CN115010987B - Low-hysteresis carbon black and preparation method thereof - Google Patents
Low-hysteresis carbon black and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a low-hysteresis carbon black, which comprises the following components: 80-90 parts of strawberry type core-shell rubber compound/white carbon black: 10-19.5 parts of lignin: 0-0.5 parts. The preparation method comprises the steps of dispersing strawberry type core-shell rubber compound/white carbon black in water, uniformly mixing the mixture with lignin aqueous solution after uniform dispersion, mixing the mixture with carbon black in a granulator, granulating, and then drying the mixture in a low-temperature vacuum dryer until the water content is less than or equal to 1%. The invention has the advantages that: the low-hysteresis carbon black has excellent wet skid resistance and lower rolling resistance, and compared with other double-phase carbon black, the low-hysteresis carbon black has the advantages that the wet skid resistance is improved by about 10-13%, and the rolling resistance is reduced by about 16-19%.
Description
Technical Field
The invention relates to the technical field of carbon black preparation, in particular to low-hysteresis carbon black and a preparation method thereof.
Background
The carbon black is a common reinforcing material for tires, has larger rolling resistance and lower wet skid resistance, causes higher energy consumption and lower safety of motor vehicles, and does not meet the requirements of green development in society. The white carbon black has the characteristics of excellent safety performance and low energy consumption, meets the requirement of green development, has poor compatibility with rubber and poor mechanical properties, and is added into the carbon black to form the dual-phase carbon black low-hysteresis carbon black.
The Chinese patent application CN103467800A discloses tread rubber for a semi-steel radial tire of a car, which is mainly prepared by mixing white carbon black, rubber and related auxiliary agents by a physical mixing method, wherein the consumption of the white carbon black is 10-20 parts, so that the wear resistance, ageing resistance, puncture resistance and wet skid resistance of the tread are improved, and the tire has excellent low hysteresis property.
The Chinese patent application CN103665460A discloses a manufacturing method of wear-resistant base rubber for a solid tire of a crane truck, which mainly comprises natural rubber, liquid polybutadiene rubber, carbon black N234, white carbon black, a silane coupling agent and other auxiliary agents, wherein the white carbon black is mainly added into a system by physical mixing, and the obtained base rubber not only has higher modulus and good wear resistance, but also has better reversion resistance and lower low hysteresis.
The Chinese patent application CN104130478A discloses a tread rubber material for a low-hysteresis antistatic oil-saving tire and a preparation method thereof, the rubber composite material takes mixed rubber of solution polymerized styrene-butadiene rubber and butadiene rubber as matrix rubber, carbon nano tube bundles, white carbon black, a silane coupling agent, carbon black and other auxiliary agents are added, and the materials are mixed on an open mill or an internal mixer in stages, so that the dynamic loss factor of the materials under 60 ℃ and 7% dynamic strain is 0.14, and meanwhile, the mechanical property and the wear resistance of the materials are superior to or equivalent to those of conventional tread rubber materials, so that the rolling resistance of the tire is reduced, and meanwhile, the problem of static accumulation of high white carbon black tire materials is solved.
The Chinese patent application CN112080161A discloses a production process of the double-phase carbon black, which mainly comprises the following steps: the water content of the raw oil is reduced to below 2 percent, and the raw oil is mixed with combustion air flow in a reaction furnace under the condition that the temperature is higher than 1500 ℃; mixing silicon lattice powder with process water by a powder jet technology, and spraying into a carbon black reaction furnace; then under the action of carbon black aggregation, a double-phase carbon black aggregate is formed; and finally, collecting and separating the flue gas through a main bag filter, and storing the carbon black after drying. The finally formed dual-phase carbon black has excellent comprehensive performance.
In summary, there are two methods for making carbon black into a dual phase carbon black: firstly, physically mixing, namely uniformly mixing carbon black, silicon dioxide and a silane coupling agent under the stirring of mechanical force; second, silica is used as a silicon source and is added into the reaction furnace during the carbon black production stage to be combined with the carbon black. Both methods use a large amount of silica in the system, and use a large amount of silane coupling agent to improve the dispersibility thereof in order to increase the compatibility, dispersibility and binding force of silica in rubber. From the physical mixing mode, the aggregated particles of the white carbon black are finally dispersed to be about 6-12 mu m, and the primary particle size is about 20-100 nm, so that when the white carbon black plays a role, a large number of particles in the white carbon black do not play a role, a large amount of white carbon black is wasted, the surface of the white carbon black is smooth, the roughness is low, the binding force is weak, the capability of puncturing a water film is weak, and the wet skid resistance is low.
Disclosure of Invention
The invention aims to remedy the defects and discloses a low-hysteresis carbon black with excellent wet skid resistance, lower rolling resistance and strong binding force with rubber and a preparation method thereof to society.
The technical scheme of the invention is realized as follows:
a low hysteresis carbon black comprising the following components:
carbon black: 80-90 parts;
strawberry type core-shell rubber compound/white carbon black: 10 to 19.5 portions;
lignin: 0 to 0.5 part.
As an improvement, the carbon black is soft carbon black or hard carbon black.
A preparation method of low-hysteresis carbon black comprises the steps of dispersing strawberry type core-shell rubber compound/white carbon black in water, uniformly mixing the mixture with lignin aqueous solution after uniform dispersion, mixing the mixture with carbon black in a granulator, granulating, and then drying the mixture in a low-temperature vacuum dryer until the water content is less than or equal to 1%.
The strawberry type core-shell rubber compound/white carbon black comprises the following components:
synthetic rubber: 25-40 parts;
natural rubber: 12-20 parts;
zinc oxide: 4-6 parts;
stearic acid: 2-4 parts;
anti-aging agent: 1-2 parts;
carbon black: 25-40 parts;
and (3) an accelerator: 0.9 to 1.5 portions;
sulfur: 6-9 parts;
white carbon black: 8-20 parts;
sulfur-containing silane coupling agent: 0.2 to 1.2 portions.
The preparation method of the strawberry type core-shell rubber compound/white carbon black comprises the following steps:
step one, preparing a rubber compound:
1a) Adjusting the roller spacing to 1.1mm, adjusting the surface temperature of the roller to 50+/-5 ℃, adding synthetic rubber and natural rubber to the front roller, and making a 3/4 cutter every 30s, wherein the steps are alternately performed from the two ends of the roller for 2min;
2a) Slowly adding sulfur and uniformly covering on the rubber for 2min;
3a) Adding stearic acid, and alternately making 3/4 cutters at two ends for 2min;
4a) Adding carbon black into the roll coating at a constant speed, adjusting the roll spacing to 1.4mm when half of carbon black is mixed, making a 3/4 cutter once, and adding the rest carbon black; when all the carbon black is mixed, the roller spacing is adjusted to 1.8mm, and the two ends are alternately provided with 3/4 cutters once for 10min;
5a) When the roll gap is 1.8mm, zinc oxide, an anti-aging agent and an accelerator are added for 3min;
6a) The two ends are alternately provided with three times of 3/4 cutters for 3min;
7a) Cutting the sizing material from the roller, adjusting the roller spacing to be 0.8mm, and rolling the sizing material between the roller gaps for six times for 2min without wrapping the roller longitudinally;
8a) Adjusting the roll gap to enable the thickness of the sizing material sheet to be 6mm, discharging the sizing material sheet, and rechecking the weight of the sizing material;
9a) Adjusting the roll gap to enable the thickness of the sizing material sheet to be 2.2 mm;
10a) Crushing the rubber compound to 6-12 mu m by using a low-temperature freezing crusher;
step two, preparing a strawberry type core-shell rubber compound/white carbon black:
1b) Placing the crushed rubber compound into an open stirring tank, spraying KH550 ethanol solution into the system under stirring, stirring for 30-60 min, and dispersing into water to obtain a rubber compound particle dispersion;
2b) Grinding the micro-nano calcium carbonate by a grinder, adding the ground micro-nano calcium carbonate into the mixed rubber particle dispersion liquid, stirring the mixed rubber particle dispersion liquid at room temperature for 6-15 min, filtering the mixed rubber particle dispersion liquid, and dispersing the mixed rubber particle dispersion liquid in water for the second time;
3b) Slowly adding 20-40 wt.% of silicon source aqueous solution into the system, heating the system to 30-60 ℃, uniformly stirring, slowly introducing carbon dioxide gas, slowly dropwise adding the rest silicon source aqueous solution when the PH value is reduced to 12-13 for 2-4 h, and aging for 12-16 h after the dropwise adding is completed to form strawberry type core-shell rubber compound/white carbon black particles;
4b) Adding an acidic solution into the system, removing calcium carbonate, centrifugally washing strawberry type core-shell rubber compound/white carbon black particles, and re-dispersing in water;
5b) The strawberry type core-shell rubber compound/white carbon black particles are subjected to a vacuum homogenizing emulsifying machine to damage part of the shell structure, so that a small amount of shell fragments are formed;
6b) And (3) spray-drying the strawberry type core-shell rubber compound/white carbon black particles, then placing the mixture in an open dry-mixing tank, spraying the ethanol solution of the sulfur-containing silane coupling agent into the open tank under the condition of stirring, and uniformly stirring.
As an improvement, the accelerator adopts an accelerator NS.
As an improvement, the synthetic rubber is at least one of butadiene rubber or styrene butadiene rubber; the calcium carbonate is at least one of heavy calcium carbonate or light calcium carbonate, the grain diameter is 8000-12000 meshes, and the dosage is 1-10 wt.% of the mass of the rubber compound; the acidic solution is at least one of hydrochloric acid solution or sulfuric acid solution; the crushed grain size of the vacuum homogenizing emulsifying machine is 0.2-2 mu m, and the grinding is carried out for 2-3 times.
As an improvement, the silicon source is at least one of sodium silicate or potassium silicate, and the solution of sodium silicate or potassium silicate can be prepared by dissolving powder of sodium silicate or potassium silicate with any modulus in water or diluting aqueous solutions of sodium silicate or potassium silicate with different moduli; the mass of the silica shell layer is 8-20 wt.% of the rubber compound.
As an improvement, the sulfur-containing silane coupling agent is at least one of bis- [ gamma- (triethoxysilane) propyl ] tetrasulfide, bis- [3- (triethoxysilane) propyl ] -disulfide and 3-thiocyanopropyl triethoxysilane, and the preparation steps of the sulfur-containing silane solution are as follows: dissolving sulfur-containing silane in ethanol, stirring at a high speed, wherein the content of the sulfur-containing silane coupling agent is 5-50 wt.%, stirring uniformly, and standing for 5-30 min to obtain the final product, wherein the content of the sulfur-containing silane coupling agent is 0.2-1.2 wt.% of the strawberry type core-shell rubber compound/white carbon black.
As an improvement, the dispersion solution used in the ethanol solution of the sulfur-containing silane coupling agent is an ethanol and water mixture, and the ethanol content is 10-99.9 wt.%.
Compared with the prior art, the invention has the advantages that:
the low-hysteresis carbon black has excellent wet skid resistance and lower rolling resistance, and compared with other double-phase carbon black, the low-hysteresis carbon black has the advantages of about 10-13% improvement in wet skid resistance and about 16-19% reduction in rolling resistance. The low-hysteresis carbon black adopts strawberry type core-shell rubber compound/white carbon black, unvulcanized rubber compound is taken as a core, white carbon black is taken as a shell, calcium carbonate is taken as a shell breaking material, silicon source aqueous solution is intermittently dripped, shell white carbon black with rich mastoid structure (so called as strawberry type core-shell rubber compound/white carbon black) is formed on the surface of the rubber compound, firstly, the calcium carbonate is removed by using an acidic solution, the generated carbon dioxide is used for propping up the shell, and then the silicon dioxide is broken by using mechanical force, so that the rubber compound in the shell is exposed, and then the shell white carbon black is modified by using a sulfur-containing silane coupling agent. When the rubber is applied to rubber products, the inner and outer rubber mixtures are contacted with each other under the action of mechanical force in the mixing process, and are connected into a whole after vulcanization is finished, so that the low hysteresis property of the rubber is better exerted; the shell white carbon black has rich mastoid structures, and in the actual application scene, the mastoid structures are easier to puncture a water film, so that the wet skid resistance is further improved, the surface is modified with the sulfur-containing silane coupling agent, and the binding force with rubber is enhanced.
Drawings
FIG. 1 is a schematic illustration of the preparation of a strawberry type core-shell compound/white carbon black of the present invention;
FIG. 2 is an SEM image of a strawberry type core-shell compound/white carbon black of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings:
a low hysteresis carbon black comprising the following components:
carbon black: 80-90 parts;
strawberry type core-shell rubber compound/white carbon black: 10 to 19.5 portions;
lignin: 0 to 0.5 part.
As an improvement, the carbon black is soft carbon black or hard carbon black.
The lignin here acts as a binder for the granular carbon.
A preparation method of low-hysteresis carbon black comprises the steps of dispersing strawberry type core-shell rubber compound/white carbon black in water, uniformly mixing the mixture with lignin aqueous solution after uniform dispersion, mixing the mixture with carbon black in a granulator, granulating, and then drying the mixture in a low-temperature vacuum dryer until the water content is less than or equal to 1%.
The strawberry type core-shell rubber compound/white carbon black comprises the following components:
synthetic rubber: 25-40 parts;
natural rubber: 12-20 parts;
zinc oxide: 4-6 parts;
stearic acid: 2-4 parts;
anti-aging agent: 1-2 parts;
carbon black: 25-40 parts;
and (3) an accelerator: 0.9 to 1.5 portions;
sulfur: 6-9 parts;
white carbon black: 8-20 parts;
Sulfur-containing silane coupling agent: 0.2 to 1.2 portions.
As shown in FIG. 1, the preparation method of the strawberry type core-shell rubber compound/white carbon black comprises the following steps:
step one, preparing a rubber compound:
1a) Adjusting the roller spacing to 1.1mm, adjusting the surface temperature of the roller to 50+/-5 ℃, adding synthetic rubber and natural rubber to the front roller, and making a 3/4 cutter every 30s, wherein the steps are alternately performed from the two ends of the roller for 2min;
2a) Slowly adding sulfur and uniformly covering on the rubber for 2min;
3a) Adding stearic acid, and alternately making 3/4 cutters at two ends for 2min;
4a) Adding carbon black into the roll coating at a constant speed, adjusting the roll spacing to 1.4mm when half of carbon black is mixed, making a 3/4 cutter once, and adding the rest carbon black; when all the carbon black is mixed, the roller spacing is adjusted to 1.8mm, and the two ends are alternately provided with 3/4 cutters once for 10min;
5a) When the roll gap is 1.8mm, zinc oxide, an anti-aging agent and an accelerator are added for 3min;
6a) The two ends are alternately provided with three times of 3/4 cutters for 3min;
7a) Cutting the sizing material from the roller, adjusting the roller spacing to be 0.8mm, and rolling the sizing material between the roller gaps for six times for 2min without wrapping the roller longitudinally;
8a) Adjusting the roll gap to enable the thickness of the sizing material sheet to be 6mm, discharging the sizing material sheet, and rechecking the weight of the sizing material;
9a) Adjusting the roll gap to enable the thickness of the sizing material sheet to be 2.2 mm;
10a) Crushing the rubber compound to 6-12 mu m by using a low-temperature freezing crusher;
step two, preparing a strawberry type core-shell rubber compound/white carbon black:
1b) Placing the crushed rubber compound into an open stirring tank, spraying KH550 ethanol solution into the system under stirring, stirring for 30-60 min, and dispersing into water to obtain a rubber compound particle dispersion;
2b) Grinding the micro-nano calcium carbonate by a grinder, adding the ground micro-nano calcium carbonate into the mixed rubber particle dispersion liquid, stirring the mixed rubber particle dispersion liquid at room temperature for 6-15 min, filtering the mixed rubber particle dispersion liquid, and dispersing the mixed rubber particle dispersion liquid in water for the second time;
3b) Slowly adding 20-40 wt.% of silicon source aqueous solution into the system, heating the system to 30-60 ℃, uniformly stirring, slowly introducing carbon dioxide gas, slowly dropwise adding the rest silicon source aqueous solution when the PH value is reduced to 12-13 for 2-4 h, and aging for 12-16 h after the dropwise adding is completed to form strawberry type core-shell rubber compound/white carbon black particles;
4b) Adding an acidic solution into the system, removing calcium carbonate, centrifugally washing strawberry type core-shell rubber compound/white carbon black particles, and re-dispersing in water;
5b) The strawberry type core-shell rubber compound/white carbon black particles are subjected to a vacuum homogenizing emulsifying machine to damage part of the shell structure, so that a small amount of shell fragments are formed;
6b) And (3) spray-drying the strawberry type core-shell rubber compound/white carbon black particles, then placing the mixture in an open dry-mixing tank, spraying the ethanol solution of the sulfur-containing silane coupling agent into the open tank under the condition of stirring, and uniformly stirring.
The accelerator adopts accelerator NS.
The synthetic rubber is at least one of butadiene rubber or styrene-butadiene rubber; the calcium carbonate is at least one of heavy calcium carbonate or light calcium carbonate, the grain diameter is 8000-12000 meshes, and the dosage is 1-10 wt.% of the mass of the rubber compound; the acidic solution is at least one of hydrochloric acid solution or sulfuric acid solution; the crushed grain size of the vacuum homogenizing emulsifying machine is 0.2-2 mu m, and the grinding is carried out for 2-3 times.
The silicon source is at least one of sodium silicate or potassium silicate, and the solution of sodium silicate or potassium silicate can be prepared by dissolving powder of sodium silicate or potassium silicate with any modulus in water, or diluted by aqueous solution of sodium silicate or potassium silicate with different moduli; the mass of the silica shell layer is 8-20 wt.% of the rubber compound.
The sulfur-containing silane coupling agent is at least one of bis- [ gamma- (triethoxysilane) propyl ] tetrasulfide, bis- [3- (triethoxysilane) -propyl ] -disulfide and 3-thiocyanopropyl triethoxysilane, and the preparation steps of the sulfur-containing silane solution are as follows: dissolving the sulfur-containing silane coupling agent in ethanol, stirring at a high speed, wherein the content of the sulfur-containing silane coupling agent is 5-50 wt.%, stirring uniformly, and standing for 5-30 min to obtain the product, wherein the content of the sulfur-containing silane coupling agent is 0.2-1.2 wt.% of the use amount of the strawberry type core-shell rubber compound/white carbon black.
The dispersion solution used in the ethanol solution of the sulfur-containing silane coupling agent is an ethanol and water mixture, and the ethanol content is 10-99.9 wt.%.
Further illustrated by the specific examples below:
example 1
The low-hysteresis carbon black comprises the following components in parts by weight:
carbon black component: n220 carbon black: 80 parts;
strawberry type core-shell rubber compound/white carbon black: 19.7 parts;
lignin: 0.3 parts.
The strawberry type core-shell rubber compound/white carbon black comprises the following components in parts by mass:
strawberry type core-shell rubber compound/white carbon black component: butadiene rubber: 15 parts; styrene-butadiene rubber: 15 parts; natural rubber: 12 parts; zinc oxide: 5 parts; stearic acid: 3 parts; anti-aging agent: 1 part; n220 carbon black: 30 parts; accelerator NS:1.0 parts; sulfur: 9 parts; white carbon black: 8 parts; sulfur-containing silane coupling agent: 1.0 parts.
The preparation steps of the rubber compound are as follows:
1a) Adjusting the roll gap to 1.1mm, adding butadiene rubber, styrene-butadiene rubber and natural rubber to the front roll (the surface temperature of the roll is 50+/-5 ℃) and making a 3/4 cutter every 30 seconds, and alternately carrying out the steps from the two ends of the roll for 2 minutes;
2a) Slowly adding all sulfur and uniformly covering the rubber for 2min;
3a) Adding stearic acid, and alternately making 3/4 cutters at two ends for 2min;
4a) The carbon black was added to the roll-coating at a constant speed, and when about half of the carbon black was mixed, the roll gap was adjusted to 1.4mm, and a 3/4 cutter was used once, and the remaining carbon black was added. When all the carbon black is mixed, the roll spacing is adjusted to 1.8mm, the 3/4 cutters are alternately arranged at the two ends, and all the carbon black falling into the receiving tray is added for 10min;
5a) When the roll gap is 1.8mm, zinc oxide, an anti-aging agent and an accelerator NS are added for 3min;
6a) The two ends are alternately provided with three times of 3/4 cutters for 3min;
7a) Cutting the sizing material from the roller, adjusting the roller spacing to be 0.8mm, and rolling the sizing material between the roller gap and the longitudinal non-wrapping roller for six times for 2min. The total operating time is 24min;
8a) Adjusting the roll gap to enable the thickness of the sizing material sheet to be about 6mm, and checking the weight of the sizing material;
9a) Adjusting the roll gap to enable the thickness of the film to be about 2.2mm for blanking;
10a) The powder is crushed to 6 to 12 mu m by using a low-temperature freezing crushing technology.
The preparation method of the strawberry type core-shell rubber compound/white carbon black comprises the following steps:
1b) Placing the crushed rubber compound into an open stirring tank, spraying KH550 ethanol solution into the system under stirring, stirring for 50min, and dispersing into water;
2b) 3wt.% (mass of rubber compound) of heavy calcium carbonate is ground by a grinder, added into the rubber compound particle dispersion liquid, stirred for 10min at room temperature, filtered and secondarily dispersed in water;
3b) Slowly adding sodium silicate aqueous solution with the modulus of 1 (30% of the total dosage) into a system, uniformly stirring, heating to 40 ℃, introducing carbon dioxide gas (throughout the whole reaction), slowly dropwise adding the rest 70% of sodium silicate aqueous solution when the PH value is reduced to 12, and aging for 12 hours after the dropwise adding is completed to form strawberry type core-shell rubber/white carbon black particles;
4b) Adding a proper amount of hydrochloric acid into the system, removing heavy calcium carbonate, centrifugally washing strawberry type core-shell rubber compound/white carbon black particles, and re-dispersing in water;
5b) The strawberry type core-shell rubber compound/white carbon black particles are subjected to a vacuum homogenizing emulsifying machine to damage part of the shell structure, so that a small amount of shell fragments are formed;
6b) And (3) spray-drying the strawberry type core-shell rubber compound/white carbon black particles, then placing the mixture in an open dry-mixed tank, spraying an ethanol solution containing 20wt.% of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide into the open tank under the condition of stirring, and uniformly stirring, wherein the dosage of the sulfur-containing silane coupling agent is 1.0wt.% of the mass of the strawberry type core-shell rubber compound/white carbon black.
And dispersing the strawberry type core-shell rubber compound/white carbon black in water, uniformly mixing the mixture with lignin aqueous solution after uniform dispersion, mixing the mixture with carbon black in a granulator, granulating, and then drying the mixture in a low-temperature vacuum dryer until the water content is less than or equal to 1%, thereby preparing the low-hysteresis carbon black.
Example two
The low-hysteresis carbon black comprises the following components in parts by weight:
carbon black component: n220 carbon black: 80 parts;
strawberry type core-shell rubber compound/white carbon black: 19.7 parts;
lignin: 0.3 parts.
The strawberry type core-shell rubber compound/white carbon black comprises the following components in parts by mass:
strawberry type core-shell rubber compound/white carbon black component: butadiene rubber: 14 parts; styrene-butadiene rubber: 14 parts; natural rubber: 10 parts; zinc oxide: 5 parts; stearic acid: 3 parts; anti-aging agent: 1 part; n220 carbon black: 28 parts; accelerator NS:1.0 parts; sulfur: 9 parts; white carbon black: 14 parts; sulfur-containing silane coupling agent: 1 part.
The preparation steps of the rubber compound are as follows:
1a) Adjusting the roll gap to 1.1mm, adding butadiene rubber, styrene-butadiene rubber and natural rubber to the front roll (the surface temperature of the roll is 50+/-5 ℃) and making a 3/4 cutter every 30 seconds, and alternately carrying out the steps from the two ends of the roll for 2 minutes;
2a) Slowly adding all sulfur and uniformly covering the rubber for 2min;
3a) Adding stearic acid, and alternately making 3/4 cutters at two ends for 2min;
4a) The carbon black was added to the roll-coating at a constant speed, and when about half of the carbon black was mixed, the roll gap was adjusted to 1.4mm, and a 3/4 cutter was used once, and the remaining carbon black was added. When all the carbon black is mixed, the roll spacing is adjusted to 1.8mm, the 3/4 cutters are alternately arranged at the two ends, and all the carbon black falling into the receiving tray is added for 10min;
5a) When the roll gap is 1.8mm, zinc oxide, an anti-aging agent and an accelerator NS are added for 3min;
6a) The two ends are alternately provided with three times of 3/4 cutters for 3min;
7a) Cutting the sizing material from the roller, adjusting the roller spacing to be 0.8mm, and rolling the sizing material between the roller gap and the longitudinal non-wrapping roller for six times for 2min. The total operating time is 24min;
8a) Adjusting the roll gap to enable the thickness of the sizing material sheet to be about 6mm, and checking the weight of the sizing material;
9a) Adjusting the roll gap to enable the thickness of the film to be about 2.2mm for blanking;
10a) The powder is crushed to 6 to 12 mu m by using a low-temperature freezing crushing technology.
The preparation method of the strawberry type core-shell rubber/white carbon black comprises the following steps:
1b) Placing the crushed rubber compound into an open stirring tank, spraying KH550 ethanol solution into the system under stirring, stirring for 50min, and dispersing into water;
2b) 3wt.% (mass of rubber compound particles) of light calcium carbonate is ground by a grinder, added into the rubber compound particle dispersion liquid, stirred for 10min at room temperature, filtered and secondarily dispersed in water;
3b) Slowly adding a potassium silicate aqueous solution (30% of the whole dosage) with the modulus of 1 into a system, uniformly stirring, heating to 40 ℃, introducing carbon dioxide gas (throughout the whole reaction), slowly dropwise adding the rest 70% of sodium silicate aqueous solution when the PH value is reduced to 12, and aging for 12 hours after the dropwise adding is completed to form the strawberry type core-shell rubber/white carbon black;
4b) Adding a proper amount of hydrochloric acid into the system, removing light calcium carbonate, centrifugally washing strawberry type core-shell rubber compound/white carbon black particles, and re-dispersing in water;
5b) The strawberry type core-shell rubber compound/white carbon black particles are subjected to a vacuum homogenizing emulsifying machine to damage part of the shell structure, so that a small amount of shell fragments are formed;
6b) And (3) spray-drying the strawberry type core-shell rubber compound/white carbon black particles, then placing the mixture in an open dry-mixed tank, spraying a 20wt.% bis- [3- (triethoxysilane) -propyl ] -disulfide ethanol solution into the open tank under the condition of stirring, and uniformly stirring, wherein the dosage of the sulfur-containing silane coupling agent is 1.0wt.% of the mass of the strawberry type core-shell rubber compound/white carbon black.
And dispersing the strawberry type core-shell rubber compound/white carbon black in water, uniformly mixing the mixture with lignin aqueous solution after uniform dispersion, mixing the mixture with carbon black in a granulator, granulating, and then drying the mixture in a low-temperature vacuum dryer until the water content is less than or equal to 1%, thereby preparing the low-hysteresis carbon black.
Example III
The low-hysteresis carbon black comprises the following components in parts by weight:
carbon black component: n220 carbon black: 80 parts;
strawberry type core-shell rubber compound/white carbon black: 19.5 parts;
lignin: 0.5 part
The strawberry type core-shell rubber compound/white carbon black comprises the following components in parts by mass:
strawberry type core-shell rubber compound/white carbon black component: butadiene rubber: 14 parts; styrene-butadiene rubber: 14 parts; natural rubber: 10 parts; zinc oxide: 4 parts; stearic acid: 3 parts; anti-aging agent: 1 part; n220 carbon black: 24 parts; accelerator NS:1 part; sulfur: 8 parts; white carbon black: 20 parts; sulfur-containing silane coupling agent: 1.0 parts.
The preparation method of the rubber compound micropowder comprises the following steps:
1a) Adjusting the roll gap to 1.1mm, adding butadiene rubber, styrene-butadiene rubber and natural rubber to the front roll (the surface temperature of the roll is 50+/-5 ℃) and making a 3/4 cutter every 30 seconds, and alternately carrying out the steps from the two ends of the roll for 2 minutes;
2a) Slowly adding all sulfur and uniformly covering the rubber for 2min;
3a) Adding stearic acid, and alternately making 3/4 cutters at two ends for 2min;
4a) The carbon black was added to the roll-coating at a constant speed, and when about half of the carbon black was mixed, the roll gap was adjusted to 1.4mm, and a 3/4 cutter was used once, and the remaining carbon black was added. When all the carbon black is mixed, the roll spacing is adjusted to 1.8mm, the 3/4 cutters are alternately arranged at the two ends, and all the carbon black falling into the receiving tray is added for 10min;
5a) When the roll gap is 1.8mm, zinc oxide, an anti-aging agent and an accelerator NS are added for 3min;
6a) The two ends are alternately provided with three times of 3/4 cutters for 3min;
7a) Cutting the sizing material from the roller, adjusting the roller spacing to be 0.8mm, and rolling the sizing material between the roller gap and the longitudinal non-wrapping roller for six times for 2min. The total operating time is 24min;
8a) Adjusting the roll gap to enable the thickness of the sizing material sheet to be about 6mm, and checking the weight of the sizing material;
9a) Adjusting the roll gap to enable the thickness of the film to be about 2.2mm for blanking;
10a) The powder is crushed to 6 to 12 mu m by using a low-temperature freezing crushing technology.
The preparation method of the strawberry type core-shell rubber/white carbon black comprises the following steps:
1b) Placing the crushed rubber compound into an open stirring tank, spraying KH550 ethanol solution into the system under stirring, stirring for 50min, and dispersing into water;
2b) 3wt.% (mass of rubber compound) of heavy calcium carbonate is ground by a grinder, added into the rubber compound particle dispersion liquid, stirred for 10min at room temperature, filtered and secondarily dispersed in water;
3b) Slowly adding sodium silicate aqueous solution with the modulus of 1 (30% of the total dosage) into a system, uniformly stirring, heating to 40 ℃, introducing carbon dioxide gas (throughout the whole reaction), slowly dropwise adding the rest 70% of sodium silicate aqueous solution when the PH value is reduced to 12, and aging for 12 hours after the dropwise adding is completed to form strawberry type core-shell rubber/white carbon black;
4b) Adding a proper amount of hydrochloric acid into the system, removing heavy calcium carbonate, centrifugally washing strawberry type core-shell rubber compound/white carbon black particles, and re-dispersing in water;
5b) The strawberry type core-shell rubber compound/white carbon black particles are subjected to a vacuum homogenizing emulsifying machine to damage part of the shell structure, so that a small amount of shell fragments are formed;
6b) And (3) spray-drying the strawberry type core-shell rubber compound/white carbon black particles, then placing the mixture in an open dry-mixed tank, spraying an ethanol solution containing 20wt.% of 3-thiocyanopropyl triethoxysilane into the open tank under the condition of stirring, and uniformly stirring, wherein the dosage of the sulfur-containing silane coupling agent is 1.0wt.% of the mass of the strawberry type core-shell rubber compound/white carbon black.
And dispersing the strawberry type core-shell rubber compound/white carbon black in water, uniformly mixing the mixture with lignin aqueous solution after uniform dispersion, mixing the mixture with carbon black in a granulator, granulating, and then drying the mixture in a low-temperature vacuum dryer until the water content is less than or equal to 1%, thereby preparing the low-hysteresis carbon black.
Example IV
The low-hysteresis carbon black comprises the following components in parts by weight:
carbon black component: n220 carbon black: 80 parts;
strawberry type core-shell rubber compound/white carbon black: 19.5 parts;
lignin: 0.5 part
The strawberry type core-shell rubber compound/white carbon black comprises the following components in parts by mass:
strawberry type core-shell rubber compound/white carbon black component: butadiene rubber: 14 parts of styrene-butadiene rubber: 14 parts of natural rubber: 10 parts of zinc oxide: 5 parts of stearic acid: 3 parts of an anti-aging agent: 1 part of N220 carbon black: 28 parts of accelerator NS:1.0 parts of sulfur: 9 parts of white carbon black: 14 parts of sulfur-containing silane coupling agent: 1.0 parts.
The preparation steps of the rubber compound are as follows:
1a) Adjusting the roll gap to 1.1mm, adding butadiene rubber, styrene-butadiene rubber and natural rubber to the front roll (the surface temperature of the roll is 50+/-5 ℃) and making a 3/4 cutter every 30 seconds, and alternately carrying out the steps from the two ends of the roll for 2 minutes;
2a) Slowly adding all sulfur and uniformly covering the rubber for 2min;
3a) Adding stearic acid, and alternately making 3/4 cutters at two ends for 2min;
4a) The carbon black was added to the roll-coating at a constant speed, and when about half of the carbon black was mixed, the roll gap was adjusted to 1.4mm, and a 3/4 cutter was used once, and the remaining carbon black was added. When all the carbon black is mixed, the roll spacing is adjusted to 1.8mm, the 3/4 cutters are alternately arranged at the two ends, and all the carbon black falling into the receiving tray is added for 10min;
5a) When the roll gap is 1.8mm, zinc oxide, an anti-aging agent and an accelerator NS are added for 3min;
6a) The two ends are alternately provided with three times of 3/4 cutters for 3min;
7a) Cutting the sizing material from the roller, adjusting the roller spacing to be 0.8mm, and rolling the sizing material between the roller gap and the longitudinal non-wrapping roller for six times for 2min. The total operating time is 24min;
8a) Adjusting the roll gap to enable the thickness of the sizing material sheet to be about 6mm, and checking the weight of the sizing material;
9a) Adjusting the roll gap to enable the thickness of the film to be about 2.2mm for blanking;
10a) The powder is crushed to 6 to 12 mu m by using a low-temperature freezing crushing technology.
The preparation method of the strawberry type core-shell rubber/white carbon black comprises the following steps:
1b) Placing the crushed rubber compound into an open stirring tank, spraying KH550 ethanol solution into the system under stirring, stirring for 50min, and dispersing into water;
2b) After 6wt.% (mass of rubber fine particles) of heavy calcium carbonate was ground by a grinder, it was added to the rubber fine particle dispersion, stirred at room temperature for 10min, filtered, and secondarily dispersed in water;
3b) Slowly adding sodium silicate aqueous solution with the modulus of 1 (30% of the total dosage) into a system, uniformly stirring, heating to 40 ℃, introducing carbon dioxide gas (throughout the whole reaction), slowly dropwise adding the rest 70% of sodium silicate aqueous solution when the PH value is reduced to 12, and aging for 12 hours after the dropwise adding is completed to form strawberry type core-shell rubber/white carbon black particles;
4b) Adding a proper amount of hydrochloric acid into the system, removing heavy calcium carbonate, centrifugally washing strawberry type core-shell rubber compound/white carbon black particles, and re-dispersing in water;
5b) The strawberry type core-shell rubber compound/white carbon black particles are subjected to a vacuum homogenizing emulsifying machine to damage part of the shell structure, so that a small amount of shell fragments are formed;
6b) And (3) spray-drying the strawberry type core-shell rubber compound/white carbon black particles, then placing the mixture in an open dry-mixed tank, spraying an ethanol solution containing 20wt.% of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide into the open tank under the condition of stirring, and uniformly stirring, wherein the dosage of the sulfur-containing silane coupling agent is 1.0wt.% of the mass of the strawberry type core-shell rubber compound/white carbon black.
And dispersing the strawberry type core-shell rubber compound/white carbon black in water, uniformly mixing the mixture with lignin aqueous solution after uniform dispersion, mixing the mixture with carbon black in a granulator, granulating, and then drying the mixture in a low-temperature vacuum dryer until the water content is less than or equal to 1%, thereby preparing the low-hysteresis carbon black.
In the embodiment, the silicon source can be sodium silicate or potassium silicate, so that the performance of the low-hysteresis carbon black is not influenced; the sulfur-containing silane coupling agent can be at least one of bis- [ gamma- (triethoxysilane) propyl ] tetrasulfide, bis- [3- (triethoxysilane) -propyl ] -disulfide and 3-thiocyanopropyl triethoxysilane, and can not affect the performance of the low hysteresis carbon black.
Comparative example one
Carbon black component: n220 carbon black: 80 parts;
white carbon black: 19.5 parts (1750 mesh, about 8 microns);
lignin: 0.5 part
Sulfur-containing silane coupling agent: 1.0 part
The preparation method of the sulfur-containing silane modified white carbon black comprises the following steps:
1a) The white carbon black is placed in an open stirring tank, and an ethanol solution containing 20wt.% of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide is sprayed into the open stirring tank under the stirring condition, and the mixture is uniformly stirred, wherein the dosage of the sulfur-containing silane coupling agent is 1.0wt.% of the mass of the strawberry type core-shell white carbon black.
Dispersing white carbon black in water, uniformly mixing the white carbon black with lignin aqueous solution after uniform dispersion, mixing the mixture with carbon black in a granulator, granulating, and then drying the mixture in a low-temperature vacuum dryer until the water content is less than or equal to 1%.
Comparative example two
Carbon black component: n220 carbon black: 80 parts;
white carbon black: 19.5 parts;
lignin: 0.5 part.
The strawberry type core-shell white carbon black comprises the following components in parts by weight:
strawberry type core-shell white carbon black component:
white carbon black: 85 parts (1750 mesh, about 8 microns, with this as the core)
White carbon black: 14 parts of
Sulfur-containing silane: 1.0 part
The preparation method of the strawberry type core-shell white carbon black comprises the following steps:
1a) Placing 1750-mesh white carbon black into an open stirring tank, spraying KH550 ethanol solution into the system under stirring, stirring for 50min, and dispersing into water;
2a) Grinding 6wt.% (mass of the rubber compound particles) of heavy calcium carbonate by a grinder, adding the ground calcium carbonate into the white carbon black dispersion liquid, stirring the mixture at room temperature for 10min, filtering the mixture, and secondarily dispersing the mixture in water;
3a) Slowly adding sodium silicate aqueous solution with the modulus of 1 (30% of the total dosage) into a system, uniformly stirring, heating to 40 ℃, introducing carbon dioxide gas (throughout the whole reaction), slowly dropwise adding the rest 70% of sodium silicate aqueous solution when the PH value is reduced to 12, and aging for 12 hours after the dropwise adding is completed to form white carbon black particles with a strawberry type core-shell structure;
4a) Adding a proper amount of hydrochloric acid into the system, removing heavy calcium carbonate, centrifugally washing strawberry type core-shell white carbon black particles, and re-dispersing in water;
5a) The method comprises the steps of (1) breaking a part of a shell structure by using strawberry type core-shell white carbon black particles through a vacuum homogenizing emulsifying machine to form a small amount of shell fragments;
6a) And (3) spray-drying the strawberry type core-shell white carbon black particles, then placing the particles in an open dry-mixed tank, spraying an ethanol solution containing 20wt.% of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide into the open tank under the condition of stirring, and uniformly stirring, wherein the dosage of the sulfur-containing silane coupling agent is 1.0wt.% of the mass of the strawberry type core-shell white carbon black.
And dispersing the strawberry type core-shell white carbon black in water, uniformly mixing the core-shell white carbon black with lignin aqueous solution after uniform dispersion, mixing the mixture with carbon black in a granulator, granulating, and then drying the mixture in a low-temperature vacuum dryer until the water content is less than or equal to 1%, thereby preparing the low-hysteresis carbon black.
Comparative example three
The low-hysteresis carbon black comprises the following components in parts by weight:
carbon black component:
n220 carbon black: 80 parts;
strawberry type core-shell rubber compound/white carbon black: 19.5 parts;
lignin: 0.5 part
The strawberry type core-shell rubber compound/white carbon black comprises the following components in parts by mass:
Strawberry type core-shell rubber compound/white carbon black component: butadiene rubber: 16 parts; styrene-butadiene rubber: 16 parts; natural rubber: 12 parts; zinc oxide: 5 parts; stearic acid: 3 parts; anti-aging agent: 1 part; n220 carbon black: 32 parts; and (3) an accelerator: 1.0 parts; sulfur: 9 parts; white carbon black: 4 parts; sulfur-containing silane coupling agent: 1.0 parts.
The preparation method of the rubber compound micropowder comprises the following steps:
1a) Adjusting the roll gap to 1.1mm, adding butadiene rubber, styrene-butadiene rubber and natural rubber to the front roll (the surface temperature of the roll is 50+/-5 ℃) and making a 3/4 cutter every 30 seconds, and alternately carrying out the steps from the two ends of the roll for 2 minutes;
2a) Slowly adding all sulfur and uniformly covering the rubber for 2min;
3a) Adding stearic acid, and alternately making 3/4 cutters at two ends for 2min;
4a) The carbon black was added to the roll-coating at a constant speed, and when about half of the carbon black was mixed, the roll gap was adjusted to 1.4mm, and a 3/4 cutter was used once, and the remaining carbon black was added. When all the carbon black is mixed, the roll spacing is adjusted to 1.8mm, the 3/4 cutters are alternately arranged at the two ends, and all the carbon black falling into the receiving tray is added for 10min;
5a) When the roll gap is 1.8mm, zinc oxide, an anti-aging agent and an accelerator are added for 3min;
6a) The two ends are alternately provided with three times of 3/4 cutters for 3min;
7a) Cutting the sizing material from the roller, adjusting the roller spacing to be 0.8mm, and rolling the sizing material between the roller gap and the longitudinal non-wrapping roller for six times for 2min. The total operating time is 24min;
8a) Adjusting the roll gap to enable the thickness of the sizing material sheet to be about 6mm, and checking the weight of the sizing material;
9a) Adjusting the roll gap to enable the thickness of the film to be about 2.2mm for blanking;
10a) The powder is crushed to 6 to 12 mu m by using a low-temperature freezing crushing technology.
The preparation method of the strawberry type core-shell rubber/white carbon black comprises the following steps:
1b) Placing the crushed rubber compound into an open stirring tank, spraying KH550 ethanol solution into the system under stirring, stirring for 50min, and dispersing into water;
2b) After 6wt.% (mass of rubber fine particles) of heavy calcium carbonate was ground by a grinder, it was added to the rubber fine particle dispersion, stirred at room temperature for 10min, filtered, and secondarily dispersed in water;
3b) Slowly adding sodium silicate aqueous solution with the modulus of 1 (30% of the total dosage) into a system, uniformly stirring, heating to 40 ℃, introducing carbon dioxide gas (throughout the whole reaction), slowly dropwise adding the rest 70% of sodium silicate aqueous solution when the PH value is reduced to 12, and aging for 12 hours after the dropwise adding is completed to form strawberry type core-shell rubber compound/white carbon black particles;
4b) Adding a proper amount of hydrochloric acid into the system, removing heavy calcium carbonate, centrifugally washing strawberry type core-shell rubber compound/white carbon black particles, and re-dispersing in water;
5b) The strawberry type core-shell rubber compound/white carbon black particles are subjected to a vacuum homogenizing emulsifying machine to damage part of the shell structure, so that a small amount of shell fragments are formed;
6b) And (3) spray-drying the strawberry type core-shell rubber compound/white carbon black particles, then placing the mixture in an open dry-mixed tank, spraying an ethanol solution containing 20wt.% of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide into the open tank under the condition of stirring, and uniformly stirring, wherein the dosage of the sulfur-containing silane coupling agent is 1.0wt.% of the mass of the strawberry type core-shell rubber compound/white carbon black.
And dispersing the strawberry type core-shell rubber/white carbon black in water, uniformly mixing the core-shell rubber/white carbon black with lignin aqueous solution after uniform dispersion, mixing the mixture with carbon black in a granulator, granulating, and then drying the mixture in a low-temperature vacuum dryer until the water content is less than or equal to 1%, thereby preparing the low-hysteresis carbon black.
Comparative example four
The low-hysteresis carbon black comprises the following components in parts by weight:
carbon black component: n220 carbon black: 80 parts;
strawberry type core-shell rubber compound/white carbon black: 19.5 parts;
Lignin: 0.5 part.
The strawberry type core-shell rubber compound/white carbon black comprises the following components in parts by mass:
strawberry type core-shell rubber compound/white carbon black component: butadiene rubber: 14 parts; styrene-butadiene rubber: 14 parts; natural rubber: 10 parts; zinc oxide: 5 parts; stearic acid: 3 parts; anti-aging agent: 1 part; n220 carbon black: 28 parts; and (3) an accelerator: 1.0 parts; sulfur: 9 parts; white carbon black: 14 parts; sulfur-containing silane coupling agent: 1.0 parts.
The preparation method of the rubber compound micropowder comprises the following steps:
1a) Adjusting the roll gap to 1.1mm, adding butadiene rubber, styrene-butadiene rubber and natural rubber to the front roll (the surface temperature of the roll is 50+/-5 ℃) and making a 3/4 cutter every 30 seconds, and alternately carrying out the steps from the two ends of the roll for 2 minutes;
2a) Slowly adding all sulfur and uniformly covering the rubber for 2min;
3a) Adding stearic acid, and alternately making 3/4 cutters at two ends for 2min;
4a) The carbon black was added to the roll-coating at a constant speed, and when about half of the carbon black was mixed, the roll gap was adjusted to 1.4mm, and a 3/4 cutter was used once, and the remaining carbon black was added. When all the carbon black is mixed, the roll spacing is adjusted to 1.8mm, the 3/4 cutters are alternately arranged at the two ends, and all the carbon black falling into the receiving tray is added for 10min;
5a) When the roll gap is 1.8mm, zinc oxide, an anti-aging agent and an accelerator are added for 3min;
6a) The two ends are alternately provided with three times of 3/4 cutters for 3min;
7a) Cutting the sizing material from the roller, adjusting the roller spacing to be 0.8mm, and rolling the sizing material between the roller gap and the longitudinal non-wrapping roller for six times for 2min. The total operating time is 24min;
8a) Adjusting the roll gap to enable the thickness of the sizing material sheet to be about 6mm, and checking the weight of the sizing material;
9a) Adjusting the roll gap to enable the thickness of the film to be about 2.2mm for blanking;
10a) The powder is crushed to 6 to 12 mu m by using a low-temperature freezing crushing technology.
The preparation method of the strawberry type core-shell rubber compound/white carbon black comprises the following steps:
1b) Placing the crushed rubber compound into an open stirring tank, spraying KH550 ethanol solution into the system under stirring, stirring for 50min, and dispersing into water;
2b) Slowly adding sodium silicate aqueous solution with the modulus of 1 (30% of the total dosage) into a system, uniformly stirring, heating to 40 ℃, introducing carbon dioxide gas (throughout the whole reaction), slowly dropwise adding the rest 70% of sodium silicate aqueous solution when the PH value is reduced to 12, and aging for 12 hours after the dropwise adding is completed to form the rubber compound/white carbon black particles with the strawberry type core-shell structure;
3b) The strawberry type core-shell rubber compound/white carbon black particles are subjected to a vacuum homogenizing emulsifying machine to damage part of the shell structure, so that a small amount of shell fragments are formed;
4b) And (3) spray-drying the strawberry type core-shell rubber compound/white carbon black particles, then placing the mixture in an open dry-mixed tank, spraying an ethanol solution containing 20wt.% of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide into the open tank under the condition of stirring, and uniformly stirring, wherein the dosage of the sulfur-containing silane coupling agent is 1.0wt.% of the mass of the strawberry type core-shell rubber compound/white carbon black.
And dispersing the strawberry type core-shell rubber/white carbon black in water, uniformly mixing the core-shell rubber/white carbon black with lignin aqueous solution after uniform dispersion, mixing the mixture with carbon black in a granulator, granulating, and then drying the mixture in a low-temperature vacuum dryer until the water content is less than or equal to 1%, thereby preparing the low-hysteresis carbon black.
Table 1: the basic properties of the low hysteresis carbon blacks prepared in examples one to four and comparative examples one to four and the heat buildup in rubber.
The components of the strawberry type core-shell compound/white carbon black in the first to third embodiments and the mass parts of the components are different from each other in the quality of the shell white carbon black, so that the performance of the low-hysteresis carbon black is different. The fourth embodiment differs from the first to third embodiments in the amount of calcium carbonate used.
Comparative example one is a low hysteresis carbon black to which ordinary white carbon black was added.
The difference of the second comparative example is that the white carbon black with the strawberry type core-shell structure is prepared by taking the rubber compound as a core, taking 1750 meshes of white carbon black as a core and taking sodium silicate as a silicon source.
The components of the strawberry type core-shell rubber compound/white carbon black are different from the components of the comparative example IV in the mass parts of the components, namely the dosage of the white carbon black; in comparative example four, no calcium carbonate was used.
As shown in Table 1, the basic physical property index of the strawberry type core-shell rubber compound/white carbon black of the invention improves the wet skid resistance and reduces the rolling resistance (namely, the loss factor at 0 ℃ is higher and the loss factor at 60 ℃ is lower) under the condition that the physical index is unchanged. Compared with other double-phase carbon black, the wet skid resistance (Tan delta (0 ℃ DMA.1%)) is improved by about 10 to 13 percent, and the rolling resistance (Tan delta (60 ℃ DMA.1%)) is reduced by about 16 to 19 percent.
The low-hysteresis carbon black is mixed with a certain amount of strawberry type core-shell rubber compound/white carbon black particles, and the particles have good dispersibility and binding force in rubber, so that the low-hysteresis carbon black has excellent wet skid resistance and lower rolling resistance, thereby reducing the energy consumption of motor vehicles and improving the safety. The strawberry type core-shell rubber compound/white carbon black particles take micron-sized rubber compound crushed by a low-temperature crushing technology as a core, white carbon black as a shell, calcium carbonate as a shell breaking material, and silicon source aqueous solution is intermittently dripped to form shell white carbon black with very high roughness on the surface of the rubber compound, firstly, the calcium carbonate is removed by using an acid solution, the generated carbon dioxide is used for propping up the shell, and then the silica is crushed by mechanical force, so that the internal rubber compound is exposed, and then the sulfur-containing silane coupling agent is used for modification; the shell layer white carbon black has rich mastoid structure (so called as strawberry type core-shell compound rubber/white carbon black), the mastoid structure is easier to puncture a water film, the wet skid resistance is further improved, the surface is modified with a sulfur-containing silane coupling agent, and the binding force with rubber is enhanced. The white carbon black with the strawberry-shaped structure, the low-hysteresis rubber and the carbon black are combined, so that the low-hysteresis performance of the tire is better exerted.
While the preferred embodiments of the present invention have been illustrated, various changes and modifications can be made by one of ordinary skill in the art without departing from the scope of the invention.
Claims (8)
1. A low hysteresis carbon black characterized by: comprises the following components:
carbon black: 80-90 parts of a lubricant;
strawberry type core-shell rubber compound/white carbon black: 10-19.5 parts of a lubricant;
lignin: 0-0.5 parts;
the strawberry type core-shell rubber compound/white carbon black comprises the following components:
synthetic rubber: 25-40 parts of a lubricant;
natural rubber: 12-20 parts of a lubricant;
zinc oxide: 4-6 parts;
stearic acid: 2-4 parts of a lubricant;
anti-aging agent: 1-2 parts of a lubricant;
carbon black: 25-40 parts of a lubricant;
and (3) an accelerator: 0.9-1.5 parts;
sulfur: 6-9 parts of a lubricant;
white carbon black: 8-20 parts of a lubricant;
sulfur-containing silane coupling agent: 0.2-1.2 parts;
the preparation method of the strawberry type core-shell rubber compound/white carbon black comprises the following steps:
step one, preparing a rubber compound:
1a) Adjusting the roller spacing to 1.1mm, adjusting the surface temperature of the roller to 50+/-5 ℃, adding synthetic rubber and natural rubber to the front roller, and making a 3/4 cutter every 30s, wherein the steps are alternately performed from the two ends of the roller for 2min;
2a) Slowly adding sulfur and uniformly covering on the rubber for 2min;
3a) Adding stearic acid, and alternately making 3/4 cutters at two ends for 2min;
4a) Adding carbon black into the roll coating at a constant speed, adjusting the roll spacing to 1.4mm when half of carbon black is mixed, making a 3/4 cutter once, and adding the rest carbon black; when all the carbon black is mixed, the roller spacing is adjusted to 1.8mm, and the two ends are alternately provided with 3/4 cutters once for 10min;
5a) When the roll gap is 1.8mm, zinc oxide, an anti-aging agent and an accelerator are added for 3min;
6a) The two ends are alternately provided with three times of 3/4 cutters for 3min;
7a) Cutting the sizing material from the roller, adjusting the roller spacing to be 0.8mm, and rolling the sizing material between the roller gaps for six times for 2min without wrapping the roller longitudinally;
8a) Adjusting the roll gap to enable the thickness of the sizing material sheet to be 6mm, discharging the sizing material sheet, and rechecking the weight of the sizing material;
9a) Adjusting the roll gap to enable the thickness of the sizing material sheet to be 2.2 mm;
10a) Crushing the rubber compound to 6-12 mu m by using a low-temperature freezing crusher;
step two, preparing a strawberry type core-shell rubber compound/white carbon black:
1b) Placing the crushed rubber compound into an open stirring tank, spraying KH550 ethanol solution into the system under stirring, stirring for 30-60 min, and dispersing into water to obtain a rubber compound particle dispersion;
2b) Grinding the micro-nano calcium carbonate by a grinder, adding the ground micro-nano calcium carbonate into a mixed rubber particle dispersion liquid, stirring the mixed rubber particle dispersion liquid at room temperature for 6-15 min, filtering the mixed rubber particle dispersion liquid, and dispersing the mixed rubber particle dispersion liquid in water for the second time;
3b) Slowly adding 20-40 wt.% of silicon source aqueous solution into the system, heating the system to 30-60 ℃, uniformly stirring, slowly introducing carbon dioxide gas, slowly dropwise adding the rest silicon source aqueous solution when the pH value is reduced to 12-13 for 2-4 hours, and aging for 12-16 hours after the dropwise adding is completed to form strawberry type core-shell rubber compound/white carbon black particles;
4b) Adding an acidic solution into the system, removing calcium carbonate, centrifugally washing strawberry type core-shell rubber compound/white carbon black particles, and re-dispersing in water;
5b) The strawberry type core-shell rubber compound/white carbon black particles are subjected to a vacuum homogenizing emulsifying machine to damage part of the shell structure, so that a small amount of shell fragments are formed;
6b) And (3) spray-drying the strawberry type core-shell rubber compound/white carbon black particles, then placing the mixture in an open dry-mixing tank, spraying the ethanol solution of the sulfur-containing silane coupling agent into the open tank under the condition of stirring, and uniformly stirring.
2. A low hysteresis carbon black according to claim 1, characterized in that: the carbon black is soft carbon black or hard carbon black.
3. The method for preparing the low-hysteresis carbon black according to claim 1, wherein the method comprises the following steps: dispersing strawberry type core-shell rubber compound/white carbon black in water, uniformly mixing the mixture with lignin aqueous solution after uniform dispersion, mixing the mixture with carbon black in a granulator, granulating, and then drying the mixture in a low-temperature vacuum dryer until the water content is less than or equal to 1%.
4. A method of preparing a low hysteresis carbon black according to claim 3, wherein: the accelerator adopts accelerator NS.
5. A method of preparing a low hysteresis carbon black according to claim 3, wherein: the synthetic rubber is at least one of butadiene rubber or styrene-butadiene rubber; the calcium carbonate is at least one of heavy calcium carbonate and light calcium carbonate, the particle size is 8000-12000 meshes, and the dosage is 1-10wt% of the mixing rubber; the acidic solution is at least one of hydrochloric acid solution or sulfuric acid solution; the crushed particle size of the vacuum homogenizing emulsifying machine is 0.2-2 mu m, and grinding is carried out for 2-3 times.
6. A method of preparing a low hysteresis carbon black according to claim 3, wherein: the silicon source is at least one of sodium silicate or potassium silicate, and the solution of sodium silicate or potassium silicate can be prepared by dissolving powder of sodium silicate or potassium silicate with any modulus in water, or diluted by aqueous solution of sodium silicate or potassium silicate with different moduli; the mass of the formed silicon dioxide shell layer is 8-20wt% of the mass of the rubber compound.
7. A method of preparing a low hysteresis carbon black according to claim 3, wherein: the sulfur-containing silane coupling agent is at least one of bis- [ gamma- (triethoxysilane) propyl ] tetrasulfide, bis- [3- (triethoxysilane) -propyl ] -disulfide and 3-thiocyanopropyl triethoxysilane, and the preparation steps of the ethanol solution of the sulfur-containing silane coupling agent are as follows: dissolving a sulfur-containing silane coupling agent in ethanol, stirring at a high speed, wherein the content of the sulfur-containing silane coupling agent is 5-50wt%, and standing for 5-30 min after stirring uniformly, wherein the content of the sulfur-containing silane coupling agent is 0.2-1.2wt% of the use amount of the strawberry type core-shell rubber compound/white carbon black.
8. A method of preparing a low hysteresis carbon black according to claim 3, wherein: the dispersion solution used in the ethanol solution of the sulfur-containing silane coupling agent is an ethanol and water mixture, and the ethanol content is 10-99.9wt%.
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