Disperse pad glue sizing material of white carbon black latex mixture and its preparation method and application containing liquid phase
Technical field
The present invention relates to rubber for tire sizing material production field, relate in particular to a kind of pad glue sizing material and its preparation method and application.
Background technology
Natural gum is widely used in tire industry and rubber industry because it has good physical and mechanical properties.Due to natural gum molecular weight high (molecular-weight average is 700,000 left and right), mixing by traditional dry method, first to plasticate to natural gum (reducing molecular weight by mechanical force and high temperature degradation) then in mechanical shear history, add required carbon black, white carbon black and other activators, anti-aging agent, vulcanizing agent.The macromole of natural gum is badly damaged in this course, so that powerful wear hardness declines.For making up decline powerful and abrasion.The a large amount of particle diameters that adopt of designer tradition are little, the in addition reinforcement of the large hard (carbon) black of specific surface area.Although powerful like this and abrasion can improve, sizing material heat-dissipating amount also improves thereupon thereupon.So that tire causes the empty and shoulder sky of early stage hat running at high speed because heat-dissipating is high.In order to reduce heat-dissipating, often add a small amount of white carbon black.White carbon black has the advantages that heat-dissipating is low, wet-sliding resistant performance is good.
The method of conventional dry compounding process a kind of acceptor modified white carbon black enhancing truck tyre pad colloidality energy as Chinese invention patent application (application number: 200910050337.2 applyings date: 2009-04-30) discloses, the method is: Nano carbon white is removed moisture through 120 ℃ of vacuum-dryings, carry out coupling agent surface treatment, the consumption of coupling agent is Nano carbon white powder weight 1%~10%; Keeping on the basis that the original production formula of rubber is constant and Production Flow Chart is constant, in rubber mixing process, add 20%~30% Nano carbon white composite granule after coupling agent modified of rubber weight, test result shows, the tensile strength, tear strength, hardness etc. of adding truck tyre pad glue after composite Nano white carbon black powder increase substantially.And mixing brute force and the wear resisting property that adds the white carbon black of volume certainly will affect sizing material of application conventional dry.
But there are two deadly defects with conventional dry compounding process: the one, white carbon black is that hydrophilic inorganics is difficult to be added in hydrophobic natural gum, must carry out too mixing (increasing mixing hop count), the globality that must destroy like this rubber molecular chain, has caused powerful reduction.The mixing integraty that cannot form natural gum and white carbon black of white carbon black application dry method in addition.The sizing material of the white carbon black of so a large amount of fillings obtains less than high-wearing feature.In a word, add the hard (carbon) black of a large amount of high-specific surface areas can obtain the rubber unvulcanizate compared with high-tenacity, but can cause undoubtedly sizing material heat-dissipating excessive, rolling resistance is high.And use the preparation method of the white carbon black natural gum of liquid phase paddling process mixing can make up above-mentioned two deficiencies completely.
Liquid phase paddling process blending means discloses a kind of preparation method of wet process mixed natural rubber material as Chinese invention patent application (application number: 201110064299.3 applyings date: 2011-03-17), its method comprises: preparation slurry 15%~40% white carbon black siccative is immersed in 60%~85% deionized water, add coupling agent, tensio-active agent mixes to grind produces latex mixed solution-get natural rubber latex-white carbon black water dispersion is joined in latex, be uniformly mixed into latex mixed solution-flocculation-add acetic acid in mixed solution, wash glue and dehydration-deliver to rubber comminutor granulation through rubber washing machine, then sizing material grain is sent in box-type drying cabinet and is dried.The tire drag that adopts the method to manufacture is little, and heat-dissipating is low, and tensile strength and tearing strength are high, and the ageing-resistant performance of sizing material is good.Realized the mixing of white carbon black and carried out in liquid phase, dispersed and homogeneity improves.But white carbon black slurry need adopt deionized water to soak in this patent, meanwhile, in the course of processing, needing, through grinding, has increased processing step like this, has improved production cost; In addition,, in whipping process, there will be and condense for natural rubber latex, occur macrobead, cause mixing inhomogeneous.
Applicant has applied for that Chinese invention patent (applying on the same day patent of invention) discloses a kind of liquid phase and be uniformly mixed the preparation method of white carbon black and natural gum, and the method comprises the following steps:
1) slurry preparation
The preparation of first component:
The liquid white carbon black of solid content 10% ~ 50%, white carbon black is in 5 ~ 120 parts of siccatives;
Add 0.5% ~ 8% silane coupling agent of white carbon black siccative weight, 0.1% ~ 2.0% stablizer, 0.1% ~ 2.0% anti-settling agent, 0.1% ~ 2.0% dispersion agent, stirs: speed 1000 ~ 4000rpm, churning time 2 ~ 10 minutes;
The preparation of second component:
The natural rubber latex of solids content 20% ~ 70%, natural rubber latex is in 100 parts of siccatives;
Add the stablizer of natural rubber latex siccative weight 0.1% ~ 2.0%, stir: rotating speed 1000-4000rpm, stirs 1~5 minute;
2) mix
In second component high-speed stirring, add first component, stirring velocity 2000 ~ 6000rpm, stirring at normal temperature 8 ~ 20 minutes;
3) solidify, dewater, wash
1. in the mixed solution after mixing, slowly add the peptizer through diluting, add-on is that the peptizer of mixed solution weight 0.01% ~ 1.5% solidifies, and reclaims raffinate;
2. the sizing material after solidifying first squeezes out partial coagulation liquid recycling with press, then the sizing material after extruding is pushed on rubber breaker, extrudes solidification liquid, and reclaims, and the sizing material after rubber breaker extruding carries out fragmentation, washing, and centrifuge dewatering, dries.
The liquid phase that this patent of invention obtains disperses white carbon black latex mixture to have following beneficial effect:
1, this invention adopts liquid-liquid high-speed stirring to mix and has effectively preserved the macromolecular original state of natural gum, makes the brute force of natural gum be able to effective reservation;
2, the mixing of liquid-liquid high-speed stirring has realized the even integraty of rubber and white carbon black effectively, thereby has increased substantially brute force and the wear resistance of epoxy glue;
3, liquid-liquid high-speed stirring is mixed the dust from flying thoroughly having solved when mixing, has obviously improved Working environment;
4, apply the sizing material brute force that this method mixes and significantly promote, heat generation and hysteresis loss obviously reduce;
5, apply the epoxy glue that this method produces and can be used alone, also can be in any proportion and natural gum, synthetical glue and natural gum carbon black rubber master batch, synthetical glue carbon black rubber master batch is also used;
6, this invention is directly uniformly mixed with liquid phase white carbon black and liquid phase natural gum, and its technique is simple, and floor space is little, and facility investment is low, no dust pollution in production process.Each rubber molding plant is easy to use, is specially adapted to tire plant.
And wear-resisting for the general design requirements of all-steel tire tread, anti-slippery, low rolling resistance.But these three performances restrict mutually, often improve wherein some performances and can more or less sacrifice two other performance, be difficult to get a promotion simultaneously.The tyre surface of the wear-resisting all-steel load-bearing radial tire of having relatively high expectations at present, what filler used substantially is super abrasion furnace black.Sometimes in order to take into account thermogenesis performance, reduce the empty ratio of shoulder, also have and use 10 ~ 15 parts of white carbon blacks, but wear hardness declines greatly.All steel load tire tread uses the carbon black of high-specific surface area in order to pursue abrasion in general, certainly will make tyre surface hysteresis loss increase, and thermogenesis performance declines, endurance quality variation.No matter be that Chinese invention patent application (application number: 201110064299.3 applyings date: 2011-03-17) or the liquid phase of applicant's application are disperseed white carbon black latex mixture, both take into account, heat-dissipating declines to a great extent, and wears away also increase (indoor wear test).More estimable is also most important, and rolling resistance significantly declines.
Summary of the invention
In order to adopt white carbon black replacing whole or most of alternative carbon black, to reduce the rolling resistance of tire, improve anti-slippery and wear resisting property, to produce energy-conserving and environment-protective tire.First object of the present invention is to provide a kind of pad glue sizing material that disperses white carbon black latex mixture containing liquid phase, should contain liquid phase and disperse not only to make heat-dissipating decline to a great extent after the pad glue rubber vulcanization of white carbon black latex mixture, and rolling resistance significantly declines.Second object of the present invention is to provide the preparation method of the above-mentioned pad glue sizing material containing liquid phase dispersion white carbon black latex mixture.The 3rd object of the present invention is to provide the application of the above-mentioned pad glue sizing material containing liquid phase dispersion white carbon black latex mixture.
In order to realize first above-mentioned object, the present invention has adopted following technical scheme:
Disperse the pad glue sizing material of white carbon black latex mixture containing liquid phase, this sizing material by weight by following component through over-mastication, mixing making:
Above-mentioned liquid phase adds the natural rubber latex of stablizer to mix after disperseing white carbon black latex mixture to add silane coupling agent, stablizer, anti-settling agent and dispersant by liquid white carbon black, after liquid phase method disperses, solidify through peptizer, push again, fragmentation, washing, dehydration, oven dry makes, and it is 5~120:100 with the siccative ratio of natural rubber latex that liquid phase is disperseed white carbon black in white carbon black latex mixture; In above-mentioned liquid phase dispersion white carbon black latex mixture, the dry weight of natural rubber latex and the summation of natural rubber are counted 100 parts; It is 40 ~ 60 parts that liquid phase is disperseed the summation of white carbon black in white carbon black latex mixture and described carbon black.As preferably, this sizing material comprises by weight:
As preferably, it is 40 ~ 60:100 with the siccative ratio of natural rubber latex that liquid phase is disperseed white carbon black in white carbon black latex mixture.
In order to realize second above-mentioned object, the present invention has adopted following technical scheme:
A preparation method who prepares the above-mentioned pad glue sizing material containing liquid phase dispersion white carbon black latex mixture, the method comprises the following steps:
(1) section of plasticating
Add liquid phase and disperse white carbon black latex mixture, stearic acid, nano zine oxide, Microcrystalline Wax, anti-aging agent RD and antioxidant 4020, rotor speed 40 ~ 50rpm presses to stick together and is retained to 130 ~ 150 ℃, carry 30 ~ 50 seconds rotor speed 20 ~ 40rpm of charging door exhaust that stick together out and press to stick together and keep 10 ~ 20 seconds to 140 ~ 160 ℃, carry 50 ~ 70 seconds rotor speed 20 ~ 30rpm of charging door exhaust that stick together out and press to stick together and be retained to 150 ~ 170 ℃ and carry the binder removal that sticks together;
(2) mixing 1 section
Add natural rubber, step () the plasticate sizing material, high aromatic oil, 204 resins, hardening filler 9010, the carbon black that obtain, rotor speed 40 ~ 50rpm presses to stick together and keeps 50 ~ 70 seconds to 130 ~ 150 ℃, carry the charging door that stick together out, exhaust 20 ~ 40 seconds, 30 ~ 50rpm presses to stick together and keeps 10 ~ 20 seconds, proposes the exhaust 30 ~ 50 seconds of opening the door that sticks together to 140 ~ 160 ℃, and 30 ~ 50rpm presses to stick together and is retained to 150 ~ 170 ℃ and carries the binder removal that sticks together;
(3) supplement mixing 2 sections
Throw the sizing material that step (two) obtains, rotor speed 30 ~ 50rpm presses to stick together and keeps carrying for 30 ~ 50 seconds sticking together, and rotor speed 30 ~ 40rpm presses to stick together and keeps carrying the binder removal that sticks together in 15 ~ 25 seconds to 140 ~ 160 ℃;
(4) add sulphur
Throw sizing material and insoluble sulfur OT20, vulcanization accelerator NS and short D that step (three) obtains, rotor speed 20 ~ 40rpm presses to stick together and keeps carrying for 20 ~ 40 seconds sticking together, and rotor speed 20 ~ 30rpm presses to stick together and keeps 15 ~ 5 seconds to 100 ~ 120 ℃.
The present invention is for plasticating, white carbon black-the latex mixture obtaining by the mixing method of liquid phase does not pass through shearing action, white carbon black phase and rubber phase do not form effective combination by silane coupling agent, white carbon black agglomeration together, rubber components is wrapped in white carbon black, make Mooney very high, be difficult to processing, need to be further mixing in Banbury mixer.
For mixer mixing, follow the tracks of discovery by scene, this mixture has obvious shear shinning feature, may be relevant with hydrogen bond, must guarantee in Banbury mixer white glue obtain fully mixing be fully heated could heat up simultaneously and open hydrogen bond Mooney is reduced guarantee dispersed, but often because of the cause of moisture skid make part white glue be stuck in rotor top can not get shearing cause disperse insufficient.After liquid phase mixture is dry, Mooney height very, so processing is very difficult, if directly drop into Banbury mixer with carbon black rubber master batch or other together with sulphur material, Yin Menni difference can make to disperse bad.Therefore the present invention preferably reduces the Mooney point of mixture early stage by plasticating, or the Mooney point of raising carbon black rubber master batch approaches both Mooneys.The hardness of comprehensive sizing material and proportion and Banbury mixer type are set suitable capacity.The selection of time that particularly easily causes the material skidding to add by rotor speed speed change, adjustment order of addition(of ingredients), improves rubber unvulcanizate dispersity.Certainly for making handling ease, also can add 2 parts of levelers, peptizer.When simultaneously mixing, preferably give silane coupling agent enough at least 3 minutes reaction times at 145 ℃ ~ 150 ℃.
As preferably, above-mentioned liquid phase disperses the preparation method of white carbon black latex mixture as follows:
1) slurry preparation
The preparation of first component:
The liquid white carbon black of solid content 10% ~ 50%, white carbon black is in 5 ~ 120 parts of siccatives;
Add 0.5% ~ 8% silane coupling agent of white carbon black siccative weight, 0.1% ~ 2.0% stablizer, 0.1% ~ 2.0% anti-settling agent, 0.1% ~ 2.0% dispersion agent, stirs: speed 1000 ~ 4000rpm, churning time 2 ~ 10 minutes;
The preparation of second component:
The natural rubber latex of solids content 20% ~ 70%, natural rubber latex is in 100 parts of siccatives;
Add the stablizer of natural rubber latex siccative weight 0.1% ~ 2.0%, stir: rotating speed 1000-4000rpm, stirs 1 ~ 5 minute;
2) mix
In second component high-speed stirring, add first component, stirring velocity 2000 ~ 6000rpm, stirring at normal temperature 8 ~ 20 minutes;
3) solidify, dewater, wash
1. in the mixed solution after mixing, slowly add the peptizer through diluting, add-on is that the peptizer of mixed solution weight 0.01% ~ 1.5% solidifies, and reclaims raffinate;
2. the sizing material after solidifying first squeezes out partial coagulation liquid recycling with press, then the sizing material after extruding is pushed on rubber breaker, extrudes solidification liquid, and reclaims, and the sizing material after rubber breaker extruding carries out fragmentation, washing, and centrifuge dewatering, dries.
As preferably, above-mentioned silane coupling agent is selected one or both mixing in two-[propyl-triethoxysilicane]-tetrasulfide, two-[propyl-triethoxysilicane]-disulphide.
As preferably, in above-mentioned step 1), to prepare the stablizer adding be 0.1% ~ 0.9% of white carbon black siccative weight to first component, and anti-settling agent is 0.1% ~ 0.9% of white carbon black siccative weight, and dispersion agent is 0.1% ~ 0.9% of white carbon black siccative weight; Stablizer selects one or more in condenses and N-methyl N-oleic acid acyl group ox acid sodium of potassium hydroxide, sodium hydroxide, ammoniacal liquor, lauric acid, casein, oxyethane and alcohol to mix; Anti-sedimentation agent is selected one or more mixing in sodium polyacrylate, tween and Si Ban; Dispersion agent is selected one or more mixing in methylene sodium dinaphthalenesulfonate, sodium dibutyl naphthalene sulfonate, methylene di-isopropyl sodium naphthalene sulfonate, methylene potassium diisopropyl naphthalene sulfonate and trisodium phosphate.
As preferably, in above-mentioned step 1), to prepare the stablizer adding be 0.1% ~ 0.9% of natural rubber latex siccative weight to second component; Stablizer selects one or more in condenses and N-methyl N-oleic acid acyl group ox acid sodium of potassium hydroxide, sodium hydroxide, ammoniacal liquor, lauric acid, casein, oxyethane and alcohol to mix.
As preferably, in above-mentioned step 3), the add-on of peptizer is 0.1% ~ 0.5%; Peptizer is selected one or more mixing in hydrochloric acid, sulfuric acid, acetic acid, formic acid, calcium chloride, nitrocalcite, fixing salt and polypropylene glycol.
In order to realize the 3rd above-mentioned object, the present invention has adopted following technical scheme:
A kind of base portion of this tire of tire adopts the above-mentioned pad glue rubber vulcanization containing liquid phase dispersion white carbon black latex mixture to make.
The present invention, owing to adopting white carbon black replacing whole or most of alternative carbon black, to reduce the rolling resistance of tire, improves anti-slippery and wear resisting property, to produce energy-conserving and environment-protective tire.But, it should be noted that owing to adopting liquid phase to disperse white carbon black latex mixture, white carbon black has a very strong delayed effect to sulfuration, has not only affected original performance of formula due to the existence of moisture and acid simultaneously, and may cause producing in tire production defect.The existence of acid has also reduced sulfuration effect, must just can make up by promotor increment.Keep better even also having the phenomenon of aging aberration rate as positive number take liquid phase mixture as main formula aged properties, illustrate that in this process, crosslinking reaction is also continuing.Existence and the white carbon black adsorption of acid, also greatly reduce the effect of promotor.
Embodiment
Embodiment 1
Adopt centrifugal concentrating natural rubber latex and white carbon black slurry
A, preparation slurry
A component
Formula |
Composition (%) |
White carbon black slurry (25% content) |
85.47 |
Water |
13.33 |
Si69 |
0.66 |
Stablizer |
0.410 |
Anti-settling agent |
0.020 |
Dispersion agent |
0.103 |
B component
Formula |
Composition (%) |
Concentrated natural latex |
56.31 |
Stablizer |
0.54 |
Water |
43.15 |
Each comfortable 1500 ~ 2500rpm stirs 2 ~ 5 minutes.
B, mix and blend slowly add A component in B component high-speed stirring, and the mass ratio of A component and B component is 0.8:1, and stirring velocity, at 2000 ~ 6000rpm, stirs 10 minutes.
C, in compound, slowly add 0.3kg Glacial acetic acid, moment solidifies.
D, press filtration are pressed on press, squeeze out partially liq, reclaim.
E, roll compacting, all have at front and back roller on the rubber breaker of tooth and roll 3 ~ 5 times, squeezes out remaining liq, reclaims.
F, pulverizing, be equipped with on the crusher cutting be in length and breadth ground into≤1mm
3particle.
G, washing, the unnecessary extremely neutrality of acetic acid of washing neutralization in the water that is 7.5 ~ 8.5 with PH.
H, dehydration, dry surperficial moisture with water extracter whizzer.
J, oven dry, at external indirect steam thermal source, dry to finished product on the box-type drying streamline with gas blower circulation.
Embodiment 2
Adopt the fresh glue and the white carbon black slurry that directly gather from rubber tree
A, preparation slurry
A component
Formula |
Composition (%) |
White carbon black slurry (25% content) |
85.47 |
Water |
13.33 |
Si69 |
0.66 |
Stablizer |
0.410 |
Anti-settling agent |
0.020 |
Dispersion agent |
0.103 |
B component
Formula |
Composition (%) |
Fresh glue |
99.056 |
Stablizer |
0.944 |
Water |
|
Each comfortable 1500 ~ 2500rpm stirs 2 ~ 5 minutes.
B, mix and blend slowly add A component in B component high-speed stirring, and the mass ratio of A component and B component is 1:1, and stirring velocity, at 2000 ~ 6000rpm, stirs 10 minutes.
C, in compound, slowly add 0.3kg Glacial acetic acid, moment solidifies.
D, press filtration are pressed on press, squeeze out partially liq, reclaim.
E, roll compacting, all have at front and back roller on the rubber breaker of tooth and roll 3 ~ 5 times, squeezes out remaining liq, reclaims.
F, pulverizing, be equipped with on the crusher cutting be in length and breadth ground into≤1mm
3particle.
G, washing, the unnecessary extremely neutrality of acetic acid of washing neutralization in the water that is 7.5 ~ 8.5 with PH.
H, dehydration, dry surperficial moisture with water extracter whizzer.
J, oven dry, at external indirect steam thermal source, dry to finished product on the box-type drying streamline with gas blower circulation.
Embodiment 3 ~ 5
Disperse the pad glue sizing material of white carbon black latex mixture containing liquid phase, this sizing material comprises the component of following table by weight, wherein comparative example is for adopting natural rubber and carbon black is mixing forms, and embodiment 3 ~ 5 disperses white carbon black latex mixture (representing with LNSC in table) to add or do not add natural rubber and carbon black is mixing forms for the liquid phase that adopts embodiment 1 or embodiment 2 and make.
Pad glue sizing material mixing the preparing by the following method of disperseing white carbon black latex mixture containing liquid phase of the above embodiments 3 ~ 5:
(1) section of plasticating
Add liquid phase and disperse white carbon black latex mixture, stearic acid, nano zine oxide, Microcrystalline Wax, anti-aging agent RD and antioxidant 4020, rotor speed 45rpm presses to stick together and is retained to 140 ℃, carry the 40 seconds rotor speed 30rpm of charging door exhaust that stick together out and press to stick together and keep 15 seconds to 150 ℃, carry the 60 seconds rotor speed 25rpm of charging door exhaust that stick together out and press to stick together and be retained to 160 ℃ and carry the binder removal that sticks together;
(2) mixing 1 section
Add natural rubber, step () the plasticate sizing material, high aromatic oil, 204 resins, hardening filler 9010, the carbon black that obtain, rotor speed 45rpm presses to stick together and keeps 60 seconds to 140 ℃, carry the charging door that stick together out, 30 seconds (oiling) 40rpm of exhaust press to stick together and keep 15 seconds, propose the exhaust 40 seconds of opening the door that sticks together to 150 ℃, 40rpm presses to stick together and is retained to 160 ℃ and carries the binder removal that sticks together;
(3) supplement mixing 2 sections
Throw the sizing material that step (two) obtains, rotor speed 40rpm presses to stick together and keeps carrying for 40 seconds sticking together, and rotor speed 35rpm presses to stick together and keeps carrying the binder removal that sticks together in 20 seconds to 150 ℃;
(4) add sulphur
Throw sizing material and insoluble sulfur OT20, vulcanization accelerator NS and short D that step (three) obtains, rotor speed 30rpm presses to stick together and keeps carrying for 30 seconds sticking together, and rotor speed 25rpm presses to stick together and keeps 20 seconds to 110 ℃.
Test example
The product that above-mentioned comparative example and embodiment 3 ~ 5 are prepared vulcanizes, and the test data of the product that sulfuration obtains is as follows:
2, dynamic property