preferably in 1 μm -10 μm of white carbon black；B) it is through high pressure liquid by rubber glue with filler serosity
Mutually mix, dynamic dry method devolatilization and make；C) vulcanizate of this elastic composites preparation is adopted to pass with using
The vulcanizate of system calendering process preparation is compared, and dynamic mechanical significantly improves, and strength and extension property is good, and hardness is low.
Present invention also offers a kind of preparation method of this elastic composites is it is characterised in that adopt liquid-phase mixing
Prepared by dispersing technology, step includes：1) in non-polar organic solvent, make modified white carbon black slurry
Liquid or white carbon black grinding milk；2) filler serosity or filler are carried out in proportion with rubber glue under high energy shear
Dispersion mixing；3) dispersion mixing is uniformly combined somaplasm glue dry removal solvent in a dynamic state；4)
The complex of desolvation is carried out shearing kneading drying, obtains product.
The solvent that filler serosity adopts is that the nonpolar class such as fat hydrocarbon, alicyclic hydrocarbon type, arene is organic molten
Agent.
The solvent that rubber solutions adopt is that the nonpolar class such as fat hydrocarbon, alicyclic hydrocarbon type, arene is organic molten
Agent.
Step 1) in, if filler is white carbon, it is needed to be ground modification.Modifying agent is silane
Coupling agent, its consumption can be the 2-50% of white carbon consumption, typically in 10-15%.The grinding of white carbon changes
Property point multistage in non-polar organic solvent carry out, temperature is at 50-150 DEG C.In modified white carbon black serosity, change
Property white carbon solid content can be 5%～20%, usual amounts be 10-15%；If filler is white carbon black, only
Multistage grinding is carried out to it.In carbon black slurry, the solid content of white carbon black can be 5%～15%, and usual amounts are
5-10%.It is multiple that the method for multistage grinding includes high shear mechanical lapping and the injection punching wound pulverizing of high pressure high energy etc.
Mode.In the filler serosity made, preferably at 100nm-5 μm, white carbon black gathers the particle diameter of white carbon aggregation
The particle diameter of collective is preferably at 1 μm -8 μm.
Step 2) in, can be by 1) in make filler serosity add rubber glue in, it is possible to use
1) method in grinds modified filler, then removes solvent, directly dry powder filler is added rubber glue.
The concentration of rubber glue can be 5%～30%, conventional solubility 15-20%.By rubber solutions and filler or fill out
Slip liquid sends into high energy dispersion equipment by a certain percentage, under high pressure effect, through turbulent flow, cavitation erosion, collision etc.
Shearing force and extruding force, filler aggregation is pulverized further and is in close contact with rubber molecule, obtains filler and exists
Finely dispersed mixed liquor in rubber.In mixed liquor, ratio in rubber for the filler can be 30-110phr,
Conventional ratio is 40-80phr.
Step 3) in, mixed liquor sent in dynamic dry method devolatilization equipment, in shearing, extrusion machinery power
Under effect, solvent removal, obtain complex.Dynamic dry method devolatilization equipment can be that one kind is provided with multistage decompression
The screw extruder of devolatilization mouth, at 40-100 DEG C, screw speed, at 100-250 rev/min, takes off temperature control
Complex volatile matters after waving<1%.
Step 4) in, the complex after devolatilization experiences mechanical kneading, the interaction of reinforcer and rubber.
Kneading process can be in banbury, masticator, continuous internal mixer, continuous masticator, double screw extruder,
Carry out in screw extruder or mill, other rubber chemicals, e.g., age resistor, processing aid, oil,
Vulcanizing activator etc. can be added in complex with here.
Raw material：
White carbon 1165MP, Que Cheng silication limited company；
White carbon black N234, Cabot Corporation；
Butadiene-Styrene Rubber 2557, Dushanzi petro-chemical corporation；
Si75, AG, Nanjing dawn Chemical Co., Ltd.；
Other rubber chemicals are commercially available laboratory reagent.
Test equipment：
Laboratory rubber mixing mill, banbury, vulcameter and vulcanizing press, are laboratory conventional machining
Equipment；Puller system, hardness tester, dynamic mechanical tester are laboratory traditional performance test equipment.
Embodiment 1
According to the modified white carbon black manufacture method disclosed in number of patent application 201410724713.2, make
Obtain the modified white carbon black serosity that white carbon aggregate particle size is 100nm-5 μm, solid content is 5%wt.
In high energy dispersion machine, above-mentioned for 13.5kg modified white carbon black serosity and 6.8kg concentration are 20%wt
Butadiene-Styrene Rubber glue mixed, the ratio of two of which solid content is, rubber：White carbon=100:50.
High energy dispersion machine is evenly dispersed between rubber molecule while grinding white carbon, prepared complex
Mixed liquor.
Complex mixed liquor is sent in devolatilization extrusion all-in-one and carries out solvent removal, all-in-one is extruded to devolatilization
The temperature range of upper eight blocks is set as 40-100 DEG C, and screw speed is 100 revs/min.Complex mixes
Liquid obtains complex after extruder, and its volatile content is less than 1%.
Using mill or banbury, kneading is carried out to complex, with promote in complex filler and rubber it
Between interaction.
Embodiment 2
According to the modified white carbon black manufacture method disclosed in number of patent application 201410724713.2, make
Obtain the modified white carbon black serosity that white carbon aggregate particle size is 100nm-5 μm, solid content is 10%wt.
In high energy dispersion machine, above-mentioned for 9kg modified white carbon black serosity and 22.5kg concentration are the molten of 5%wt
Poly- butadiene-styrene rubber glue is mixed, and the ratio of two of which solid content is, rubber：White carbon=100:80.High
Can dispersion machine be evenly dispersed between rubber molecule while grinding white carbon, prepared complex mixes
Close liquid.
Complex mixed liquor is sent in devolatilization extrusion all-in-one and carries out solvent removal, all-in-one is extruded to devolatilization
The temperature range of upper eight blocks is set as 40-100 DEG C, and screw speed is 150 revs/min.Complex mixes
Liquid obtains complex after extruder, and its volatile content is less than 1%.
Using mill or banbury, kneading is carried out to complex, with promote in complex filler and rubber it
Between interaction.
Embodiment 3
According to the modified white carbon black manufacture method disclosed in number of patent application 201410724713.2, make
Obtain the modified white carbon black serosity that white carbon aggregate particle size is 100nm-5 μm, solid content is 20%wt.
In high energy dispersion machine, above-mentioned for 5.3kg modified white carbon black serosity and 19.3kg concentration are 5%wt's
Butadiene-Styrene Rubber glue is mixed, and the ratio of two of which solid content is, rubber：White carbon=100:110.
High energy dispersion machine is evenly dispersed between rubber molecule while grinding white carbon, prepared complex
Mixed liquor.
Complex mixed liquor is sent in devolatilization extrusion all-in-one and carries out solvent removal, all-in-one is extruded to devolatilization
The temperature range of upper eight blocks is set as 40-100 DEG C, and screw speed is 200 revs/min.Complex mixes
Liquid obtains complex after extruder, and its volatile content is less than 1%.
Using mill or banbury, kneading is carried out to complex, with promote in complex filler and rubber it
Between interaction.
Embodiment 4
According to the modified white carbon black manufacture method disclosed in number of patent application 201410724713.2, make
Obtain the modified white carbon black serosity that white carbon aggregate particle size is 100nm-5 μm, solid content is 5%wt.
In high energy dispersion machine, above-mentioned for 9kg modified white carbon black serosity and 5kg concentration are the molten of 30%wt
Poly- butadiene-styrene rubber glue is mixed, and the ratio of two of which solid content is, rubber：White carbon=100:30.High
Can dispersion machine be evenly dispersed between rubber molecule while grinding white carbon, prepared complex mixes
Close liquid.
Complex mixed liquor is sent in devolatilization extrusion all-in-one and carries out solvent removal, all-in-one is extruded to devolatilization
The temperature range of upper eight blocks is set as 40-100 DEG C, and screw speed is 150 revs/min.Complex mixes
Liquid obtains complex after extruder, and its volatile content is less than 1%.
Using mill or banbury, kneading is carried out to complex, with promote in complex filler and rubber it
Between interaction.
Embodiment 5
According to the modified white carbon black manufacture method disclosed in number of patent application 201410724713.2, make
Obtain the modified white carbon black that white carbon aggregate particle size is 100nm-5 μm.
In high energy dispersion machine, above-mentioned for 0.65kg modified white carbon black dry powder and 6.5kg concentration are 20%wt
Butadiene-Styrene Rubber glue mixed, the ratio of two of which solid content is, rubber：White carbon=100:50.
High energy dispersion machine is evenly dispersed between rubber molecule while grinding white carbon, prepared complex
Mixed liquor.
Complex mixed liquor is sent in devolatilization extrusion all-in-one and carries out solvent removal, all-in-one is extruded to devolatilization
The temperature range of upper eight blocks is set as 40-100 DEG C, and screw speed is 150 revs/min.Complex mixes
Liquid obtains complex after extruder, and its volatile content is less than 1%.
Using mill or banbury, kneading is carried out to complex, with promote in complex filler and rubber it
Between interaction.
Embodiment 6
Ground using high energy dispersion machine and carbon black slurry is obtained, solid content is 5%wt, wherein carbon black aggregate
Particle diameter is 1 μm -5 μm.
In high energy dispersion machine, above-mentioned for 14.5kg carbon black slurry and 6.6kg concentration are containing intermingle with of 20%wt
Butadiene-styrene rubber glue is mixed, and the ratio of two of which solid content is, rubber：White carbon black=100:55.High energy divides
Scattered machine is evenly dispersed between rubber molecule while grinding white carbon black, prepared complex mixed liquor.
Complex mixed liquor is sent in devolatilization extrusion all-in-one and carries out solvent removal, all-in-one is extruded to devolatilization
The temperature range of upper eight blocks is set as 40-100 DEG C, and screw speed is 100 revs/min.Complex mixes
Liquid obtains complex after extruder, and its volatile content is less than 1%.
Using mill or banbury, kneading is carried out to complex, with promote in complex filler and rubber it
Between interaction.
Embodiment 7
Ground using high energy dispersion machine and carbon black slurry is obtained, solid content is 10%wt, wherein carbon black aggregate
Particle diameter is 1 μm -5 μm.
In high energy dispersion machine, above-mentioned for 6.5kg carbon black slurry and 26kg concentration are the solution polymerized butylbenzene of 5%wt
Glue glue is mixed, and the ratio of two of which solid content is, rubber：White carbon black=100:50.High energy dispersion machine
It is evenly dispersed between rubber molecule while grinding white carbon black, prepared complex mixed liquor.
Complex mixed liquor is sent in devolatilization extrusion all-in-one and carries out solvent removal, all-in-one is extruded to devolatilization
The temperature range of upper eight blocks is set as 40-100 DEG C, and screw speed is 200 revs/min.Complex mixes
Liquid obtains complex after extruder, and its volatile content is less than 1%.
Using mill or banbury, kneading is carried out to complex, with promote in complex filler and rubber it
Between interaction.
Embodiment 8
Ground using high energy dispersion machine and carbon black slurry is obtained, solid content is 15%wt, wherein carbon black aggregate
Particle diameter is 1 μm -5 μm.
In high energy dispersion machine, above-mentioned for 4.5kg carbon black slurry and 27kg concentration are the solution polymerized butylbenzene of 5%wt
Glue glue is mixed, and the ratio of two of which solid content is, rubber：White carbon black=100:50.High energy dispersion machine
It is evenly dispersed between rubber molecule while grinding white carbon black, prepared complex mixed liquor.
Complex mixed liquor is sent in devolatilization extrusion all-in-one and carries out solvent removal, all-in-one is extruded to devolatilization
The temperature range of upper eight blocks is set as 40-100 DEG C, and screw speed is 150 revs/min.Complex mixes
Liquid obtains complex after extruder, and its volatile content is less than 1%.
Using mill or banbury, kneading is carried out to complex, with promote in complex filler and rubber it
Between interaction.
Embodiment 9
In high energy dispersion machine, above-mentioned for 0.65kg modified carbon black dry powder and 6.5kg concentration are 20%wt's
Butadiene-Styrene Rubber glue is mixed, and the ratio of two of which solid content is, rubber：White carbon black=100:50.High
Can dispersion machine be evenly dispersed between rubber molecule while grinding white carbon black, prepared complex mixing
Liquid.
Complex mixed liquor is sent in devolatilization extrusion all-in-one and carries out solvent removal, all-in-one is extruded to devolatilization
The temperature range of upper eight blocks is set as 40-100 DEG C, and screw speed is 100 revs/min.Complex mixes
Liquid obtains complex after extruder, and its volatile content is less than 1%.
Using mill or banbury, kneading is carried out to complex, with promote in complex filler and rubber it
Between interaction.
Comparative example 1
The preparation of all comparative examples, according to tradition routine mixing program, is mixed using 1.6 liters of banburies
Refining, program such as table 1：
The traditional dry pigmentation complex mixing program of table 1.
1. banbury program：Rotor revolution number：80rpm；Ram piston pressure：2.8bar；Open cooling water
2. mill program：Bowl temperature：Front rolling 32 degree；Roll 38 degree afterwards
Complex performance is evaluated
1. vulcanizate formula
Comparative example is identical with the vulcanizate formula of embodiment, is shown in Table 2.
Table 2. vulcanizate formula
2. knead
All using two-stage mixing, mixing program is shown in Table 3 to two species complexs (embodiment and comparative example).
Table 3. complex kneads program
One section of mixing program：
1. banbury program：Rotor revolution number：80rpm；Ram piston pressure：2.8bar；Open cooling water
Terminal section kneads program：
1. banbury program：Rotor revolution number：60rpm；Ram piston pressure：2.8bar；Open cooling water
2. mill program：Bowl temperature：Front rolling 32 degree；Roll 38 degree afterwards
3. performance
The vulcanizate of wet method mixing preparation is listed in table 4 with the performance of the vulcanizate of conventional dry mixing preparation.
Table 4. cured properties
The cured properties of the complex that contrast same recipe Different Preparation makes, uses wet method calendering process
The vulcanizate making, in processing characteristics and curability, the vulcanizate being made with traditional dry mixing process is not had
Very big difference, but in hardness, strength and extension property and dynamic mechanical are better than traditional dry mixing process preparation
Vulcanizate.Therefore, on tire and the existing process units of products factory, using liquid phase mixing complex it is
Raw material makes product, and not only technique simplifies, and energy-conserving and environment-protective are moreover it is possible to enhance product performance.
Claims (11)
1. a kind of elastic composites, including following components：Polymerisation in solution synthetic rubber and filler, described fill out
Expect for modified white carbon black or white carbon black；The ratio of rubber and filler is 100:30～110；Filler aggregate particle size is
100nm-10μm；Described elastic composite production procedure comprises the steps：
(1) in non-polar organic solvent, modified white carbon black grinding milk or white carbon black grinding milk are made,
Modified white carbon black grinding milk or white carbon black grinding milk are denoted as filler serosity, modified white carbon black or white carbon black are denoted as
Filler；
(2) above-mentioned filler serosity or filler carry out dispersion mixing in proportion with rubber glue under high energy shear,
Form compound somaplasm glue；
(3) above-mentioned dispersion mixing is uniformly combined somaplasm glue dry removal solvent in a dynamic state；
(4) complex of above-mentioned desolvation is carried out shearing kneading drying, obtain product；
Wherein, non-polar organic solvent described in step (1), rubber glue solvent for use in step (2)
It is fat hydrocarbon, alicyclic hydrocarbon type or arene non-polar organic solvent.
2. elastic composites according to claim 1 it is characterised in that：Described rubber and filler
Ratio is 100:40-80.
3. elastic composites according to claim 1 it is characterised in that：Described modified white carbon black gathers
Collective's particle diameter is 100nm-5 μm.
4. elastic composites according to claim 1 it is characterised in that：Described carbon black aggregate grain
Footpath is 1 μm -10 μm.
5. elastic composites according to claim 1 it is characterised in that：Described rubber is to contain intermingle with fourth
Benzene glue, rare earth cis-butadiene cement, cis-butadiene cement, rare-earth isoprene rubber or isoprene rubber.
6. the elastic composites according to any one of Claims 1 to 5 it is characterised in that：Step (1)
Described in non-polar organic solvent, in step (2) rubber glue solvent for use be respectively pentane, Pentamethylene.,
Hexane, hexamethylene, heptane, toluene or petroleum ether.
7. the elastic composites according to any one of Claims 1 to 5 it is characterised in that：Modified Linesless charcoal
In black wash liquid, the solid content of modified white carbon black is 5%～20%；In carbon black slurry, the solid content of white carbon black is
5%～15%.
8. elastic composites according to claim 7 it is characterised in that：In modified white carbon black serosity,
The solid content of modified white carbon black is 10-15%；In carbon black slurry, the solid content of white carbon black is 5-10%.
9. the elastic composites according to any one of Claims 1 to 5 it is characterised in that：Step (2)
The concentration of middle rubber glue is 5%～30%.
10. elastic composites according to claim 9 it is characterised in that：Rubber in step (2)
The concentration of glue is 15-20%.
11. elastic composites according to any one of Claims 1 to 5 it is characterised in that：Step (3)
In dynamically descend the equipment of dry removal solvent to have multistage to reduce pressure the screw extruder of devolatilization mouth, temperature control exists
40-100 DEG C, the complex volatile matters at 100-250 rev/min, after devolatilization for the screw speed<1%.
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| CN107216504A (en) * | 2017-07-31 | 2017-09-29 | 中国皮革和制鞋工业研究院（晋江）有限公司 | A kind of high abrasion rare-earth rubber material for shoes and preparation method thereof |
| CN110092953A (en) * | 2019-02-22 | 2019-08-06 | 益凯新材料有限公司 | A kind of smart dispersing method of new packing in synthesis glue |
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| CN103205001A (en) * | 2013-01-10 | 2013-07-17 | 怡维怡材料研究院有限公司 | Dispersion method for filling material in rubber solution |
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| CN102153792A (en) * | 2011-03-17 | 2011-08-17 | 株洲安宝麟锋新材料有限公司 | Preparation method of wet process mixed natural rubber material |
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| CN110092953A (en) * | 2019-02-22 | 2019-08-06 | 益凯新材料有限公司 | A kind of smart dispersing method of new packing in synthesis glue |
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