CN111138714A - Ultra-dispersed white carbon black and preparation method thereof - Google Patents
Ultra-dispersed white carbon black and preparation method thereof Download PDFInfo
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- CN111138714A CN111138714A CN202010072857.XA CN202010072857A CN111138714A CN 111138714 A CN111138714 A CN 111138714A CN 202010072857 A CN202010072857 A CN 202010072857A CN 111138714 A CN111138714 A CN 111138714A
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- carbon black
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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
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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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
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—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
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a super-dispersed white carbon black and a preparation method thereof, and the preparation method of the super-dispersed white carbon black comprises the following steps: (1) preparing a silicon dioxide precursor: after the reaction of water glass and sulfuric acid, filtering and washing to obtain silicic acid, and preparing a silicon dioxide precursor; (2) preparing a metal-organic coordination polymer; (3) and (3) adding the silicon dioxide precursor prepared in the step (1) and the metal-organic coordination polymer prepared in the step (2) into water to prepare slurry, further uniformly stirring, and drying at the temperature of 320-380 ℃ to finally prepare the ultra-dispersed white carbon black. The metal-organic coordination polymer can resist the temperature of more than 400 ℃, and the white carbon black modified by the metal-organic coordination polymer can resist the high temperature required by the decomposition of silicic acid, thereby ensuring the modification effect.
Description
Technical Field
The invention relates to the technical field of chemistry, and particularly relates to ultra-dispersed white carbon black and a preparation method thereof.
Background
The white carbon black is used as a reinforcing agent, so that the rolling resistance of the tire and the hysteresis loss of the tire tread are reduced, the wet gripping performance is improved, and the wear resistance of the tire tread is improved, so that the white carbon black is the key for manufacturing the green tire. However, the "green tire" standard is only met when the white carbon loading is large.
The surface of the silica particles contains more hydroxyl groups, and generally, 3 kinds of free hydroxyl groups, continuous hydroxyl groups and double hydroxyl groups are available. Due to the special structure, the special characteristics of the white carbon black are formed, for example, the polarity of the particle surface is very strong, the surface energy is very high, and the white carbon black has very strong water absorption, so that the particle agglomeration phenomenon is caused. In addition, the organic phase is difficult to disperse, and the polymer composite material is difficult to combine with the organic phase, so that various performance indexes are poor. Thus, it is required to perform a modification treatment.
The conventional method for modifying the white carbon black comprises the following steps: organic modifiers such as stearic acid, silane coupling agent, sodium gluconate and the like are selected to modify the white carbon black by a wet method or a dry method, and the wet method has higher process complexity than the dry method, but has good comprehensive modification effect. But has the disadvantages that: the aqueous silicon dispersion obtained by the precipitation reaction needs to be decomposed at a temperature higher than 350 ℃ to obtain silicon dioxide, the high drying temperature puts high requirements on the modifier, and the high temperature can influence the modification effect of the conventional modifier, so that the effect cannot be exerted optimally.
Disclosure of Invention
The invention aims to provide ultra-dispersed white carbon black with obviously improved dispersibility and a preparation method thereof.
The technical scheme of the invention is as follows: the ultra-dispersed white carbon black comprises silicon dioxide and a metal-organic coordination polymer, wherein the mass percentage of the silicon dioxide to the metal-organic coordination polymer is 80-95: 20-5.
The preparation method of the ultra-dispersed white carbon black comprises the following steps:
(1) preparing a silicon dioxide precursor: after the reaction of water glass and sulfuric acid, filtering and washing to obtain silicic acid, and preparing a silicon dioxide precursor;
(2) preparation of Metal-organic coordination Polymer:
under the condition of continuous stirring, adding an organic ligand into a sodium hydroxide solution with the concentration of 5-30% according to the stoichiometric relation, and completely dissolving to obtain an organic sodium solution; adding a prepared inorganic metal compound aqueous solution into the organic sodium salt solution under continuous stirring, continuously stirring and reacting for 20-90 min at the rotating speed of 200-700 r/min, filtering and washing to obtain a metal-organic coordination polymer for later use;
(3) and (3) adding the silicon dioxide precursor prepared in the step (1) and the metal-organic coordination polymer prepared in the step (2) into water to prepare slurry, further uniformly stirring, and drying at the temperature of 350-400 ℃ to finally prepare the ultra-dispersed white carbon black.
Further, in the step (2), the inorganic metal compound is one or a combination of several of calcium chloride, calcium nitrate, zinc chloride and zinc nitrate.
Further, in the step (2), the mass concentration of the inorganic metal compound is 20-50%.
Further, in step (2), the organic ligand should have at least one multi-dentate functional group.
Further, in the step (2), the organic ligand is one or a combination of several of terephthalic acid, trimesic acid, oxalic acid or succinic acid.
Compared with the prior art, the invention has the following advantages:
(1) the metal-organic coordination polymer can resist the temperature of more than 400 ℃, and the white carbon black modified by the metal-organic coordination polymer can resist the high temperature required by the decomposition of silicic acid, thereby ensuring the modification effect.
(2) Under the condition of not influencing abrasion, the ultra-dispersed white carbon black can improve the wet skid resistance and reduce the rolling resistance, can balance the contradiction of 'magic triangles', and improve the performance of 'green tires'.
(3) The product of the invention has excellent dispersion performance, obviously reduces the Mooney viscosity of rubber compound, and improves the processing performance of rubber compound under the condition of not influencing the comprehensive performance of vulcanized rubber, thereby reducing the number of mixing stages and reducing the energy consumption.
(4) The product of the invention can improve the surface smoothness and brightness of rubber products, reduce the phenomena of pitted surfaces and broken edges and improve the production qualification rate.
Detailed Description
The invention is further illustrated by the following examples. It should be understood that these examples are illustrative and exemplary of the present invention, and are not intended to limit the scope of the present invention in any way.
Example 1
The ultra-dispersed white carbon black comprises silicon dioxide and a zinc-oxalic acid coordination polymer, wherein the mass percentage of the silicon dioxide to the zinc-oxalic acid coordination polymer is 80: 20.
The preparation method of the ultra-dispersed white carbon black comprises the following steps:
(1) preparing a silicon dioxide precursor: after the reaction of water glass and sulfuric acid, filtering and washing to obtain silicic acid, and preparing a silicon dioxide precursor;
(2) preparation of Metal-organic coordination Polymer: under the condition of continuous stirring, adding an organic ligand into a sodium hydroxide solution with the concentration of 5% according to the stoichiometric relation, and completely dissolving to obtain an organic sodium solution; adding a prepared inorganic metal compound aqueous solution into the organic sodium salt solution under continuous stirring, continuously stirring and reacting for 20min at the rotating speed of 700r/min, filtering and washing to obtain a metal-organic coordination polymer for later use; the inorganic metal compound is zinc chloride, and the mass concentration of the inorganic metal compound is 20%; the organic ligand is oxalic acid.
(3) And (3) adding the silicon dioxide precursor prepared in the step (1) and the zinc-oxalic acid coordination polymer prepared in the step (2) into water to prepare slurry, further uniformly stirring, and drying at the temperature of 350 ℃ to finally prepare the ultra-dispersed white carbon black.
Example 2
Example 2 differs from example 1 in that:
the ultra-dispersed white carbon black comprises silicon dioxide and a calcium-tribenzoic acid coordination polymer, wherein the mass percentage of the silicon dioxide to the calcium-tribenzoic acid coordination polymer is 95: 5.
The preparation method of the ultra-dispersed white carbon black comprises the following steps:
in step (2), preparation of a metal-organic coordination polymer:
under the condition of continuous stirring, adding the organic ligand into a sodium hydroxide solution with the concentration of 30% according to the stoichiometric relation, and completely dissolving to obtain an organic sodium solution; adding a prepared inorganic metal compound aqueous solution into the organic sodium salt solution under continuous stirring, continuously stirring and reacting for 90min at the rotating speed of 200r/min, filtering and washing to obtain a metal-organic coordination polymer for later use; the inorganic metal compound is calcium nitrate, and the mass concentration of the inorganic metal compound is 50%; the organic ligand is trimesic acid.
In the step (3), the silicon dioxide precursor prepared in the step (1) and the calcium-trimesic acid coordination polymer prepared in the step (2) are added into water to be mixed into slurry, and after the slurry is further stirred uniformly, the slurry is dried at the temperature of 400 ℃ to finally prepare the ultra-dispersed white carbon black.
Example 3
Example 3 differs from example 1 in that:
the ultra-dispersed white carbon black comprises silicon dioxide and a calcium/zinc-terephthalic acid/succinic acid coordination polymer, wherein the mass percentage of the silicon dioxide to the calcium/zinc-terephthalic acid/succinic acid coordination polymer is 90: 10.
The preparation method of the ultra-dispersed white carbon black comprises the following steps:
in step (2), preparation of a metal-organic coordination polymer:
under the condition of continuous stirring, adding the organic ligand into a sodium hydroxide solution with the concentration of 20% according to the stoichiometric relation, and completely dissolving to obtain an organic sodium solution; adding a prepared inorganic metal compound aqueous solution into the organic sodium salt solution under continuous stirring, continuously stirring and reacting for 50min at the rotating speed of 500r/min, filtering and washing to obtain a metal-organic coordination polymer for later use; the inorganic metal compound is a combination of calcium chloride and zinc chloride, and the total mass concentration of the inorganic metal compound is 35%; the organic ligand is a combination of terephthalic acid and succinic acid.
In the step (3), adding the silicon dioxide precursor prepared in the step (1) and the calcium/zinc-terephthalic acid/succinic acid coordination polymer obtained in the step (2) into water to prepare slurry, further uniformly stirring, and drying at the temperature of 360 ℃ to finally prepare the ultra-dispersed white carbon black.
Comparative example 1
Difference between comparative example 1 and example 1:
and (2) drying the silicon dioxide precursor obtained in the step (1) at the temperature of 350 ℃ to finally prepare the white carbon black.
Test 1
Applying different types of white carbon black to tire tread formulas, wherein the formulas are as follows: BR 10, SBR 90, carbon black N2348, V500 Oil 17.5, 373N 5, stearic acid 1, ZnO 2, anti-aging agent 2, DPG 1.2, accelerator 1.5, S2.3, coupling agent Si696.2 and white carbon black (variant: the ultra-dispersed white carbon black prepared in example 1, the white carbon black prepared in comparative example 1 and the commercially available Lodige sub-high-dispersion white carbon black 1165 MP) 78, and the specific formula is shown in Table 1.
Plasticating rubber on a double-roller open mill, adding various auxiliaries to obtain mixed rubber, and vulcanizing at 151 ℃ for normal vulcanization time to obtain vulcanized rubber. The test was carried out according to the national standard and the properties obtained are shown in Table 2.
TABLE 1 formulation
TABLE 2 Performance data
Analysis of the data in Table 2: (1) the Tan delta 0 ℃ value of the formula 1 is the largest, which shows that the anti-slippery performance is the best; the Tan delta 60 ℃ value is minimum, which indicates that the rolling resistance is minimum; the maximum value of resilience at 60 ℃; the abrasion data is basically unchanged; these data demonstrate that the ultra-dispersed white carbon black prepared in example 1 can improve wet skid resistance and reduce rolling resistance without affecting abrasion, thereby balancing the contradiction of the magic triangle and improving the performance of the green tire.
(2) The Mooney viscosity of the formula 1 is only 75, which is obviously less than 107 of the formula 2 and 91 of the formula 3, and the performances of the three formulas such as tensile strength, elongation, M100, M300 and the like are almost the same, which shows that the ultra-dispersed white carbon black of the example 1 can improve the processability of the rubber material;
(3) comparing the specific gravity data of 3 formulas shows that formula 1 is the lowest, which indicates that the white carbon black prepared in example 1 can reduce the volume cost of products such as tires.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the foregoing description only for the purpose of illustrating the principles of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims, specification, and equivalents thereof.
Claims (6)
1. The ultra-dispersed white carbon black is characterized in that: the ultra-dispersed white carbon black comprises silicon dioxide and a metal-organic coordination polymer, wherein the mass percentage of the silicon dioxide to the metal-organic coordination polymer is 80-95: 20-5.
2. The preparation method of the ultra-dispersed white carbon black of claim 1, which is characterized by comprising the following steps:
(1) preparing a silicon dioxide precursor: after the reaction of water glass and sulfuric acid, filtering and washing to obtain silicic acid, and preparing a silicon dioxide precursor;
(2) preparation of Metal-organic coordination Polymer:
under the condition of continuous stirring, adding an organic ligand into a sodium hydroxide solution with the concentration of 5-30% according to the stoichiometric relation, and completely dissolving to obtain an organic sodium solution; adding a prepared inorganic metal compound aqueous solution into the organic sodium salt solution under continuous stirring, continuously stirring and reacting for 20-90 min at the rotating speed of 200-700 r/min, filtering and washing to obtain a metal-organic coordination polymer for later use;
(3) and (3) adding the silicon dioxide precursor prepared in the step (1) and the metal-organic coordination polymer prepared in the step (2) into water to prepare slurry, further uniformly stirring, and drying at the temperature of 350-400 ℃ to finally prepare the ultra-dispersed white carbon black.
3. The preparation method of the ultra-dispersed white carbon black according to claim 2, which is characterized by comprising the following steps: in the step (2), the inorganic metal compound is one or a combination of calcium chloride, calcium nitrate, zinc chloride or zinc nitrate.
4. The preparation method of the ultra-dispersed white carbon black according to claim 2, which is characterized by comprising the following steps: in the step (2), the mass concentration of the inorganic metal compound is 20-50%.
5. The preparation method of the ultra-dispersed white carbon black according to claim 2, which is characterized by comprising the following steps: in step (2), the organic ligand should have at least one multi-dentate functional group.
6. The preparation method of the ultra-dispersed white carbon black according to claim 2, which is characterized by comprising the following steps: in the step (2), the organic ligand is one or a combination of more of terephthalic acid, trimesic acid, oxalic acid or succinic acid.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114539814A (en) * | 2022-02-26 | 2022-05-27 | 江苏爱特恩高分子材料有限公司 | Preparation method of high-dispersion white carbon black |
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| US20160304791A1 (en) * | 2014-10-31 | 2016-10-20 | Chevron U.S.A. Inc. | Process, method, and system for removing heavy metals from fluids |
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| CN114539814A (en) * | 2022-02-26 | 2022-05-27 | 江苏爱特恩高分子材料有限公司 | Preparation method of high-dispersion white carbon black |
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Application publication date: 20200512 |