CN111171607A - Method for preparing hydrophilic carbon black, hydrophilic carbon black and application thereof - Google Patents
Method for preparing hydrophilic carbon black, hydrophilic carbon black and application thereof Download PDFInfo
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
Abstract
The invention discloses a method for preparing hydrophilic carbon black, which comprises the following steps: (1) mixing furnace carbon black with a hypochlorite aqueous solution, and reacting to obtain a carbon black dispersion liquid; (2) and (2) carrying out solid-liquid separation and drying on the carbon black dispersion liquid obtained in the step (1) to obtain hydrophilic carbon black. The method has the advantages that the carbon black after hypochlorite oxidation under the condition does not need further grading and purification treatment, thereby simplifying the production process, reducing the cost and protecting the environment. After the hydrophilic carbon black is added into the rubber, the elongation at break of the rubber is improved, and the rolling resistance and the compression fatigue temperature rise are reduced.
Description
Technical Field
The invention relates to preparation of hydrophilic carbon black and application of the hydrophilic carbon black in rubber, in particular to a method for preparing carbon black dispersion liquid by reacting furnace carbon black with hypochlorite aqueous solution, obtaining hydrophilic carbon black by centrifugal separation and drying, and applying the prepared hydrophilic carbon black in rubber.
Background
Carbon black is one of important industrial raw materials, and has characteristics of good weather resistance, chemical stability, colorability, conductivity and the like, so that carbon black is widely used in industrial fields such as rubber, paint, ink, printing and dyeing.
The carbon black has small particle size, large specific surface area and strong intermolecular force, so the carbon black is easy to agglomerate; at the same time, since the carbon black has a small number of oxygen-containing functional groups (carboxyl groups, hydroxyl groups, etc.) on the surface thereof and is hydrophobic and has low wettability, it is extremely difficult to stably disperse the carbon black in water at a high concentration, which affects the application of the carbon black in the industrial fields of ink, printing and dyeing, etc.
The method for improving the dispersion stability of the carbon black in water comprises the following steps: direct dispersion method, graft modification method, surface coating method and oxidation modification method.
The direct dispersion method is a method in which a dispersant and carbon black are mixed in water and the carbon black is dispersed under the action of a suitable external force. Although the direct dispersion method is simple to operate and easy to control conditions, the dispersion system can generate the phenomenon of inverse coarseness along with the increase of time, and the use of the product is not facilitated.
The graft modification method is to graft a polymer on the surface of carbon black through a chemical bond, and a certain steric hindrance repulsion is provided due to the long chain of the polymer. However, the use of the graft modification method is related to the type of carbon black, and the graft modification method has complex process flow and higher requirements on process conditions, and is difficult to be widely applied in industry.
The surface coating method is to coat a layer of hydrophilic polymer on the surface of the carbon black so that the carbon black can be stably dispersed in water. The surface coating method is independent of the type of carbon black, but the steps are complicated, and the industrial popularization is difficult.
The oxidation modification method is classified into a liquid-phase oxidation method, a gas-phase oxidation method, a plasma oxidation method, and a metal catalytic oxidation method.
The liquid phase oxidation method is a method of obtaining hydrophilic carbon black by subjecting carbon black and a strong oxidizing agent to oxidation-reduction reaction in water to form oxygen-containing functional groups such as hydrophilic carboxyl groups, carbonyl groups, hydroxyl groups, and the like on the surface of carbon black having a small volatile content.
The gas-phase oxidation method selects a gas-phase oxidant (mainly oxygen, air, ozone, oxynitride and the like) to oxidize and modify the surface of the carbon black, and is one of the traditional carbon black oxidation methods in industry.
The plasma oxidation method mainly comprises three types of microwave plasma, radio frequency plasma and arc plasma. Although the plasma oxidation method has a great development prospect in industrial production, the research on how to uniformly oxidize carbon black in a reaction vessel and how to reduce energy consumption is still the focus of the current stage.
The metal catalytic oxidation method is a method of catalytically oxidizing ordinary carbon black with a catalyst such as a metal chloride, a metal oxide, or a nitrogen oxide. At present, the method is still in a laboratory stage and is not industrialized.
In summary, liquid phase oxidation is a fast and efficient method for modifying carbon black. The liquid phase oxidation method, which is the earliest Surface oxidation modification method used in the carbon black industry, is widely reported in the literature, and the Oxidizing agent used is generally a strongly Oxidizing solution, such as nitric acid solution (Trawczy ń ski J, Japan S, Sayag C, et al. Surface acid of activated CBC [ J ]. Fuel Processing Technology, 2002, 77-78:317-324.), sulfuric acid solution (Borah D, Satokawa S, Kato S, et al. Characterisation of chemical modification carbon black for application [ J ]. Applied Surface Science,2008, 10, 3049-3056), perchloric acid solution (Choma J, Bureawicz-Mortka W, Jaonic M, Chaitance Science,2008, Journal of research 254, J.35, and filtration of chemical engineering, biological and biological solutions (biological and biological technologies, biological and biological sources, biological sources and biological sources, biological sources, preparing high-dispersity carbon black by oxidizing hydrogen peroxide [ J ], reporting silicate, 2008, 27(6):1124-1128), an ammonium persulfate solution (Korean, Liulianying, Yangwitai, carbon black surface oxidation modification and water dispersibility research [ J ], Beijing university of chemical industry, journal of 2010,37 (1): 78-84), diazonium salts (U.S. Pat. No.5,630,868, U.S. Pat. No.5,672,198), and the like. Of course, the physical properties of carbon blacks obtained by different oxidizing agents and different production methods vary due to different oxidizing effects. After oxidation, the oxygen-containing groups on the surface of the carbon black are increased, the wettability of the carbon black with water is improved, and a stable water-based carbon black dispersion system is easily obtained.
US2439442, US668724 disclose a process for treating carbon black with hypochlorite, which carbon black is acidified with hydrochloric acid to obtain a hydrophilic carbon black paste.
US3347632 discloses a process for treating carbon black with sodium hypochlorite which requires that the carbon black have an average particle size of less than 100nm, otherwise the treated carbon black is not dispersible in water.
US5609671, JPH107968, discloses a method of treating commercial acidic carbon black (preferably pH <4) with hypochlorite as an aqueous pigment ink, preferably at a temperature of 95 ℃ to 105 ℃ for a time of preferably 10 to 15 hours, which requires reverse osmosis membrane desalination until the conductivity of the dispersion becomes 0.2 mS/cm.
US5718746 discloses a process for treating low oil absorption carbon black (oil absorption <100ml/100g) with 1.6mol/L hypochlorite as an aqueous pigment ink, preferably at a temperature of 95 ℃ to 105 ℃ for a time of 3 to 20 hours, and requiring desalting and purification of the carbon black with an ultrafiltration membrane.
US7220304 discloses a process for using 1.6mol/L hypochlorite-treated carbon black as a water-based ink, the dispersion/pulverization step is carried out while oxidizing at a temperature of preferably 40 to 60 c for a time of preferably 3 to 10 hours at a dispersion/pulverization rotation speed of at least 500 rpm. Desalting and purification are carried out by using an ultrafiltration membrane, and secondary desalting and purification are carried out by using an electrodialyzer until the electrical conductivity of the filtrate is not more than 1.5 mS/cm. If the desalting is stopped outside this range, the ink contains a large amount of impurities such as NaCl, and the storage stability of the ink is therefore poor.
JP2000345085, JP20003455095 disclose methods in which carbon black is ground in advance or hypochlorite is added while grinding to prepare hydrophilic carbon black.
JP2007002068, JP2007084597 disclose a method for preparing hydrophilic carbon black by liquid phase oxidation using hypochlorite solution. In this method, a dispersant is added, and the carbon black is pre-pulverized in water.
JP2008195837 discloses a method for obtaining carbon black having dispersion stability after oxidation treatment of the surface of carbon black with hypochlorite and then surface treatment with a hydrophilic organic surface treating agent, oxidation treatment alone or surface treatment with only hydrophilicity being not possible to achieve the above object.
JP2012102158 discloses a method for producing hydrophilic carbon black using hypochlorite, which requires addition of an alkali solution to control the pH of the reaction solution, and the pH of the reaction solution is maintained at 9.0 or more throughout the period from the start to the end of the oxidation step.
Hydrophilic carbon blacks prepared by liquid phase oxidation have been used in rubber applications such as carbon blacks oxidized by hydrogen peroxide solutions for butyl rubber, delayed scorch, reduced gas transmission (Nagornaya M.N., Razdyakonova G.I., Khodakova S.ya, The effect of functional groups of carbon black on rubber Engineering [ J ]. Procedia Engineering 2016,152, 563-569); in US3330799, example 6 uses sodium hypochlorite to oxidize carbon black for 24 hours at room temperature, and the oxidized carbon black is added to butyl rubber for application to electrical insulation. US4075140 uses dilute nitric acid oxidized carbon black in rubber, which reduces the modulus of the rubber and increases the scorch time. US20190061424 uses hydrogen peroxide and/or ozone oxidized carbon black in heavy tires, slightly reducing the hysteresis properties of the rubber.
The technical solutions reported in the above documents have a common problem in that, in order to achieve a good oxidation effect, the oxidized carbon black needs to be subjected to desalting and purification treatment for many times. According to the invention, a large number of experiments are carried out to screen out proper carbon black and proper hypochlorite concentration, so that the consumption of hypochlorite is reduced as much as possible while the carbon black is ensured to be oxidized, and multiple desalting and purification treatments are avoided after the carbon black is oxidized.
The above documents report that the hydrophilic carbon black prepared by hypochlorite oxidation is rarely applied to rubber, and the oxidation degree of the used carbon black is low, so that the carbon black cannot be stably dispersed in water. The highly hydrophilic carbon black prepared by hypochlorite aqueous solution is used in rubber, so that the dispersion of the carbon black in the rubber can be improved, and the internal heat generation and the rolling resistance are effectively reduced.
Disclosure of Invention
The invention provides a method for preparing hydrophilic carbon black, which comprises the following steps:
(1) mixing furnace carbon black with a hypochlorite aqueous solution, and reacting to obtain a carbon black dispersion liquid;
(2) and (2) carrying out solid-liquid separation and drying on the carbon black dispersion liquid obtained in the step (1) to obtain hydrophilic carbon black.
In the process of the present invention, at least one aqueous hypochlorite solution is used to contact furnace carbon black particles in water and undergo liquid phase oxidation. The hypochlorite aqueous solution used in the present invention is not particularly limited, and is at least one selected from the group consisting of aqueous solutions of sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, lithium hypochlorite, barium hypochlorite, magnesium hypochlorite, ammonium hypochlorite, zinc hypochlorite, copper hypochlorite, and the like.
The pH value of the furnace carbon black is 7-10; preferably 8 to 9.
The DBP absorption of the furnace carbon black is 50 cm-180 cm3100g of; preferably 80-150 cm3/100g。
The nitrogen adsorption specific surface area of the furnace carbon black is 300m2The ratio of the total carbon content to the total carbon content is below g; preferably 100 to 300m2/g。
The average grain diameter of the furnace carbon black is 100-300 nm; preferably 200-300 nm.
The concentration of the hypochlorite aqueous solution is less than 1 mol/L; preferably 0.01 to 0.9 mol/L.
The carbon black concentration of the carbon black dispersion liquid is 30-200 g/L; preferably 50 to 100 g/L.
The reaction temperature is 30-100 ℃, and preferably 40-90 ℃. When the treatment temperature is lower than 30 ℃, hypochlorite hardly generates oxygen-containing functional groups on the surface of the carbon black, and when the treatment temperature is higher than 100 ℃, hypochlorite decomposition speed is accelerated.
The reaction time is 5 min-5 h, preferably 10 min-2 h.
The stirring is mechanical stirring or ultrasonic stirring, preferably mechanical stirring; the mechanical stirring speed is 50-500 rpm, preferably 50-400 rpm.
The solid-liquid separation is centrifugal separation or filtration separation, preferably centrifugal separation.
In the method of the present invention, the carbon black is subjected to liquid-phase oxidation treatment using hypochlorite to form an acid group on the surface, thereby obtaining hydrophilic carbon black.
The invention also discloses the hydrophilic carbon black obtained by the method.
The invention also discloses application of the hydrophilic carbon black in rubber.
The invention also discloses a preparation method of the rubber, which is characterized by comprising the following steps:
(1) mixing 70-40 parts by weight of hydrophilic carbon black with 30-60 parts by weight of raw rubber or latex, adding a rubber additive, and uniformly mixing to obtain a rubber compound;
(2) and (3) carrying out plate vulcanization on the rubber compound in the step (1) to obtain vulcanized rubber.
The raw rubber can be one or more of natural rubber, styrene butadiene rubber, butyl rubber and nitrile butadiene rubber; the latex can be one or more of natural latex, styrene-butadiene latex, butyronitrile latex and butyl latex.
The method disclosed by the invention has the advantages that the proper carbon black is selected, at least one hypochlorite aqueous solution is used, and the hypochlorite aqueous solution and the carbon black are subjected to liquid-phase oxidation reaction under the proper reaction condition, so that the oxidized carbon black has good hydrophilicity and can have excellent dispersion stability in water.
And under the appropriate condition, the hypochlorite with lower concentration is used, so that the waste of the oxidant is reduced under the condition of ensuring the dispersion stability of the carbon black in water, the cost is saved, and the subsequent purification and classification treatment of the hydrophilic carbon black can be effectively avoided. The hydrophilic carbon black is applied to the rubber, so that the breaking elongation of the rubber is improved, and the rolling resistance and the compression fatigue temperature rise are reduced.
The terms "above," "below," "greater than," "less than," and the like in this specification are intended to denote ranges of values which include the end point value itself.
The terms "comprising," "including," "containing," "having," and the like, as used herein, are not intended to exclude the inclusion of other elements or steps not listed in the present invention.
The carbon black has a DBP value (absorption of carbon black) which is the DBP value. Under the specified test conditions, 100g of carbon black absorbs dibutyl phthalate (DBP, di-n-butyl phthalate) in volume (cm)3) And (4) counting. To characterize the degree of aggregation of the carbon black. The DBP value allows calculation of the void volume between carbon black aggregates, which is a measure of the degree of aggregation and agglomeration of the carbon black. When carbon black is used as a rubber filler, the degree of aggregation of its particles affects the performance properties of the carbon black vulcanizate.
Drawings
1. FIG. 1 is a graph showing the change in storage modulus with strain of rubber 1 and rubber 1 (RPA-2000 rubber Analyzer, Taiwan high-speed railway testing Instrument Co., Ltd., NR-HCB denotes rubber 1 of example 1, and NR-CB denotes rubber 1 obtained in comparative example 1). FIG. 1 shows that rubber 1 has a low Δ G', indicating that hydrophilic carbon black HBC-1 has better dispersing properties in natural rubber.
2. FIG. 2 is a graph showing the loss factors of rubber 1 and rubber 1 as a function of strain (RPA-2000 rubber Analyzer, Taiwan high-speed railway testing Instrument Co., Ltd., NR-HCB denotes rubber 1 obtained in example 1, and NR-CB denotes rubber 1 obtained in comparative example 1). FIG. 2 shows that the loss factor of rubber 1 is lower than that of rubber 1, indicating that the hydrophilic carbon black HBC-1 has a lower rolling resistance in natural rubber.
Examples
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
Example 1
Commercially available furnace carbon black (DBP absorption 150 cm)3100g, nitrogen adsorption specific surface area of 240m2And/g) 300g of the carbon black is added into 3L of 0.89mol/L sodium hypochlorite solution, and the mixture is subjected to ultrasonic vibration in an ultrasonic cleaner (KH7200 type), so that the carbon black is uniformly dispersed in the sodium hypochlorite solution, the temperature is controlled to be 60 ℃, and the reaction is carried out for 3 hours under continuous heat preservation and stirring.
And (3) after the liquid-phase oxidation reaction is finished, dehydrating the carbon black solution in a centrifugal machine, controlling the rotating speed of the centrifugal machine to be 9000rpm, and separating the hydrophilic carbon black from the aqueous solution. And drying to obtain the hydrophilic carbon black HCB-1.
The obtained hydrophilic carbon black is mixed according to a formula (100 parts by weight of natural rubber, 50 parts by weight of hydrophilic carbon black HCB-1, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of anti-aging agent 4010NA, 1.2 parts by weight of accelerator CZ and 2 parts by weight of sulfur) to obtain a rubber compound. And vulcanizing the mixed rubber at 145 ℃ for positive vulcanization time to obtain hydrophilic carbon black/natural rubber vulcanized rubber which is marked as rubber 1.
Example 2
Commercially available furnace carbon black (DBP absorption of 130 cm)3100g, nitrogen adsorption specific surface area of 210m2Per gram) 200 grams of the carbon black is added into 3 liters of 0.54mol/L potassium hypochlorite solution and stirred at the rotating speed of 200rpm, so that the carbon black is evenly dispersed in the potassium hypochlorite solution, the temperature is controlled to be 60 ℃, and the heat preservation is continuously carried outThe reaction was stirred for 2 hours.
And (3) after the liquid-phase oxidation reaction is finished, dehydrating the carbon black solution in a centrifugal machine, controlling the rotating speed of the centrifugal machine to be 9000rpm, and separating the hydrophilic carbon black from the aqueous solution. And drying to obtain the hydrophilic carbon black HCB-2.
The obtained hydrophilic carbon black is mixed according to a formula (100 parts by weight of styrene butadiene rubber, 50 parts by weight of hydrophilic carbon black HCB-2, 3 parts by weight of zinc oxide, 1 part by weight of stearic acid, 1.34 parts by weight of accelerator NS and 1.2 parts by weight of sulfur) to obtain a rubber compound. And vulcanizing the mixed rubber at 151 ℃ for normal vulcanization time to obtain hydrophilic carbon black/styrene butadiene rubber vulcanized rubber, which is marked as rubber 2.
Example 3
Commercially available furnace carbon black (DBP absorption 120 cm)3100g, nitrogen adsorption specific surface area of 190m2Per gram) 150g of the carbon black is added into 3L of 0.68mol/L sodium hypochlorite solution and stirred at the rotating speed of 300rpm, so that the carbon black is uniformly dispersed in the sodium hypochlorite solution, the temperature is controlled to be 80 ℃, and the reaction is carried out for 1 hour by continuous heat preservation and stirring.
And (3) after the liquid-phase oxidation reaction is finished, dehydrating the carbon black solution in a centrifugal machine, controlling the rotating speed of the centrifugal machine to be 7000rpm, and separating the hydrophilic carbon black from the aqueous solution. And drying to obtain the hydrophilic carbon black HCB-3.
The obtained hydrophilic carbon black was mixed according to the formulation (100 parts by weight of butyl rubber, 50 parts by weight of hydrophilic carbon black HCB-3, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 2 parts by weight of antioxidant 4010NA, 1.5 parts by weight of accelerator CZ, 0.2 parts by weight of accelerator M, 2.5 parts by weight of sulfur) to obtain a rubber compound. And vulcanizing the rubber compound at 160 ℃ for positive vulcanization time to obtain hydrophilic carbon black/butyl rubber vulcanized rubber, which is marked as rubber 3.
Example 4
Commercially available furnace carbon black (DBP absorption of 146 cm)3100g, nitrogen adsorption specific surface area of 230m2Per g)200g of the carbon black was added to 3.5L of 0.89mol/L potassium hypochlorite solution and stirred at 240rpm to uniformly disperse the carbon black in the potassium hypochlorite solution, and the temperature was controlled toThe reaction was continued with stirring at 70 ℃ for 0.5 hour.
And (3) after the liquid-phase oxidation reaction is finished, dehydrating the carbon black solution in a centrifugal machine, controlling the rotating speed of the centrifugal machine to be 8000rpm, and separating the hydrophilic carbon black from the water solution. And drying to obtain the hydrophilic carbon black HCB-4.
Mixing the obtained hydrophilic carbon black according to a formula (100 parts by weight of styrene-butadiene latex, 50 parts by weight of hydrophilic carbon black HCB-4, 3 parts by weight of zinc oxide and 1 part by weight of stearic acid), drying in an oven at 80 ℃ for 24 hours, and then sequentially adding 1.34 parts by weight of accelerator NS and 1.2 parts by weight of sulfur, and uniformly mixing to obtain the rubber compound. And vulcanizing the mixed rubber at 151 ℃ for normal vulcanization time to obtain hydrophilic carbon black/styrene butadiene rubber vulcanized rubber which is marked as rubber 4.
Example 5
Commercially available furnace carbon black (DBP absorption of 125 cm)3100g, nitrogen adsorption specific surface area 253m2And/g) 200g of the carbon black is added into 3L of 0.54mol/L sodium hypochlorite solution and stirred at the rotating speed of 240rpm, so that the carbon black is uniformly dispersed in the sodium hypochlorite solution, the temperature is controlled to be 60 ℃, and the reaction is continuously kept for 4 hours under stirring.
And (3) after the liquid-phase oxidation reaction is finished, dehydrating the carbon black solution in a centrifugal machine, controlling the rotating speed of the centrifugal machine to be 7000rpm, and separating the hydrophilic carbon black from the aqueous solution. And drying to obtain the hydrophilic carbon black HCB-5.
The obtained hydrophilic carbon black is mixed according to a formula (100 parts by weight of natural rubber, 50 parts by weight of hydrophilic carbon black HCB-5, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of anti-aging agent 4010NA, 1.2 parts by weight of accelerator CZ and 2 parts by weight of sulfur) to obtain a rubber compound. And vulcanizing the mixed rubber at 145 ℃ for positive vulcanization time to obtain hydrophilic carbon black/natural rubber vulcanized rubber, which is marked as rubber 5.
Example 6
Commercially available furnace carbon black (DBP absorption 120 cm)3100g, nitrogen adsorption specific surface area of 260m2Per g)300g was added to 3.5L of 0.54mol/L potassium hypochlorite solution and stirred at 240rpmSo that the carbon black is uniformly dispersed in the potassium hypochlorite solution, the temperature is controlled at 60 ℃, and the reaction is continuously carried out for 1 hour by heat preservation and stirring.
And (3) after the liquid-phase oxidation reaction is finished, dehydrating the carbon black solution in a centrifugal machine, controlling the rotating speed of the centrifugal machine to be 8000rpm, and separating the hydrophilic carbon black from the water solution. And drying to obtain the hydrophilic carbon black HCB-6.
The obtained hydrophilic carbon black is mixed according to a formula (100 parts by weight of natural rubber, 50 parts by weight of hydrophilic carbon black HCB-6, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of anti-aging agent 4010NA, 1.2 parts by weight of accelerator CZ and 2 parts by weight of sulfur) to obtain a rubber compound. And vulcanizing the mixed rubber at 145 ℃ for positive vulcanization time to obtain hydrophilic carbon black/natural rubber vulcanized rubber, which is marked as rubber 6.
Comparative example 1
Commercially available furnace carbon black (DBP absorption 150 cm)3100g, nitrogen adsorption specific surface area of 240m2Per g) according to the formula (100 parts by weight of natural rubber, 50 parts by weight of furnace carbon black, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 1 part by weight of anti-aging agent 4010NA, 1.2 parts by weight of accelerator CZ, 2 parts by weight of sulfur) to obtain the rubber compound. The rubber mix was vulcanized at 145 ℃ for a positive cure time to give a commercial furnace black/natural rubber vulcanizate designated as rubber 1.
Comparative example 2
Commercially available furnace carbon black (DBP absorption of 130 cm)3100g, nitrogen adsorption specific surface area of 210m2And/g) mixing according to a formula (100 parts by weight of styrene-butadiene rubber, 50 parts by weight of furnace carbon black, 3 parts by weight of zinc oxide, 1 part by weight of stearic acid, 1.34 parts by weight of accelerator NS and 1.2 parts by weight of sulfur) to obtain a rubber compound. And vulcanizing the mixed rubber at 151 ℃ for positive vulcanization time to obtain the commercial furnace carbon black/styrene butadiene rubber vulcanized rubber which is marked as rubber 2.
Comparative example 3
Commercially available furnace carbon black (DBP absorption 120 cm)3100g, nitrogen adsorption specific surface area of 190m2Per g) according to the formula (100 parts by weight)Butyl rubber, 50 parts by weight of furnace carbon black, 3 parts by weight of zinc oxide, 1 part by weight of stearic acid, 1.34 parts by weight of accelerator NS and 1.2 parts by weight of sulfur) to obtain a rubber compound. The rubber compound was vulcanized at 160 ℃ for a positive vulcanization time to give a commercial furnace black/butyl rubber vulcanizate, designated as rubber 3.
The hydrophilic carbon black obtained in examples 1 to 6, after drying, had a soft surface, and no white crystals were precipitated on the wall of the beaker, and could be used directly without purification and classification post-treatment.
Sedimentation stability analysis of hydrophilic carbon Black
And (3) carrying out sedimentation stability analysis on the obtained hydrophilic carbon black, adding a certain amount of unoxidized furnace carbon black and hydrophilic carbon black into water respectively, shaking up, and observing the change condition of the carbon black solution. Observation shows that after the sample is stood for 7 days, the unoxidized furnace carbon black solution is completely layered, and the upper layer solution is completely transparent; the hydrophilic carbon black solution is uniform and has no delamination phenomenon.
Table 1 shows the particle size and potential of unoxidized furnace blacks and carbon blacks from examples 1-6 (test equipment: nanometer laser particle size potential Analyzer ZETASIZER/Nano ZS90, Malvern, UK).
TABLE 1 particle size and potential of unoxidized furnace blacks and hydrophilic blacks obtained in examples 1-6
Note: CB represents a commercially available furnace carbon black
HCB represents hydrophilic carbon black
Conclusion
The granularity of the carbon black after oxidation is reduced, and the potential value of the carbon black solution is changed from a positive value to a negative value, which shows that the dispersion stability of the carbon black in water is greatly improved.
XPS elemental analysis of carbon black
Table 2 shows XPS elemental analysis (test equipment: X-ray photoelectron spectrometer ESCALB 250, ThermoFisher Scientific Co., U.S.A.) of carbon blacks from examples 1-6.
TABLE 2 carbon Black element analysis of hydrophilic carbon blacks obtained in inventive examples 1-6
Note: CB represents a commercially available furnace carbon black
HCB represents hydrophilic carbon black
C% and O% are mass percentages.
Conclusion
The oxygen content of the oxidized carbon black is increased rapidly, which shows that the oxygen-containing functional groups on the surface of the carbon black are increased, and the hydrophilic acid functional groups are increased. Therefore, the water solubility of the carbon black after hypochlorite oxidation is greatly improved.
Performance testing of rubber
Table 3 shows the comparison of the properties of the rubbers obtained in examples 1 to 6 with those obtained in comparative examples 1 to 3 (scorch time: MR-C3 rotor-less vulcanizer, Beijing Ruidayuchen instruments Ltd.; elongation at break: tensile testing machine AI-7000S, Taiwan high-speed rail testing instruments Ltd., compression fatigue temperature rise: rubber compression heat generation testing machine RH-2000N, Taiwan high-speed rail testing instruments Ltd., hardness: Shore durometer, Shanghai Sichuan land measuring instruments Ltd.).
TABLE 3 comparison of the properties of the rubbers obtained in examples 1 to 6 with those of comparative examples 1 to 3
Conclusion
After hydrophilic carbon black is added to rubber, the scorch time is reduced, but the elongation at break is improved and the compression fatigue temperature rise is reduced.
Comparison of RPA tests of rubber 1 and rubber 1
Conclusion
By comparing FIGS. 1 and 2(RPA-2000 rubber Analyzer, Taiwan high-speed railway testing Instrument Co., Ltd., NR-HCB denotes rubber 1 of example 1, and NR-CB denotes rubber 1 obtained in comparative example 1), it can be seen that rubber 1 has a lower Δ G' than rubber 1, indicating that hydrophilic carbon black HBC-1 has a better dispersion property in natural rubber. The loss factor of rubber 1 was lower than that of rubber 1, indicating that the hydrophilic carbon black HBC-1 has a lower rolling resistance in natural rubber.
Claims (6)
1. A method of making a hydrophilic carbon black comprising the steps of:
(1) mixing furnace carbon black with a hypochlorite aqueous solution, and reacting to obtain a carbon black dispersion liquid;
(2) carrying out solid-liquid separation and drying on the carbon black dispersion liquid obtained in the step (1) to obtain hydrophilic carbon black;
the pH value of the furnace carbon black is 7-10;
the carbon black concentration of the carbon black dispersion liquid is 30-200 g/L;
the DBP absorption of the furnace carbon black is 50-180 cm3/100g；
The nitrogen adsorption specific surface area of the furnace carbon black is 300m2The ratio of the total carbon content to the total carbon content is below g;
the average particle size of the furnace carbon black is 100-300 nm;
the concentration of hypochlorite is less than 1 mol/L;
the reaction temperature is 30-100 ℃;
the reaction time is 5 min-5 h;
the furnace carbon black is stirred and contacted with the hypochlorite aqueous solution in a mechanical stirring or ultrasonic stirring mode;
the solid-liquid separation is centrifugal separation or filtration separation.
2. The method of claim 1, wherein the hypochlorite is at least one selected from the group consisting of sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, lithium hypochlorite, barium hypochlorite, magnesium hypochlorite, ammonium hypochlorite, zinc hypochlorite, and copper hypochlorite.
3. A hydrophilic carbon black obtained by the method of any one of claims 1-2.
4. Use of the hydrophilic carbon black according to claim 3 in rubber.
5. A rubber, characterized by being prepared by the following method:
(1) mixing 70-40 parts by weight of the hydrophilic carbon black of claim 3 with 30-60 parts by weight of raw rubber or latex, adding a rubber auxiliary agent, uniformly mixing,
obtaining the rubber compound;
(2) and (3) vulcanizing the rubber compound in the step (1) to obtain vulcanized rubber.
6. The preparation method of claim 5, wherein the raw rubber is one or more of natural rubber, styrene butadiene rubber, butyl rubber and nitrile butadiene rubber; the latex can be one or more of natural latex, styrene-butadiene latex, butyronitrile latex and butyl latex.
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