CN111471216A - Modified thermal cracking carbon black - Google Patents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
Abstract
The invention relates to a modified thermal cracking carbon black and a preparation method thereof, wherein the modified thermal cracking carbon black comprises hydroxylated thermal cracking carbon black, hydroxylated carbon fiber and a coupling agent.
Description
Technical Field
The invention relates to modified thermal cracking carbon black and a modification method thereof. In particular to modified thermal cracking carbon black modified by carbon fiber and a coupling agent. The modified thermal cracking carbon black is applied to rubber products, so that the strength of the rubber products can be improved, and the using amount of the thermal cracking carbon black is increased.
Background
Today, with the rapid development of economy and society, the contradiction between resources, environment and the like becomes more and more acute, the family cars gradually enter thousands of households, and the quantity of waste tires is more and more. The prior method for treating the waste tires mainly comprises the following steps: renewing used tyre, direct burying, producing rubber powder and producing thermal cracking carbon black. The tire retreading requires that the tire body is intact, but the number of tires for retreading is small, and the tires have certain limitations; although the burying treatment is simple, the pollution to underground water quality and surrounding soil can be caused; the rubber powder production process needs freezing, crushing and grinding, but the process needs higher energy consumption and energy-intensive equipment; the production process of the thermal cracking carbon black has no waste or waste residue, the cracking product can be completely utilized, and the method has strong economic and social benefits.
Thermal cracking carbon black is Bouier J.M. of France, etc. in the beginning of the 80 s of the 20 th century, heavy oil is adopted as a reaction medium, waste rubber is pyrolyzed at 340-380 ℃ in nitrogen, desulfurized oligomer and thermal cracking carbon black are obtained, the thermal cracking carbon black is different from the traditional carbon black, the thermal cracking carbon black contains about 15% of ash (consisting of white carbon black or Zn substances) and residual cracking oil, the specific surface area, the structure degree and the surface activity of the produced thermal cracking carbon black are very low, the dispersion and the mechanical property in rubber are poor, and the thermal cracking carbon black can be used in rubber products after being generally subjected to modification treatment. The existing technology for modifying thermal cracking carbon black mainly comprises superfine grinding modification, modifier modification and modification by an acid washing ash removal method.
The superfine modified thermal cracking carbon black is prepared by grinding thermal cracking carbon black by a vibration mill or a grinding mill, carrying out superfine treatment, and grading according to the particle size. The surface activity of the thermal cracking carbon black after the superfine modification is improved to some extent, which is beneficial to improving the physical and mechanical properties of vulcanized rubber, but the defects are that the particle size of the thermal cracking carbon black is reduced, the particles are more easily agglomerated, the dispersion in rubber is poor, the rotating speed required by the superfine modification equipment is very high, and the requirement of high rotating speed cannot be met by large-scale superfine equipment, so that the superfine modification method cannot realize industrialization.
The modifier modified thermal cracking carbon black is obtained by modifying thermal cracking carbon black in special equipment by using different modifiers, stearic acid is used by Shenbloc of environmental science and engineering college of southern Kai university, one part of stearic acid is adsorbed on the surface of thermal cracking carbon black particles by Van der Waals force, and the other part of stearic acid is subjected to esterification reaction by terminal carboxyl and hydroxyl of thermal cracking carbon black. Although the modification method has simple process, the surface activity of the thermal cracking carbon black is increased, and the dispersibility of the thermal cracking carbon black in rubber is improved, the modified product has lower strength and mechanical property in rubber, and only a small amount of the modified thermal cracking carbon black can be mixed to ensure the product performance, so that the use amount of the thermal cracking carbon black in rubber is limited.
The acid-washing modified thermal cracking carbon black is mainly used for removing ash in the thermal cracking carbon black, and HNO is used by beauty red and the like3And stearic acid/HNO3Modifying thermal cracking carbon black; shenbloxiong et al use H2SO4Carrying out acid washing modification on the thermal cracking; mtifide Banar et al used 50% HN03After the thermal cracking carbon black is subjected to acid washing by the method, the ash content is obviously reduced, the specific surface area is increased, and the performance of the modified thermal cracking carbon black is greatly improved.
Chinese patent No. 201410150841.0 discloses a method for preparing an oxidized modified thermal cracking carbon black, which can improve the reactivity and adsorption capacity of the thermal cracking carbon black, and although the binding force between the modified thermal cracking carbon black and rubber is enhanced, the strength of the modified thermal cracking carbon black is relatively low, and when the modified thermal cracking carbon black of the patent is used in a tire rubber formula, the mechanical property and hardness of a vulcanized rubber material are relatively low, which restricts the use of the thermal cracking carbon black.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and seek to design a high-strength modified thermal cracking carbon black, so as to further improve the mechanical property and strength of thermal cracking carbon black rubber and increase the using amount of the thermal cracking carbon black in the rubber.
In order to achieve the above object, the present invention provides a modified thermal cracking carbon black comprising thermal cracking carbon black and carbon fibers.
In a preferred embodiment of the present invention, the modified thermal cracking carbon black is composed of thermal cracking carbon black and carbon fiber.
The invention also discloses modified thermal cracking carbon black, which comprises hydroxylated thermal cracking carbon black, hydroxylated carbon fiber and a coupling agent.
The coupling agent is one or a mixture of silane coupling agent, titanate coupling agent and borate coupling agent.
The invention also discloses a modified thermal cracking carbon black, which comprises
70-80 parts of hydroxylation thermal cracking carbon black;
10-30 parts by weight of hydroxylated carbon fiber;
5-15 parts of coupling agent.
The hydroxylated thermal cracking carbon black is prepared from 80-90 parts by weight of thermal cracking carbon black and 10-20 parts by weight of hydroxylated modifier. The hydroxylation modifier is one or more of NaOH aqueous solution, sodium hypochlorite aqueous solution and phenolphthalein aqueous solution; the solute mass fraction of the NaOH aqueous solution, the sodium hypochlorite aqueous solution and the phenolphthalein aqueous solution is 1-4%.
The hydroxylated carbon fiber is prepared from 80-90 parts by weight of carbon fiber and 10-20 parts by weight of hydroxylated modifier. The hydroxylation modifier is one or more of NaOH aqueous solution, sodium hypochlorite aqueous solution and phenolphthalein aqueous solution; the solute mass fraction of the NaOH aqueous solution, the sodium hypochlorite aqueous solution and the phenolphthalein aqueous solution is 1-4%.
The length of the carbon fiber is 0.1-6 mm; preferably 1-5 mm.
The invention also discloses a preparation method of the modified thermal cracking carbon black of claim 1, which comprises the following steps:
(1) carrying out surface hydroxylation on the thermal cracking carbon black and/or the carbon fiber by using a hydroxylation modifier to prepare hydroxylation thermal cracking carbon black and hydroxylation carbon fiber;
(2) and adding a coupling agent into the mixture of the hydroxylated thermal cracking carbon black and the hydroxylated carbon fiber to prepare the modified thermal cracking carbon black.
The surface functionalization in step (1) of the preparation method of the modified thermal cracking carbon black related to the invention is hydroxylation, and the hydroxylated thermal cracking carbon black and the hydroxylated carbon fiber are obtained by grinding the thermal cracking carbon black and/or the carbon fiber and a hydroxylation modifier in a grinding machine.
The rotating speed of the grinder is 800r/min-2000r/min, preferably 1000 r/min-1500 r/min; the treatment time is 0.5h-1h, preferably 1h-4 h.
The modification equipment used in the step (2) is one of a high-speed mixer, a kneader, an internal mixer, a single-screw extruder or a double-screw extruder. Granulating the ground mixture of the hydroxylated thermal cracking carbon black and the hydroxylated carbon fiber by using a granulator at the rotating speed of 150-500r/min, wherein the proportion of granulating water to the mixture of the carbon black is as follows: 0.5:1-0.7: 1 (mass ratio), drying by a dryer at the drying temperature of 125-220 ℃ until the moisture content is below 1 percent.
In a preferred embodiment of the invention, the high-speed mixer has a rotational speed of 1000r/min to 2000r/min, preferably 1200r/min to 1800 r/min.
The temperature is 60 ℃ to 100 ℃, preferably 70 ℃ to 90 ℃.
The running time is 20min-50 min.
In a preferred embodiment of the invention, the single screw extruder has a rotational speed of 80r/min to 120r/min, preferably 90r/min to 110r/min.
The ball milling time is 0.5h-5h, preferably 1h-4 h.
The coupling agent in the step (2) is one or a mixture of silane coupling agent, titanate coupling agent and borate coupling agent. The coupling agent has a coupling effect between the thermal cracking carbon black and the carbon fiber, so that the dispersibility and the compatibility of the carbon fiber in the thermal cracking carbon black are improved.
The invention also discloses application of the modified thermal cracking carbon black in rubber modification.
The invention also discloses a modified rubber containing the modified thermal cracking carbon black.
The invention also discloses a rubber composition comprising
100 portions of rubber and 130 portions of rubber
40-70 parts of modified thermal cracking carbon black
Stearic acid 1-3 weight portions
2-5 parts of zinc oxide
1-4 parts of anti-aging agent
0.5-2 parts of microcrystalline wax
1-3 parts of accelerator
0 to 0.5 weight portion of scorch retarder
0.5 to 2 weight portions of sulfur.
The rubber can be one or more of natural rubber, styrene butadiene rubber, butadiene rubber and butyl rubber.
The thermal cracking carbon black of the invention is different from the traditional carbon black, and mainly refers to the thermal cracking carbon black of waste tires. Thermal cracking of scrap tires refers to the thermal cracking in the absence of oxygen (e.g., vacuum or N)2In atmosphere), small waste tires in the reactor are thermally cracked by high temperature or catalyst, and products such as gas, oil, thermal cracking carbon black, solid carbon, steel wires and the like are finally obtained. The thermal cracking method not only can thoroughly and effectively treat and recycle the waste tires, but also can obtain products with higher added values. Such as pyrolysis gas, pyrolysis oil, and thermally cracked carbon black. In addition, the thermal cracking treatment method can treat the waste tires in large batch, has higher economic benefit, hardly pollutes the environment, and better accords with the principle of recycling the waste tires from the perspective of economy and environmental protection. The thermal carbon black of the present invention may be produced by a normal pressure pyrolysis processThermal cracking carbon black obtained by a vacuum pyrolysis process, a supercritical pyrolysis process and the like. The thermal cracking carbon black of the invention contains 13-16wt% of ash (consisting of white carbon black or Zn substances) and residual cracking oil, the produced thermal cracking carbon black has low specific surface area, structure degree and surface activity, has poor dispersion and mechanical properties in rubber, and can be used in rubber products after being generally modified.
The hydroxylated thermal cracking carbon black refers to the hydroxylated thermal cracking carbon black obtained by grinding the thermal cracking carbon black and a hydroxylation modifier in a grinding machine.
The hydroxylated carbon fiber according to the present invention is a hydroxylated carbon fiber obtained by grinding a carbon fiber with NaOH in a hydroxylation modifier grinder.
The hydroxylated thermal cracking carbon black is prepared from 80-90 parts by weight of thermal cracking carbon black and 10-20 parts by weight of hydroxylated modifier. The hydroxylation modifier is one or more of NaOH aqueous solution, sodium hypochlorite aqueous solution and phenolphthalein aqueous solution; the solute mass fraction of the NaOH aqueous solution, the sodium hypochlorite aqueous solution and the phenolphthalein aqueous solution is 1-4%.
The words comprising, including, containing and the like, as used herein, are intended to mean that the listed ingredients are not excluded.
Compared with the prior art, the preparation process is simple, the design principle is safe and reliable, the carbon fiber has high strength, the carbon fiber is grafted to the surface of the thermal cracking carbon black, and the mechanical property and the strength of the thermal cracking carbon black rubber material can be improved by means of the grafted carbon fiber. The modified thermal cracking carbon black has improved strength, can be widely applied to rubber products, enhances the strength and mechanical property of thermal cracking carbon black rubber, and improves the usage amount of thermal cracking carbon black in rubber.
Detailed Description
The invention is further illustrated by the following examples. It is to be understood that the following examples are intended to illustrate the invention and are not intended to limit its scope.
TABLE 1 trade Mark and Source of the raw materials
Example 1:
modifying 90 parts by weight of thermal cracking carbon black and 10 parts by weight of NaOH aqueous solution (the mass fraction of NaOH is 2%) in a grinding machine for 0.5h, wherein the rotating speed of the grinding machine is 1000r/min, and preparing hydroxylated thermal cracking carbon black; modifying 90 parts by weight of carbon fiber and 10 parts by weight of NaOH aqueous solution (the mass fraction of NaOH is 2%) in a grinding machine for 0.5h, wherein the rotating speed of the grinding machine is 1000r/min, and preparing hydroxylated carbon fiber; 5 parts by weight of Si69 (silane coupling agent), 80 parts by weight of hydroxylated thermal cracking carbon black and 15 parts by weight of hydroxylated carbon fiber are poured into a high-speed mixer to be treated for 20min, the rotating speed of the mixer is 1000r/min, and the temperature is 60 ℃. The ratio of the granulating water to the carbon black mixture is as follows: 0.5:1 (mass ratio), drying by a dryer at the drying temperature of 125-220 ℃ until the moisture content is below 1%.
Testing the performance of the modified thermal carbon blacks in rubber the formulations used are shown in table 2; the test results are shown in Table 3
TABLE 2
Example 2:
modifying 85 parts by weight of thermal cracking carbon black and 15 parts by weight of NaOH aqueous solution (the mass fraction of NaOH is 2%) in a grinding machine for 0.5h, wherein the rotating speed of the grinding machine is 1000r/min, and preparing hydroxylation thermal cracking carbon black; modifying 90 parts by weight of carbon fiber and 10 parts by weight of NaOH aqueous solution (the mass fraction of NaOH is 2%) in a grinding machine for 0.5h, wherein the rotating speed of the grinding machine is 1000r/min, and preparing hydroxylated carbon fiber; 10 parts by weight of Si69, 70 parts by weight of hydroxylated thermal cracking carbon black and 30 parts by weight of hydroxylated carbon fiber are poured into a high-speed mixer to be treated for 50min, the rotating speed of the mixer is 2000r/min, and the temperature is 80 ℃. The ratio of the granulating water to the carbon black mixture is as follows: 0.5:1 (mass ratio), drying by a dryer at the drying temperature of 125-220 ℃ until the moisture content is below 1%.
Testing of the properties of the modified thermal carbon blacks in rubber the same formulation as in example 1 was used and the compound properties are given in Table 3.
Example 3:
modifying 80 parts by weight of thermal cracking carbon black and 20 parts by weight of NaOH aqueous solution (the mass fraction of NaOH is 2%) in a grinding machine for 0.5h, wherein the rotating speed of the grinding machine is 1000r/min, and preparing the hydroxylated thermal cracking carbon black; modifying 90 parts by weight of carbon fiber and 10 parts by weight of NaOH aqueous solution (the mass fraction of NaOH is 2%) in a grinding machine for 0.5h, wherein the rotating speed of the grinding machine is 1000r/min, and preparing hydroxylated carbon fiber; 10 parts by weight of isopropyl trititanate, 70 parts by weight of hydroxylated thermal cracking carbon black and 30 parts by weight of hydroxylated carbon fiber are poured into a high-speed mixer to be treated for 50min, the rotating speed of the mixer is 2000r/min, and the temperature is 80 ℃. The ratio of the granulating water to the carbon black mixture is as follows: 0.5:1 (mass ratio), drying by a dryer at the drying temperature of 125-220 ℃ until the moisture content is below 1%.
Testing of the properties of the modified thermal carbon blacks in rubber the same formulation as in example 1 was used and the compound properties are given in Table 3.
Example 4:
modifying 85 parts by weight of thermal cracking carbon black and 15 parts by weight of NaOH aqueous solution (the mass fraction of NaOH is 2%) in a grinding machine for 0.5h, wherein the rotating speed of the grinding machine is 1000r/min, and preparing hydroxylation thermal cracking carbon black; modifying 85 parts by weight of carbon fiber and 15 parts by weight of NaOH aqueous solution (the mass fraction of NaOH is 2%) in a grinding machine for 0.5h, wherein the rotating speed of the grinding machine is 1000r/min, and preparing hydroxylated carbon fiber; 15 parts by weight of triethanolamine borate, 75 parts by weight of hydroxylated thermal cracking carbon black and 10 parts by weight of hydroxylated carbon fiber are poured into a high-speed mixer for treatment for 35min, the rotating speed of the mixer is 1500r/min, and the temperature is 100 ℃. The ratio of the granulating water to the carbon black mixture is as follows: 0.5:1 (mass ratio), drying by a dryer at the drying temperature of 125-220 ℃ until the moisture content is below 1%.
Testing of the properties of the modified thermal carbon blacks in rubber the same formulation as in example 1 was used and the compound properties are given in Table 3.
Example 5:
modifying 90 parts by weight of thermal cracking carbon black and 10 parts by weight of NaOH aqueous solution (the mass fraction of NaOH is 2%) in a grinding machine for 0.5h, wherein the rotating speed of the grinding machine is 1000r/min, and preparing hydroxylated thermal cracking carbon black; modifying 85 parts by weight of carbon fiber and 15 parts by weight of NaOH aqueous solution (the mass fraction of NaOH is 2%) in a grinding machine for 0.5h, wherein the rotating speed of the grinding machine is 1000r/min, and preparing hydroxylated carbon fiber; 10 parts of KH-550 (silane coupling agent), 75 parts of hydroxylated thermal cracking carbon black and 15 parts of hydroxylated carbon fiber are poured into a single-screw extruder, the rotating speed is 80r/min, and the operation is carried out for 0.5 h. The ratio of the granulating water to the carbon black mixture is as follows: 0.5:1 (mass ratio), drying by a dryer at the drying temperature of 125-220 ℃ until the moisture content is below 1%.
Testing of the properties of the modified thermal carbon blacks in rubber the same formulation as in example 1 was used and the compound properties are given in Table 3.
Example 6
Modifying 80 parts by weight of thermal cracking carbon black and 20 parts by weight of NaOH aqueous solution (the mass fraction of NaOH is 2%) in a grinding machine for 0.5h, wherein the rotating speed of the grinding machine is 1000r/min, and preparing the hydroxylated thermal cracking carbon black; modifying 80 parts by weight of carbon fiber and 20 parts by weight of NaOH aqueous solution (the mass fraction of NaOH is 2%) in a grinding machine for 0.5h, wherein the rotating speed of the grinding machine is 1000r/min, and preparing hydroxylated carbon fiber; 10 parts of Si69, 75 parts of hydroxylated thermal cracking carbon black and 15 parts of hydroxylated carbon fiber are poured into a single-screw extruder, the rotating speed is 120r/min, and the operation is carried out for 5 hours. The ratio of the granulating water to the carbon black mixture is as follows: 0.5:1 (mass ratio), drying by a dryer at the drying temperature of 125-220 ℃ until the moisture content is below 1%.
Testing of the properties of the modified thermal carbon blacks in rubber the same formulation as in example 1 was used and the compound properties are given in Table 3.
Example 7:
modifying 80 parts by weight of thermal cracking carbon black and 20 parts by weight of NaOH aqueous solution (the mass fraction of NaOH is 2%) in a grinding machine for 0.5h, wherein the rotating speed of the grinding machine is 1000r/min, and preparing the hydroxylated thermal cracking carbon black; modifying 90 parts by weight of carbon fiber and 10 parts by weight of NaOH aqueous solution (the mass fraction of NaOH is 2%) in a grinding machine for 0.5h, wherein the rotating speed of the grinding machine is 1000r/min, and preparing hydroxylated carbon fiber; 10 parts of Si69, 75 parts of hydroxylated thermal cracking carbon black and 15 parts of hydroxylated carbon fiber are poured into a single-screw extruder, the rotating speed is 100r/min, and the operation is carried out for 3 hours. The ratio of the granulating water to the carbon black mixture is as follows: 0.5:1 (mass ratio), drying by a dryer at the drying temperature of 125-220 ℃ until the moisture content is below 1%.
Testing of the properties of the modified thermal carbon blacks in rubber the same formulation as in example 1 was used and the compound properties are given in Table 3.
Comparative example 1
Unmodified thermal carbon black was added to the rubber according to the formulation of Table 2 and the rubber properties obtained are shown in Table 3.
TABLE 3 rubber Properties
And (4) conclusion: compared with the comparative examples, the rubber added with the modified thermal cracking carbon black has improved hardness, tensile strength and wear resistance.
The auxiliaries used in example 8 and example 9 are both commercially available and the modified thermal cracking carbon black used in example 8 and example 9 is the modified thermal cracking carbon black obtained in example 5.
The equipment used in examples 8 and 9 was an internal mixer, XSM-1/10-120, from Shanghai scientific Co., Ltd.; open mill, XK L-150, from Zhan Yangjiang machinery shop.
Example 8
TABLE 4
The rubber material is prepared by adopting a two-stage mixing process for mixing, wherein the first-stage mixing process and the second-stage mixing process are both carried out by using an internal mixer, the initial temperature of an internal mixing chamber is 90 ℃, the rotating speed of a first-stage rotor is 70 r/min, and the rotating speed of a second-stage rotor is 60 r/min.
The rubber material first-stage mixing process comprises the following steps: starting an internal mixer, lifting a top bolt, adding raw rubber, dropping the top bolt, and mixing for 60 s; lifting the top plug, adding 1/2 filler, dropping the top plug, mixing for 60s, adding the rest 1/2 filler, dropping the top plug, mixing for 120s, lifting the top plug, adding the auxiliary agent, mixing for 120s, discharging rubber, passing through a roller in an open mill, respectively carrying out three cutters on the left side and the right side, and discharging to obtain a section of master batch. And parking for 4 h.
The rubber two-stage mixing process comprises the following steps: starting an internal mixer, lifting a top bolt, adding a section of master batch, dropping the top bolt, and mixing for 60 s; lifting the top plug, adding the medicine, and dropping the top plug for mixing for 90 s; and lifting the top plug, removing the rubber, and thinly packaging for 6 times in an open mill to obtain the two-stage masterbatch.
Sulfur, promoter, and scorch retarder are added in the second stage, and other medicines are added in the first stage.
Example 9
TABLE 5
The rubber material is prepared by adopting a two-stage mixing process for mixing, wherein the first-stage mixing process and the second-stage mixing process are both carried out by using an internal mixer, the initial temperature of an internal mixing chamber is 90 ℃, the rotating speed of a first-stage rotor is 90r/min, and the rotating speed of a second-stage rotor is 70 r/min;
the rubber material first-stage mixing process comprises the following steps: starting an internal mixer, lifting a top bolt, adding raw rubber, dropping the top bolt, and mixing for 60 s; lifting the top plug, adding 1/2 filler, dropping the top plug, mixing for 60s, adding the rest 1/2 filler, dropping the top plug, mixing for 120s, lifting the top plug, adding the auxiliary agent, mixing for 120s, discharging rubber, passing through a roller in an open mill, respectively carrying out three cutters on the left side and the right side, and discharging to obtain a section of master batch. And parking for 4 h.
The rubber two-stage mixing process comprises the following steps: starting an internal mixer, lifting a top bolt, adding a section of master batch, dropping the top bolt, and mixing for 60 s; lifting the top plug, adding the auxiliary agent, and dropping the top plug for mixing for 90 s; and lifting the top plug, removing the rubber, and thinly packaging for 6 times in an open mill to obtain the two-stage masterbatch.
Sulfur, promoter, and scorch retarder are added in the second stage, and other medicines are added in the first stage.
The properties of the rubber compositions obtained are shown in Table 6
TABLE 6
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications can be made without departing from the principle of the present invention, and these modifications should also fall into the protection scope of the present invention.
Claims (7)
1. A modified thermal cracking carbon black comprises hydroxylated thermal cracking carbon black, hydroxylated carbon fiber and a coupling agent.
2. The modified thermal cracking carbon black of claim 1, wherein the coupling agent is one or more of silane coupling agent, titanate coupling agent and borate coupling agent.
3. The modified thermally cracked carbon black of claim 1, comprising
70-80 parts of hydroxylation thermal cracking carbon black;
10-30 parts by weight of hydroxylated carbon fiber;
5-15 parts of coupling agent.
4. The modified thermally cracked carbon black of claim 1, wherein: the hydroxylated thermal cracking carbon black is prepared from 80-90 parts by weight of thermal cracking carbon black and 10-20 parts by weight of hydroxylated modifier.
5. The modified thermally cracked carbon black of claim 1, wherein: the hydroxylated carbon fiber is prepared from 80-90 parts by weight of carbon fiber and 10-20 parts by weight of hydroxylated modifier.
6. The modified thermal cracking carbon black according to claim 4 or 5, wherein the hydroxylation modifier is one or more of an aqueous NaOH solution, an aqueous sodium hypochlorite solution and an aqueous phenolphthalein solution; the solute mass fraction of the NaOH aqueous solution, the sodium hypochlorite aqueous solution and the phenolphthalein aqueous solution is 1-4%.
7. The modified thermally cracked carbon black of claim 1, said carbon fibers having a length of from 0.1 to 6 mm; preferably 1-5 mm.
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| CN113150578A (en) * | 2021-04-23 | 2021-07-23 | 双星集团有限责任公司 | Novel modified pyrolysis carbon black and preparation method thereof |
| CN114854093A (en) * | 2022-04-24 | 2022-08-05 | 太原克林泰尔环保科技有限公司 | Carbon black applied to modified pyrolysis and preparation process thereof |
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