CN114316369A - Modified white carbon black and preparation method thereof - Google Patents
Modified white carbon black and preparation method thereof Download PDFInfo
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- CN114316369A CN114316369A CN202210008269.9A CN202210008269A CN114316369A CN 114316369 A CN114316369 A CN 114316369A CN 202210008269 A CN202210008269 A CN 202210008269A CN 114316369 A CN114316369 A CN 114316369A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 239000006229 carbon black Substances 0.000 title claims abstract description 132
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910000077 silane Inorganic materials 0.000 claims abstract description 67
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 24
- 238000005507 spraying Methods 0.000 claims abstract description 24
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 18
- FPLYNRPOIZEADP-UHFFFAOYSA-N octylsilane Chemical compound CCCCCCCC[SiH3] FPLYNRPOIZEADP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000000413 hydrolysate Substances 0.000 claims abstract description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- -1 n-octyl group Chemical group 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 5
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000006011 modification reaction Methods 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 19
- 239000005060 rubber Substances 0.000 abstract description 19
- 239000012855 volatile organic compound Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 10
- 239000000047 product Substances 0.000 abstract description 7
- 235000019241 carbon black Nutrition 0.000 description 114
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000012986 modification Methods 0.000 description 19
- 230000004048 modification Effects 0.000 description 19
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 16
- 230000002209 hydrophobic effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- GHBKQPVRPCGRAQ-UHFFFAOYSA-N octylsilicon Chemical compound CCCCCCCC[Si] GHBKQPVRPCGRAQ-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 238000010074 rubber mixing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
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- 239000011164 primary particle Substances 0.000 description 2
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- 238000005070 sampling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 241001672018 Cercomela melanura Species 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- HXOGQBSDPSMHJK-UHFFFAOYSA-N triethoxy(6-methylheptyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCC(C)C HXOGQBSDPSMHJK-UHFFFAOYSA-N 0.000 description 1
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Images
Abstract
The invention provides modified white carbon black and a preparation method thereof, wherein the preparation method comprises the steps of mixing octyl alkoxy silane and an alcohol solvent, heating to a preset temperature, adjusting the pH value of the mixed solution to be within 26 by using an acid regulator, and carrying out hydrolysis reaction to obtain an octyl silane hydrolysate; uniformly mixing the octyl silane hydrolysate with mercaptoalkoxy silane to prepare a silane mixture; adding the precipitated white carbon black into a high-speed mixer, and spraying the silane mixture onto the surface of the precipitated white carbon black in a spraying manner to obtain the modified white carbon black. The modified white carbon black prepared by the invention can be applied to mixing of tire rubber materials, has the advantages of no VOC (volatile organic compounds) emission and good scorching safety, and can effectively improve the tensile strength, the tearing strength and the wear resistance of rubber finished products.
Description
Technical Field
The invention relates to the technical field of organic silicon chemistry, and particularly relates to modified white carbon black and a preparation method and application thereof.
Background
White carbon black is a white, nontoxic, amorphous and fine powder, has super strong adhesion and tear resistance, heat resistance and aging resistance, and is mainly used as a filler of products such as rubber, plastics, papermaking, paint and coating. At present, about 70 percent of white carbon black is used in the rubber industry all over the world to obtain high-quality rubber products, such as off-road tires, engineering tires, radial tires and the like. However, the white carbon black has more silicon hydroxyl groups on the surface and strong polarity, so that the dispersibility of the white carbon black in rubber materials is poor, and the application of the white carbon black is influenced, so that the improvement of the surface hydrophobicity of the white carbon black and the improvement of the performance of the carbon black are particularly important.
In the prior art, there are many reports about modifying white carbon black to improve the performance of the white carbon black, but the white carbon black has various defects. For example, patent CN107474313B adopts long-chain alkyl silane carbon black for modification, which sufficiently improves the dispersion performance of the carbon black, but the main disadvantage is that the amount of silane is larger. In patent CN101798473A, a solvent, water, a catalyst and a coupling agent are mixed to prepare a coupling agent sol solution, the white carbon black is uniformly dispersed to form a sol by using an ultrasonic dispersion or shearing method, and finally, a reaction treatment is performed to obtain modified white carbon black. According to the patent CN101798473A, polysulfide silane is slowly and uniformly added into a mixture of precipitated white carbon black and fumed silica in a spraying mode to obtain a silane-modified white carbon black-carbon black composite filler, only single sulfur-containing silane is added in the method, and the method has an obvious effect on improving the crosslinking performance of white carbon black and rubber, but the dispersion performance effect of white carbon black is limited, and the improvement on the physical performance of rubber is limited.
Therefore, the development of the modification research of the white carbon black has important significance.
Disclosure of Invention
In view of the above, the invention provides modified white carbon black and a preparation method thereof, which are used for solving the problems of complex preparation process and poor performance of the modified white carbon black in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of modified white carbon black comprises the following steps:
s1, mixing octyl alkoxy silane and an alcohol solvent, heating to a preset temperature, and adjusting the pH value of the mixed solution to be within 26 by using an acid regulator to perform hydrolysis reaction to obtain an octyl silane hydrolysate;
s2, uniformly mixing the octyl silane hydrolysate with mercaptoalkoxy silane to prepare a silane mixture;
and S3, adding the precipitated white carbon black into a high-speed mixer, and spraying the silane mixture onto the surface of the precipitated white carbon black in a spraying manner to obtain the modified white carbon black.
Further, in step S1, the mass ratio of the octylalkoxysilane to the alcoholic solvent is in the range of 1:0.8 to 1: 1.2.
Further, in the octylsilane hydrolysate of step S1, the molar ratio of the water to the octylalkoxysilane is in a range of 1.82:1 to 1.98: 1.
Further, the octyl group in the octyl alkoxysilane includes a n-octyl group or an iso-octyl group, and the alkoxy group in the octyl alkoxysilane includes at least one of a methoxy group, an ethoxy group, a n-propoxy group, and an isopropoxy group; the alcohol solvent comprises one of methanol, ethanol, n-propanol and isopropanol; the acid regulator comprises acidic deionized water prepared by hydrochloric acid, sulfuric acid or nitric acid.
Further, the mass of the acid regulator is in the range of 300ppm to 600ppm of the mass of the octylalkoxysilane.
Further, in the silane mixture of step S2, the molar ratio of the octyl silane to the mercaptoalkoxysilane is in the range of 0.63:1 to 0.47: 1.
Further, the alkoxy group in the mercaptoalkoxysilane includes at least one of a methoxy group, an ethoxy group, a n-propoxy group, and an isopropoxy group.
Further, in step S3, spraying the silane mixture onto the surface of the precipitated silica in a form of spray, specifically including the steps of: setting the rotating speed of the high-speed mixer to be 100-120r/min, heating the precipitated white carbon black to be 110-120 ℃, spraying the silane mixture on the surface of the precipitated white carbon black for modification reaction for 2-3h, stopping stirring after spraying is finished, keeping the temperature for 1-2h, cooling and discharging.
Further, the nitrogen adsorption specific surface area of the precipitated silica is 136m2G to 190m2In the range of/g.
The second purpose of the invention is to provide modified white carbon black prepared by the preparation method of the modified white carbon black.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation method provided by the invention, n-octyl triethoxysilane is introduced, so that the problems of poor dispersity and large silane consumption of single sulfur-containing silane modified white carbon black are solved, and the improvement of the tensile strength, tear strength and wear resistance of a rubber finished product is promoted; on the other hand, octyl alkoxy silane can form certain masking on mercaptopropyl alkoxy silane, so that the speed of mercapto functional groups participating in vulcanization is delayed, and the scorching safety is further improved.
(2) According to the preparation method provided by the invention, the silica white is uniformly contacted with the silane mixture as far as possible by atomizing the silane mixture, in the spraying process, the alkoxy is fully hydrolyzed, the generated low-boiling-point alcohol and the solvent are condensed and recovered together, and no VOC is discharged when the rubber material is mixed at the later stage, so that the scorching safety is high.
Drawings
In order to more clearly illustrate the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic view of a high-speed mixer according to an embodiment of the present invention.
List of reference numerals:
1. a sprayer; 2. a reaction kettle jacket; 3. a solid discharge port; 4. a double helix agitator; 5. a stirring motor; 6. a low-boiling discharge port; 7. a condenser; 8. a receiving tank.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "first" and "second" mentioned in the embodiments of the present invention are only used for descriptive purposes and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
In the description of embodiments of the present application, the description of the term "some embodiments" means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. Throughout this specification, the schematic representations of the terms used above do not necessarily refer to the same implementation or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The white carbon black belongs to amorphous hydrated silicon dioxide, the internal structure of the white carbon black contains part of crystal water, and the molecular formula of the white carbon black is 3SiO2˙nH2O, having a density of 2.319-2.653 g/cm, is insoluble in water and is capable of reacting with strong bases. The white carbon black primary particles are between 10 and 40nm, and the typical size of aggregates formed by the primary particles is 100-200 nm. The surface of the material is rich in polar silicon hydroxyl, has high surface energy and is easy to agglomerate, so the surface modification and promotion are neededIt is dispersed.
Common modifying agents in modification include silane coupling agents, alcohol ester modifying agents, organic acids, organic salts and the like. The process for modifying the white carbon black by the silane coupling agent mainly comprises a wet modification process, a dry modification process and an in-situ modification process. Although the white carbon black modification process is simplified by the in-situ modification and the dry modification, the defects of nonuniform mixing, slow modification speed, insufficient reaction of a silane coupling agent and the like exist, and the wet modification also has the problems of low utilization rate of the silane coupling agent, complex process, poor hydrophobicity of the modified white carbon black and the like.
In order to solve the above problems, an embodiment of the present invention provides a method for preparing modified white carbon black, including the following steps:
s1, mixing octyl alkoxy silane and an alcohol solvent, heating to a preset temperature, and adjusting the pH value of the mixed solution to be within 26 by using an acid regulator to perform hydrolysis reaction to obtain an octyl silane hydrolysate;
s2, uniformly mixing the octyl silane hydrolysate with mercaptoalkoxy silane to prepare a silane mixture;
and S3, adding the precipitated white carbon black into a high-speed mixer, and spraying the silane mixture onto the surface of the precipitated white carbon black in a spraying manner to obtain the modified white carbon black.
It can be understood that, in the process of modifying the white carbon black, the self-characteristics of the modifier play a deterministic role in the modification of the white carbon black, and the self-characteristics of the modifier comprise a functional group and a hydrolytic group, wherein the functional group plays a dominant role. Such as n-octyltriethoxysilane and mercaptopropyltriethoxysilane, all conform to the general formula Y-Si-X of the silane coupling agent3The hydrolysis groups of the both are ethoxy groups which have chemical reaction with the surface of the white carbon black, the hydrolysis activities are consistent, the modification effects of the both on the white carbon black are generally considered to be similar, but experiments show that the hydrophobic modification effect of the mercaptopropyltriethoxysilane on the precipitated white carbon black is poor when n-octyltriethoxysilane is not introduced as an auxiliary modifier.
According to the invention, octyl silane is hydrolyzed, then compounded with mercaptosilane, and then dispersed on the surface of the precipitated white carbon black in a spraying manner, and the solvent and alcohol generated by hydrolysis are condensed and recovered by a condenser, so that the modified white carbon black is finally obtained. By introducing n-octyl triethoxysilane, on one hand, the problems of poor dispersity and large silane consumption of single sulfur-containing silane modified white carbon black are solved, and the improvement of the tensile strength, tear strength and wear resistance of a rubber finished product is promoted; on the other hand, octyl alkoxy silane can form certain masking on mercaptopropyl alkoxy silane, so that the speed of mercapto functional groups participating in vulcanization is delayed, and the scorching safety is further improved.
To further prove the effect of the compounded silane mixture provided by the invention on modifying the white carbon black, the following tests are carried out.
1000g of white carbon black is put into a double-helix conical mixer (high-speed mixer), heated to 110 ℃ and 120 ℃, and then sprayed with n-octyltriethoxysilane and mercaptopropyltriethoxysilane respectively. And observing the hydrophobic rate of the modified white carbon black under the same treatment condition. The test results are shown in table 1. The hydrophobic rate is detected by adding 5g of modified white carbon black into 50g of deionized water, oscillating for 3-5 times, standing for 24h, and observing, wherein the mass ratio of the white carbon black floating on the water surface is the hydrophobic rate.
TABLE 1 hydrophobicity of white carbon black modified with silane coupling agent
As can be seen from Table 1, the effect of modifying the white carbon black with mercaptosilane alone is not good. The addition of the octyl silane improves the hydrophobic rate of the white carbon black, but when the using amount of the octyl silane is less than 10% of the using amount of the white carbon black, the hydrophobic rate of the white carbon black starts to be obviously reduced, and the modification requirement cannot be met.
Preferably, the molar ratio of octylsilane to mercaptoalkoxysilane is in the range of 0.63:1 to 0.47: 1. The alkoxy group in the mercaptoalkoxysilane includes at least one of a methoxy group, an ethoxy group, a n-propoxy group, and an isopropoxy group.
Specifically, in step S1, in order to increase the degree of the hydrolysis reaction, the system is heated to a preset temperature, wherein the preset temperature is 75-78 ℃, then the acid regulator is added dropwise under a stirring state to adjust to an acidic system, after the addition is completed, the temperature is kept continuously for the hydrolysis reaction, and when the moisture content is detected to be reduced to 1.0-1.5%, the temperature is reduced to obtain the octylsilane hydrolysate.
The n-octyl triethoxysilane is prehydrolyzed, so that the dispersibility of the n-octyl triethoxysilane in the white carbon black is improved, and the hydrophobic modification of the white carbon black by the mercaptopropyl triethoxysilane under the action of a small amount of the n-octyl triethoxysilane is realized.
In addition, the reaction activity of the octylalkoxysilane can be improved by controlling the molar ratio of the octylalkoxysilane to water and the pH of the system mixed solution, thereby precisely controlling the degree of hydrolysis of the octylalkoxysilane.
Wherein, octyl in octyl alkoxy silane comprises n-octyl or iso-octyl, and alkoxy in octyl alkoxy silane comprises at least one of methoxyl, ethoxyl, n-propoxyl and isopropoxy.
The alcohol solvent comprises one of methanol, ethanol, n-propanol and isopropanol.
The acid regulator comprises acidic deionized water prepared by hydrochloric acid, sulfuric acid or nitric acid.
Further, the prehydrolysis of n-octyltriethoxysilane requires the following conditions to be met:
one is to use deionized water and the amount is appropriate. In embodiments of the present invention, it is preferred that the molar ratio of water to octylalkoxysilane in the octylsilane hydrolysate is in the range of 1.82:1 to 1.98: 1. Below or above this amount of water, the dispersibility of n-octyltriethoxysilane deteriorates.
Secondly, the amount of the catalyst is proper. The catalyst adopts strong acid such as hydrochloric acid, sulfuric acid, nitric acid and the like, but the concentration is proper, too little strong acid is easy to be interfered by impurities to lose activity, and too much strong acid can cause excessive polycondensation of n-octyl silane to cause poor dispersibility. Experiments prove that in the embodiment of the invention, the mass of the acid regulator is preferably in the range of 300ppm to 600ppm of the mass of the octyl alkoxy silane.
Thirdly, a proper amount of alcohol substances are used as a solvent, and the alcohol substances not only can inhibit the polycondensation of the silane, but also can improve the dispersion effect of the n-octyl silane and reduce the dosage of the n-octyl silane. In the embodiment of the present invention, it is preferable that the mass ratio of the octylalkoxysilane to the alcoholic solvent is in the range of 1:0.8 to 1: 1.2.
After the three conditions are met, the using amount of the n-octyl triethoxysilane can be greatly reduced. In the embodiment of the invention, after the conditions are adopted, the using amount of the n-octyl triethoxysilane is reduced to 2.8% from 5% of the white carbon black by mass, and the hydrophobic rate can reach 100%.
Specifically, in step S3, adding the precipitated silica into a high-speed mixer, and spraying the silane mixture onto the surface of the precipitated silica in a form of spray, including the steps of:
setting the rotating speed of the high-speed mixer at 120r/min for 100-.
Referring to FIG. 1, the present invention modifies the surface of white carbon black using a high-speed mixer. The high-speed mixer comprises a reaction kettle and a receiving tank 8 communicated with the reaction kettle through a condenser 7, the reaction kettle comprises a mixing cavity and a reaction kettle jacket 2 wrapped outside the mixing cavity, and the reaction kettle jacket 2 has a heating function and can control the temperature of materials in the reaction kettle; the double helix agitator 4 is located the compounding intracavity, drives through the agitator motor 5 that sets up on reation kettle and stirs. The reaction kettle further comprises a sprayer 1, a solid discharge port 3 and a low-boiling discharge port 6, the solid discharge port 3 is arranged at the bottom of the reaction kettle and used for discharging solid materials, the low-boiling discharge port 6 is arranged at the top of the reaction kettle and communicated with a condenser, low-boiling gas can be discharged through the low-boiling discharge port 6 and is condensed by the condenser 7 and then recycled into the receiving tank 8.
Specifically, in the production process, the precipitated white carbon black is added into a mixing cavity of a reaction kettle, a silane mixture is added into a sprayer 1, reaction parameters are set, a stirring motor 5 is started, the precipitated white carbon black is heated to 110-120 ℃ through a reaction kettle jacket 2, the sprayer 1 is controlled to spray the silane mixture onto the surface of the precipitated white carbon black in a spraying mode, alcohol and an alcohol solvent generated by hydrolysis of the silane mixture are discharged from a low-boiling discharge port 6, the alcohol and the alcohol solvent are collected into a receiving tank 8 after being condensed by a condenser 7, the stirring motor 5 is closed after spraying is completed, heat preservation is continued for 1-2 hours, and the modified white carbon black is discharged from a solid discharge port 3 after cooling.
Wherein, the amount of the precipitated white carbon black is calculated according to the amount of the mercaptoalkoxysilane in the silane mixture, and 0.22 to 0.29mol of the mercaptoalkoxysilane is consumed by 1kg of the white carbon black.
Further, the nitrogen adsorption specific surface area of the precipitated silica was 136m2G to 190m2In the range of/g.
Therefore, according to the preparation method provided by the invention, the white carbon black is uniformly contacted with the silane mixture as much as possible by atomizing the silane mixture, in the spraying process, the alkoxy is fully hydrolyzed, the generated low-boiling-point alcohol and the solvent are condensed and recovered together, no atmospheric volatile organic compound is discharged when the rubber material is mixed at the later stage, and the scorching safety is high.
The other embodiment of the invention provides modified white carbon black prepared by the preparation method of the modified white carbon black.
On the basis of the above embodiments, the present invention is further illustrated by the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are examples of experimental procedures not specified under specific conditions, generally according to the conditions recommended by the manufacturer. Unless otherwise indicated, percentages and parts are by mass.
Example 1
The embodiment provides a preparation method of modified white carbon black, which comprises the following steps:
1) preparing octyl alkoxy silane hydrolysate, mixing 138g of n-octyl triethoxysilane and 138g of ethanol and heating; 0.07g of concentrated hydrochloric acid is dissolved in 17.8g of deionized water to prepare acidic deionized water; when the temperature of the silane solution is raised to 75-78 ℃, acid deionized water is added, and after the acid deionized water is added, the reaction is continued for 4.5 hours, the water content is 1.5 percent through sampling detection, and the temperature is reduced, so that n-octyl silane hydrolysate is obtained;
2) mixing the n-octyl silane hydrolysate with 238g of mercaptopropyl triethoxysilane at normal temperature, and uniformly stirring to form a silane mixture;
3) spray modification, namely adding 4kg of precipitated silica into a double-helix conical high-speed mixer with a sprayer and a jacket heating function, opening double helix stirring, setting the rotating speed at 110r/min, heating the silica to 110 and 120 ℃, and spraying the silane mixture onto the surface of the silica in a spraying manner for 2.5 hours; and recovering alcohol and solvent generated by the reaction through a condenser, stopping stirring after spraying is finished, continuing keeping the temperature for 1h, and then cooling and discharging to obtain the modified white carbon black.
The modified white carbon black prepared in example 1 was tested to find that the hydrophobic rate was 100%. According to the rubber mixing experiment carried out by HG/T2404-2008 'identification of precipitated hydrated white carbon black in styrene-butadiene rubber', the Mooney viscosity is 80.02, the scorch time is 26.4min, the tensile strength is 18.23MPa, the elongation at break is 682.75%, the tear strength is 42.89kN/m, and the Akron abrasion is 0.18cm3。
In order to further illustrate the excellent effect of the modified white carbon black by adopting the compound silane mixture, the following two aspects are compared and illustrated:
testing VOC content of atmospheric volatile organic compounds
The emission of VOC (volatile organic compounds) in the atmosphere, which is generated by liquid sulfur-containing silane and white carbon black modified in example 1, was tested, wherein the sulfur-containing silane adopts Si69 and S1891, Si69 is bis- [3- (triethoxy silicon) propyl) ] -tetrasulfide), S1891 is 3-mercaptopropyl triethoxysilane, and the results are shown in Table 2:
TABLE 2 VOC emissions
| Species of | Si69 | S1891 | Modified white carbon black |
| VOC content | 512g/L | 403g/L | 0 |
As can be seen from Table 2, when the composite silane modified white carbon black is applied to mixing of tire rubber materials, no sulfur-containing silane needs to be added, alcohols with low boiling point cannot be generated during mixing, and VOC pollution is avoided.
(II) Performance testing
In the application of the modified white carbon black in the rubber, the modified white carbon black is tested according to the HG/T2404-2008 standard, and the processing test of the unvulcanized rubber compound is tested according to the GB/T1232.1 standard. Wherein, the white carbon blackaIs unmodified white carbon black and white carbon blackbIs 3-mercaptopropyltriethoxysilane modified white carbon black and white carbon blackcThe test results of the white carbon black modified by compounding n-octyl triethoxysilane and mercaptopropyl triethoxysilane are shown in tables 3 and 4:
TABLE 3 processability of various white carbon blacks in rubber
As can be seen from Table 3, the white carbon black modified by the complex silane mixturecThe Mooney viscosity of the white carbon black is 80.02 which is higher than that of the unmodified white carbon blackaWhite carbon black modified by mercaptopropyltriethoxysilanebThe viscosity is low, and the processing energy consumption is reduced; white carbon black modified by composite silane mixturecThe scorching time is 26 minutes and 25 seconds, which is compared with the unmodified white carbon blackaMercaptopropyltriethoxySilane modified white carbon blackbThe scorching time is greatly prolonged, and the scorching safety is improved.
TABLE 4 physical properties of various white carbon blacks used in rubber
As can be seen from Table 4, the white carbon black modified by composite silanecThe tensile strength is 18.23Mpa, the tearing strength is 42.89KN/m, and the product is compared with the unmodified white carbon blackaWhite carbon black modified by mercaptosilanebA small increase is achieved; the elongation at break is slightly increased by 682.75%; the Akron abrasion loss is 0.18cm3Compared with the unmodified white carbon blackaWhite carbon black modified by mercaptosilanebObviously reduced, which shows that the wear resistance is greatly improved.
Example 2
The embodiment provides a preparation method of modified white carbon black, which is different from embodiment 1 in that: in the step 1), 0.07g of concentrated hydrochloric acid is dissolved in 16.4g of deionized water to prepare acidic deionized water; when the temperature of the silane solution is raised to 75-78 ℃, acid deionized water is added, and after the acid deionized water is added, the reaction is continued for 4.5 hours, the water content is 1.0 percent through sampling detection, and the temperature is reduced, so that n-octyl silane hydrolysate is obtained;
the remaining steps and parameters were the same as in example 1.
The modified white carbon black prepared in example 2 was tested to find that the hydrophobic rate was 100%. According to the rubber mixing experiment carried out by HG/T2404-2008 'identification of precipitated hydrated white carbon black in styrene-butadiene rubber', the Mooney viscosity is 81.54, the scorch time is 23.8min, the tensile strength is 18.15MPa, the elongation at break is 640.35%, the tear strength is 41.69kN/m, and the Akron abrasion is 0.19cm3。
Example 3
The embodiment provides a preparation method of modified white carbon black, which is different from embodiment 1 in that:
in the step 1), replacing n-octyl triethoxysilane by iso-octyl triethoxysilane with equal molar amount;
the remaining steps and parameters were the same as in example 1.
The modified white carbon black prepared in example 3 was tested to find that the hydrophobic rate was 100%. According to the rubber mixing experiment carried out by HG/T2404-2008 'identification of precipitated hydrated white carbon black in styrene-butadiene rubber', the Mooney viscosity is 79.14, the scorch time is 25.8min, the tensile strength is 18.35MPa, the elongation at break is 676.35%, the tear strength is 42.69kN/m, the Akron abrasion is 0.18cm3。
Example 4
The embodiment provides a preparation method of modified white carbon black, which is different from embodiment 1 in that:
in the step 1), n-octyltriethoxysilane is replaced by n-octyltrimethoxysilane with an equal molar amount; the ethanol is changed into methanol with equal mass;
in the step 2), mercaptopropyltriethoxysilane is replaced by mercaptopropyltrimethoxysilane with equal mass;
the remaining steps and parameters were the same as in example 1.
The modified white carbon black prepared in example 4 was tested to find that the hydrophobic rate was 100%. According to the rubber mixing experiment carried out by HG/T2404-2008 'identification of precipitated hydrated white carbon black in styrene-butadiene rubber', the Mooney viscosity is 82.34, the scorch time is 24.6min, the tensile strength is 18.05MPa, the elongation at break is 672.35%, the tear strength is 42.39kN/m and the Akron abrasion is 0.18cm3。
In conclusion, the embodiment shows that the modified white carbon black prepared by the preparation method has no VOC emission and high scorching safety when the rubber material is mixed at the later stage; meanwhile, due to the compounding of octyl alkoxy silane and mercaptopropyl alkoxy silane, the problems of poor dispersity and large silane dosage of the single sulfur-containing silane modified white carbon black are solved, and the improvement of the tensile strength, the tearing strength and the wear resistance of a rubber finished product is promoted; in addition, octyl alkoxy silane can form certain masking on mercaptopropyl alkoxy silane, so that the speed of mercapto functional groups participating in vulcanization is delayed, and the scorching safety is further improved.
It should be noted that the above examples are only for further illustration and description of the technical solution of the present invention, and are not intended to further limit the technical solution of the present invention, and the method of the present invention is only a preferred embodiment, and is not intended to limit the protection scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the modified white carbon black is characterized by comprising the following steps:
s1, mixing octyl alkoxy silane and an alcohol solvent, heating to a preset temperature, and adjusting the pH value of the mixed solution to be within 26 by using an acid regulator to perform hydrolysis reaction to obtain an octyl silane hydrolysate;
s2, uniformly mixing the octyl silane hydrolysate with mercaptoalkoxy silane to prepare a silane mixture;
and S3, adding the precipitated white carbon black into a high-speed mixer, and spraying the silane mixture onto the surface of the precipitated white carbon black in a spraying manner to obtain the modified white carbon black.
2. The method for preparing modified white carbon black according to claim 1, wherein in step S1, the mass ratio of the octylalkoxysilane to the alcohol solvent is in the range of 1:0.8 to 1: 1.2.
3. The method for preparing modified silica white according to claim 2, wherein the molar ratio of the water to the octylalkoxysilane in the octylsilane hydrolysate of step S1 is in the range of 1.82:1 to 1.98: 1.
4. The method for preparing modified silica white according to any one of claims 1-3, wherein the octyl group in the octyl alkoxysilane comprises n-octyl group or i-octyl group, and the alkoxy group in the octyl alkoxysilane comprises at least one of methoxy group, ethoxy group, n-propoxy group and i-propoxy group;
the alcohol solvent comprises one of methanol, ethanol, n-propanol and isopropanol;
the acid regulator comprises acidic deionized water prepared by hydrochloric acid, sulfuric acid or nitric acid.
5. The method for preparing modified white carbon black according to claim 4, wherein the mass of the acid regulator is within a range of 300ppm to 600ppm of the mass of the octylalkoxysilane.
6. The method for preparing modified silica white according to claim 5, wherein the molar ratio of the octyl silane to the mercaptoalkoxy silane in the silane mixture of step S2 is in the range of 0.63:1 to 0.47: 1.
7. The method for preparing modified silica white according to claim 5, wherein the alkoxy group in the mercaptoalkoxysilane includes at least one of methoxy group, ethoxy group, n-propoxy group and isopropoxy group.
8. The method for preparing modified white carbon black according to claim 1, wherein the step of spraying the silane mixture onto the surface of the precipitated white carbon black in a form of spray in step S3 specifically comprises the steps of:
setting the rotating speed of the high-speed mixer to be 100-120r/min, heating the precipitated white carbon black to be 110-120 ℃, spraying the silane mixture on the surface of the precipitated white carbon black for modification reaction for 2-3h, stopping stirring after spraying is finished, keeping the temperature for 1-2h, cooling and discharging.
9. The method for preparing modified silica white according to claim 8, wherein the nitrogen adsorption ratio of the precipitated silica whiteThe surface area is 136m2G to 190m2In the range of/g.
10. Modified white carbon black, characterized by being prepared by the method for preparing modified white carbon black according to claims 1 to 9.
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| CN101180344A (en) * | 2005-03-24 | 2008-05-14 | 株式会社普利司通 | Compounding silica-reinforced rubber with low volatile organic compound (voc) emission |
| CN101798473A (en) * | 2010-02-10 | 2010-08-11 | 广州吉必盛科技实业有限公司 | Silane-modified white carbon black-carbon black composite filling and preparation method thereof |
| CN107022126A (en) * | 2017-04-25 | 2017-08-08 | 成都硅宝科技股份有限公司 | White carbon filled rubber composite containing many sulfhydryl compounds and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101180344A (en) * | 2005-03-24 | 2008-05-14 | 株式会社普利司通 | Compounding silica-reinforced rubber with low volatile organic compound (voc) emission |
| CN101798473A (en) * | 2010-02-10 | 2010-08-11 | 广州吉必盛科技实业有限公司 | Silane-modified white carbon black-carbon black composite filling and preparation method thereof |
| CN107022126A (en) * | 2017-04-25 | 2017-08-08 | 成都硅宝科技股份有限公司 | White carbon filled rubber composite containing many sulfhydryl compounds and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116396626A (en) * | 2023-03-27 | 2023-07-07 | 江门市胜鹏化工实业有限公司 | Modified white carbon black and preparation method thereof |
| CN116396626B (en) * | 2023-03-27 | 2024-03-01 | 江门市胜鹏化工实业有限公司 | Modified white carbon black and preparation method thereof |
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