CN115521502B - Modified white carbon black micron aggregate and preparation method and application thereof - Google Patents
Modified white carbon black micron aggregate and preparation method and application thereof Download PDFInfo
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- CN115521502B CN115521502B CN202110715969.7A CN202110715969A CN115521502B CN 115521502 B CN115521502 B CN 115521502B CN 202110715969 A CN202110715969 A CN 202110715969A CN 115521502 B CN115521502 B CN 115521502B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000006229 carbon black Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims description 7
- 229920001971 elastomer Polymers 0.000 claims abstract description 10
- 239000005060 rubber Substances 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 241000872198 Serjania polyphylla Species 0.000 claims abstract description 3
- 230000004931 aggregating effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 67
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 238000003756 stirring Methods 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- 239000006185 dispersion Substances 0.000 claims description 26
- 239000004115 Sodium Silicate Substances 0.000 claims description 16
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 7
- FIADVASZMLCQIF-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octamethyl-1,3,5,7,2,4,6,8-tetrazatetrasilocane Chemical compound C[Si]1(C)N[Si](C)(C)N[Si](C)(C)N[Si](C)(C)N1 FIADVASZMLCQIF-UHFFFAOYSA-N 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 5
- SUUYDMDGZWFQNU-UHFFFAOYSA-N diethoxy(phenyl)silane Chemical compound CCO[SiH](OCC)C1=CC=CC=C1 SUUYDMDGZWFQNU-UHFFFAOYSA-N 0.000 claims description 4
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 4
- BUEPLEYBAVCXJE-UHFFFAOYSA-N [ethenyl-methyl-(trimethylsilylamino)silyl]ethene Chemical compound C(=C)[Si](N[Si](C)(C)C)(C=C)C BUEPLEYBAVCXJE-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 claims description 3
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 claims description 3
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 3
- ZSMNRKGGHXLZEC-UHFFFAOYSA-N n,n-bis(trimethylsilyl)methanamine Chemical compound C[Si](C)(C)N(C)[Si](C)(C)C ZSMNRKGGHXLZEC-UHFFFAOYSA-N 0.000 claims description 3
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 229920002379 silicone rubber Polymers 0.000 abstract description 12
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008719 thickening Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 238000010907 mechanical stirring Methods 0.000 description 16
- ROAYSRAUMPWBQX-UHFFFAOYSA-N ethanol;sulfuric acid Chemical compound CCO.OS(O)(=O)=O ROAYSRAUMPWBQX-UHFFFAOYSA-N 0.000 description 13
- ADMWVBXCJSMQLF-UHFFFAOYSA-N C(C)O.[Si] Chemical compound C(C)O.[Si] ADMWVBXCJSMQLF-UHFFFAOYSA-N 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- -1 silicon halide Chemical class 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003153 chemical reaction reagent 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
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012758 reinforcing additive Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08K9/10—Encapsulated ingredients
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
A modified white carbon black micron aggregate is formed by aggregating a sheet structure, wherein the sheet structure is gas-phase white carbon black with the surface coated by inorganic silicon. The hydrophobicity, tap density and dispersibility of the aggregate are higher than those of the gas-phase white carbon black, so that the aggregate has good low thickening property, the filling amount of the white carbon black in the silicon rubber is effectively increased, the viscosity of the silica and the rubber compound is reduced, and the mechanical property and the processing property of the white carbon black reinforced rubber are effectively improved.
Description
Technical Field
The invention relates to the field of inorganic nanometer new materials, in particular to a modified white carbon black micron aggregate, a preparation method and application thereof.
Background
White carbon black, also called silicon dioxide, is white and nontoxic powder developed from nonmetallic ore quartz sand, and is an important inorganic fine chemical product. White carbon black can be classified into precipitated white carbon black and fumed white carbon black according to its production method. Wherein the fumed silica is white amorphous flocculent nano silica powder (particle diameter is less than 100 nm) generated by high-temperature hydrolysis of silicon halide, and has large specific surface area (generally more than 100 m) 2 And/g), has excellent stability, reinforcement, thickening property and thixotropic property, and is an indispensable reinforcing agent and additive in rubber, paint, plastic, papermaking, medicine, printing ink and other industries.
The main application of the white carbon black is as a crosslinking reinforcing agent in the silicon rubber, wherein the main chain of the silicon rubber consists of an inorganic Si-O chain, and the side group is a hydrocarbon organic group, so that the silicon rubber has excellent low-temperature performance, heat resistance and ageing resistance. However, since the intermolecular force is weak, crystallization does not occur under the condition of stress, so that the mechanical strength of the rubber is extremely weak, the rubber which is not filled with the reinforcing filler has little use value, and the tensile strength, the elongation, the adhesive strength, the hardness, the tearing strength and the mechanical property of the silicon rubber can be limited and improved after the white carbon black is added into the silicon rubber, the physical and mechanical properties of the silicon rubber which uses the gas-phase white carbon black as the reinforcing filler are far better than those of the silicon rubber which uses the precipitated white carbon black or other fillers.
However, because the active silicon hydroxyl exists on the surface of the fumed silica, carboxylic acid bonds are formed in the adsorption water and the preparation process, so that acid areas appear on the surface of the fumed silica, the fumed silica is difficult to infiltrate and disperse in an organic phase and cannot be well compatible and disperse with polymers in a rubber vulcanization system, thereby reducing the vulcanization efficiency and the reinforcing performance, and the fumed silica cannot be used in certain fields with special requirements.
Meanwhile, the tap density of the fumed silica is low, dust is easy to generate and is not easy to add during operation, and the viscosity of the system is easily increased when the fumed silica is added into the silicone rubber, so that the addition amount of the fumed silica in the silicone rubber is low.
Although the compatibility of the filler and the rubber can be properly improved by carrying out surface modification on the fumed silica, the adding amount of the fumed silica in the silicone rubber can be slightly increased, and the problems of improving the adding amount and reducing the viscosity of the system can not be fundamentally solved.
The dispersibility and compatibility of the white carbon black in the organic phase can be improved by modifying the surface of the white carbon black by a gas phase method, so that the application field of the product is widened, and the added value of the white carbon black is improved.
The surface modification of the white carbon black by the gas phase method mainly comprises inorganic matter modification and organic matter modification, wherein the inorganic matter modification is TiO 2 Coating SiO 2 The organic matter modification is a main method for modifying the surface of the prior fumed silica, and uses organic groups to replace hydroxyl groups on the surface of the fumed silica, namely organic silanization, and the modified fumed silica almost inherits all the superior properties of the common fumed silica, and has special hydrophobicity, so that the application field of the fumed silica is wider.
However, the conventional gas phase method for modifying the white carbon black has the defects of complex steps, high processing precision requirement and high difficulty.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a modified white carbon black micron aggregate, which is formed by aggregating sheet structures, wherein the sheet structures are gas-phase white carbon black with the surface coated by inorganic silicon.
The particle size of the aggregate is 1-6 μm, and the length of the sheet structure is 20-40nm.
Preferably, the aggregate has a particle size of 1 μm to 5 μm, for example 2 μm, 3 μm, 4 μm.
Preferably, the sheet structure has a length of 25nm to 35nm, for example 20nm, 25nm, 35nm, 40nm.
Preferably, the aggregate has a hydrated particle size of 2 μm to 4 μm.
Preferably, the aggregates are inorganic micrometer aggregates.
Preferably, the aggregate is a powder structure.
According to the present invention, the aggregate has a transmission electron microscope image as described in fig. 1, 2, 4 or 5.
According to the invention, the aggregate has a hydrated particle size distribution profile as described in fig. 3 or fig. 6.
The invention also provides a preparation method of the white carbon black micron aggregate, which comprises the following steps:
s1, placing the white carbon black obtained by the gas phase method into a reaction kettle, adding a silanol solution, stirring until the white carbon black is completely dispersed, and heating the dispersion to 70-90 ℃, such as 75-85 ℃, for example 80 ℃.
S2, adjusting the pH value of the solution to be acidic, and adding sodium silicate aqueous solution for reaction to obtain an aggregate.
According to the invention, the mass concentration of the fumed silica in the dispersion is 10-50mg/mL, preferably 20-40mg/mL, preferably 25-35mg/mL, for example 15mg/mL, 25mg/mL, 40mg/mL, 50mg/mL.
Preferably, the fumed silica is fumed hydrophobic silica.
According to the present invention, the silanol solution is a solution obtained by dissolving silane in an alcohol solvent.
Preferably, the silane is one, a combination of two or more of hexamethyldisiloxane, hexamethyldisilazane, heptamethyldisilazane, octamethylcyclotetrasilazane, tetramethyldivinyl disiloxane, tetramethyldivinyl disilazane, diethoxymethylvinyl silane, dimethoxymethylphenyl silane, diethoxyphenyl silane, phenyltrimethoxy silane, and phenyltriethoxy silane.
Preferably, the alcohol solvent is a C2-C5 alcohol, preferably ethanol, propanol, isopropanol, butanol, isobutanol or pentanol, for example ethanol.
According to the invention, the step S1 and the step S2 are also comprised of the following steps, wherein the pH value of the dispersion liquid is adjusted to be alkaline and stable.
Preferably, the alkaline pH is not less than 8, preferably not less than 9, for example, the alkaline pH is not less than 9.5.
Preferably, the pH of the dispersion is adjusted using NaOH, for example, by adding a NaOH solution to the dispersion to adjust the pH to 9.5.
Preferably, the concentration of the NaOH solution is 1M.
Preferably, after the pH of the dispersion is adjusted to be alkaline and stabilized to adjust the pH of the dispersion to 9.5, the dispersion is stirred for 0.5 to 1 hour, and the pH is stabilized to 9.5 during the stirring.
According to the invention, said step S2 is carried out under stirring at a temperature of 80 ℃.
According to the present invention, the step S2 of adjusting the pH of the solution to acidity is performed using an acidic alcohol solution obtained by dissolving an inorganic acid in alcohol.
Preferably, the mineral acid is sulfuric acid or nitric acid.
Preferably, the alcohol is a C2-C5 alcohol, preferably ethanol, propanol, isopropanol, butanol, isobutanol or pentanol, for example ethanol.
For example, the acidic alcohol solution is an ethanol sulfuric acid solution, and preferably, the mass concentration of sulfuric acid in the ethanol sulfuric acid solution is 1%.
Preferably, the concentration of the aqueous sodium silicate solution is 0.15M.
According to the invention, the volume ratio of the sodium silicate aqueous solution to the sulfuric acid ethanol solution is 1:1.
Preferably, the addition amount of the sodium silicate aqueous solution and the sulfuric acid ethanol solution is 50-100mL/kg.
According to the invention, the reaction time after the addition of the aqueous sodium silicate solution in step S2 is 4 to 8 hours.
The use of the white carbon black micron aggregate as a rubber additive.
Advantageous effects
Through simple one-step operation, under the action of a silane modifier, inorganic silicon grows on the surface of fumed silica and seals and wraps fumed silica, and meanwhile, the wrapped fumed silica is gathered under the mechanical action to form a sheet aggregate structure, so that an inorganic micron aggregate which is changed from a random unstable aggregation state to stability is realized, the hydrophobicity, tap density and dispersibility of the aggregate are all higher than those of fumed silica, the aggregate has good low thickening property, the filling amount of the fumed silica in silicone rubber is effectively increased, the viscosity of the fumed silica in rubber compound is reduced, and the mechanical property and the processing property of the rubber reinforced by the fumed silica are effectively improved.
Drawings
FIG. 1 shows a transmission electron micrograph of a stable white carbon black micro aggregate obtained in example 1 of the present invention at a scale of 20 nm;
FIG. 2 shows a transmission electron micrograph of a stable white carbon black micro aggregate obtained in example 1 of the present invention at a scale of 50 nm;
FIG. 3 shows the hydrated particle size distribution of the stable white carbon black micro aggregate obtained in example 1 of the present invention;
FIG. 4 shows a transmission electron micrograph of a stable white carbon black micro aggregate obtained in example 2 of the present invention at a scale of 20 nm;
FIG. 5 shows a transmission electron micrograph of a stable white carbon black micro aggregate obtained in example 2 of the present invention at a scale of 100 nm;
fig. 6 shows the hydrated particle size distribution of the stable white carbon black micro aggregate obtained in example 2 of the present invention.
Detailed Description
The materials according to the invention, as well as the methods of preparation and use thereof, will be described in further detail below in connection with specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
1kg of fumed silica is placed in a reaction kettle, 60L of silane ethanol solution (hexamethyldisilazane, tetramethyl divinyl disiloxane and ethanol in the ratio of 4:1:7) is added, and after mechanical stirring and dispersion are completed, the reaction kettle is heated while mechanical stirring is still maintained. When the temperature of the solution in the reaction kettle is close to 80 ℃, naOH solution is added to adjust the pH value to 9.5; continuously stirring until the pH value is stable, adding 75mL of 1% sulfuric acid ethanol solution into a reaction kettle under the stirring condition of 80 ℃, stirring and dispersing, preparing 75mL of 0.15M sodium silicate aqueous solution after the dispersion is completed, adding the solution into the reaction kettle, and continuously stirring at 80 ℃ for reaction for 6 hours; the product is finally obtained in the form of a powder.
Referring to fig. 1 and 2, the aggregates prepared in this example have good dispersibility under SEM, and the sheet structure is clearly visible, with a length of 20-40nm.
Referring to fig. 3, the aggregate prepared in this example has good dispersibility in a solvent and a relatively uniform particle size distribution.
Example 2
1kg of fumed silica is placed in a reaction kettle, 60L of silane ethanol solution (hexamethyldisiloxane, tetramethyl divinyl disilazane and ethanol in a ratio of 4:1:7) is added, and after mechanical stirring is performed until the silica is completely dispersed, the reaction kettle is heated while mechanical stirring is still maintained. When the temperature of the solution in the reaction kettle is close to 80 ℃, naOH solution is added to adjust the pH value to 9.5; continuously stirring until the pH value is stable, adding 75mL of 1% sulfuric acid ethanol solution into a reaction kettle under the stirring condition of 80 ℃, stirring and dispersing, preparing 75mL of 0.15M sodium silicate aqueous solution after dispersing completely, adding into the reaction kettle, and continuously stirring at 80 ℃ for reaction for 6 hours; the product is finally obtained in the form of a powder.
Referring to fig. 4 and 5, the aggregates prepared in this example had good dispersibility under SEM, and the sheet structure was clearly visible, with the length of the sheet structure being 20-40nm.
Referring to fig. 6, the aggregate prepared in this example has good dispersibility in a solvent and a relatively uniform particle size distribution.
Example 3
1kg of fumed silica is placed in a reaction kettle, 100L of silane ethanol solution (heptamethyldisilazane, diethoxymethylvinylsilane and ethanol in the ratio of 3:2:7) is added, and after mechanical stirring and dispersion are completed, the reaction kettle is heated while mechanical stirring is still maintained. When the temperature of the solution in the reaction kettle is close to 80 ℃, adding NaOH solution to adjust the pH value to 9.5, stirring until the pH value is stable, adding 50mL of 1% sulfuric acid ethanol solution into the reaction kettle under the stirring condition of 80 ℃, stirring and dispersing, preparing 50mL of 0.15M sodium silicate aqueous solution after the dispersion is complete, adding the solution into the reaction kettle, and continuing to stir and react for 4 hours at 80 ℃; the product is finally obtained in the form of a powder.
Example 4
1kg of fumed silica is placed in a reaction kettle, 100L of silane ethanol solution (octamethyl cyclotetrasilazane, dimethoxymethylphenyl silane and ethanol in the ratio of 2:2:7) is added, and after mechanical stirring and dispersion are completed, the reaction kettle is heated while mechanical stirring is still maintained. When the temperature of the solution in the reaction kettle is close to 80 ℃, adding NaOH solution to adjust the pH value to 9.5, stirring until the pH value is stable, adding 50mL of 1% sulfuric acid ethanol solution into the reaction kettle under the stirring condition of 80 ℃, stirring and dispersing, preparing 50mL of 0.15M sodium silicate aqueous solution after the dispersion is complete, adding the solution into the reaction kettle, and continuing to stir and react for 4 hours at 80 ℃; the product is finally obtained in the form of a powder.
Example 5
1kg of fumed silica is placed in a reaction kettle, 100L of silane ethanol solution (octamethyl cyclo-tetra-silazane, diethoxyphenyl silane and ethanol in the ratio of 2:2:7) is added, and after mechanical stirring and dispersion are completed, the reaction kettle is heated while mechanical stirring is still maintained. When the temperature of the solution in the reaction kettle is close to 80 ℃, adding NaOH solution to adjust the pH value to 9.5, stirring until the pH value is stable, adding 50mL of 1% sulfuric acid ethanol solution into the reaction kettle under the stirring condition of 80 ℃, stirring and dispersing, preparing 50mL of 0.15M sodium silicate aqueous solution after the dispersion is complete, adding the solution into the reaction kettle, and continuing to stir and react for 4 hours at 80 ℃; the product is finally obtained in the form of a powder.
Example 6
1kg of fumed silica is placed in a reaction kettle, 20L of silane ethanol solution (octamethyl cyclo-tetra-silazane, phenyl trimethoxy silane and ethanol in the ratio of 2:1:7) is added, and after mechanical stirring and dispersion are completed, the reaction kettle is heated while mechanical stirring is still maintained. When the temperature of the solution in the reaction kettle is close to 80 ℃, naOH solution is added to adjust the pH value to 9.5; after the pH is stable, the reaction kettle is continuously stirred at 80 ℃; preparing 100mL of 1% sulfuric acid ethanol solution, adding the solution into a reaction kettle, stirring and dispersing, preparing 100mL of 0.15M sodium silicate aqueous solution after the solution is completely dispersed, adding the solution into the reaction kettle, and continuing stirring and reacting for 8 hours at 80 ℃; the product is finally obtained in the form of a powder.
Example 7
1kg of fumed silica is placed in a reaction kettle, 20L of silane ethanol solution (octamethyl cyclo-tetra-silazane, phenyl triethoxysilane and ethanol in the ratio of 2:1:7) is added, and after mechanical stirring and dispersion are completed, the reaction kettle is heated while mechanical stirring is still maintained. When the temperature of the solution in the reaction kettle is close to 80 ℃, adding NaOH solution to adjust the pH value to 9.5, stirring until the pH value is stable, adding 100mL of 1% sulfuric acid ethanol solution into the reaction kettle under the stirring condition of 80 ℃, stirring and dispersing, preparing 100mL of 0.15M sodium silicate aqueous solution after the dispersion is complete, adding into the reaction kettle, and continuing to stir and react for 8 hours at 80 ℃; the product is finally obtained in the form of a powder.
Example 8
1kg of fumed silica is placed in a reaction kettle, 60L of silane ethanol solution (hexamethyldisilazane, tetramethyl divinyl disiloxane, diethoxyphenyl silane and ethanol in the ratio of 2:1:1:7) is added, and after the dispersion is completed, the reaction kettle is heated while mechanical stirring is maintained. When the temperature of the solution in the reaction kettle is close to 80 ℃, adding NaOH solution to adjust the pH to 9.5, stirring until the pH is stable, and stirring at 80 ℃; adding 75mL of 1% sulfuric acid ethanol solution into a reaction kettle, stirring and dispersing, preparing 75mL of 0.15M sodium silicate aqueous solution after dispersing completely, adding into the reaction kettle, and continuing stirring at 80 ℃ for reaction for 6h; the product is finally obtained in the form of a powder.
Example 9
1kg of fumed silica is placed in a reaction kettle, 60L of a silanol solution (hexamethyldisilazane, tetramethyl divinyl disiloxane, phenyl trimethoxy silane and ethanol in the ratio of 2:1:1:7) is added, the mixture is mechanically stirred and dispersed, and after the dispersion is completed, the reaction kettle is heated while the mechanical stirring is still maintained. When the temperature of the solution in the reaction kettle is close to 80 ℃, adding NaOH solution to adjust the pH value to 9.5, stirring until the pH value is stable, adding 75mL of 1% sulfuric acid ethanol solution into the reaction kettle under the stirring condition of 80 ℃, stirring and dispersing, preparing 75mL of 0.15M sodium silicate aqueous solution after the dispersion is complete, adding the solution into the reaction kettle, and continuing to stir and react for 6 hours at 80 ℃; the product is finally obtained in the form of a powder.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. The modified white carbon black micron aggregate used as a rubber additive is characterized in that the aggregate is formed by aggregating a sheet structure, wherein the sheet structure is gas-phase white carbon black with the surface coated by inorganic silicon;
the preparation method of the modified white carbon black micron aggregate comprises the following steps:
s1, placing white carbon black by a gas phase method in a reaction kettle, adding a silanol solution, stirring until the white carbon black is completely dispersed, and heating a dispersion liquid to 70-90 ℃;
s2, adjusting the pH value of the solution to be acidic, and adding sodium silicate aqueous solution for reaction to obtain an aggregate.
2. The modified white carbon black micro aggregate according to claim 1, wherein the particle size of the aggregate is 1 μm to 6 μm, and the length of the sheet structure is 20nm to 40nm.
3. The modified white carbon black micro aggregate according to claim 2, wherein the particle size of the aggregate is 1 μm to 5 μm, and the length of the sheet structure is 25nm to 35nm.
4. A modified white carbon black micro aggregate according to any one of claims 1 to 3, wherein the hydrated particle size of the aggregate is 2 μm to 4 μm.
5. The modified white carbon black micro aggregate according to claim 1, wherein the aggregate is a powder structure; the aggregate has a transmission electron microscope map as described in fig. 1, 2, 4, or 5; the aggregate has a hydrated particle size distribution profile as described in fig. 3 or fig. 6.
6. The modified white carbon black micro aggregate according to any one of claims 1 to 3, wherein the mass concentration of the fumed white carbon black in the dispersion is 10 to 50mg/mL.
7. The modified white carbon black microaggregates of any one of claims 1 to 3, wherein the silanol solution is a solution obtained by dissolving silane in an alcohol solvent.
8. The modified white carbon black microaggregates of claim 7, wherein the silane is one, a combination of two or more of hexamethyldisiloxane, hexamethyldisilazane, heptamethyldisilazane, octamethyl cyclotetrasilazane, tetramethyl divinyl disiloxane, tetramethyl divinyl disilazane, diethoxymethylvinylsilane, dimethoxymethylphenyl silane, diethoxyphenyl silane, phenyl trimethoxysilane, and phenyl triethoxysilane;
the alcohol solvent is C2-C5 alcohol.
9. A modified white carbon black micro aggregate according to any of claims 1-3, further comprising the step of adjusting the pH of the dispersion to alkaline and stabilizing between steps S1 and S2.
10. The modified white carbon black micro aggregate according to claim 9, wherein the pH of the dispersion is not less than 8.
11. The modified white carbon black micro aggregate according to any one of claims 1 to 3, wherein the step S2 of adjusting the pH of the solution to be acidic is performed with an acidic alcohol solution, wherein the acidic alcohol solution is a solution obtained by dissolving a mineral acid in an alcohol.
12. The modified white carbon black micro aggregate according to any one of claims 1 to 3, wherein the step S2 is performed under stirring at a temperature of 80 ℃, and the reaction time after adding the aqueous solution of sodium silicate in the step S2 is 4 to 8 hours.
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| US4882133A (en) * | 1986-03-14 | 1989-11-21 | Sumitomo Chemical Company, Limited | Method for producing a flaky material |
| JPH1129317A (en) * | 1997-05-14 | 1999-02-02 | Doukai Kagaku Kogyo Kk | Scaly low crystalline silica and its production |
| JP2001262067A (en) * | 2000-03-23 | 2001-09-26 | Dokai Chemical Industries Co Ltd | Curable composition for heat insulating coating material containing scaly silica particle and heat insulating cured product |
| JP2012025596A (en) * | 2010-07-20 | 2012-02-09 | Shin-Etsu Chemical Co Ltd | Method for producing agglomerated silica microparticle |
| CN103937293A (en) * | 2014-04-28 | 2014-07-23 | 北京化工大学 | Carbon-coated white carbon black |
| CN109354876A (en) * | 2018-10-09 | 2019-02-19 | 河南骏化发展股份有限公司 | A kind of preparation method of silicon rubber modified white carbon black |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008044873A1 (en) * | 2006-10-10 | 2008-04-17 | Korea Institute Of Industrial Technology | Method for preparing permanently hydrophobic aerogel and permanently hydrophobic aerogel prepared by using the method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4882133A (en) * | 1986-03-14 | 1989-11-21 | Sumitomo Chemical Company, Limited | Method for producing a flaky material |
| JPH1129317A (en) * | 1997-05-14 | 1999-02-02 | Doukai Kagaku Kogyo Kk | Scaly low crystalline silica and its production |
| JP2001262067A (en) * | 2000-03-23 | 2001-09-26 | Dokai Chemical Industries Co Ltd | Curable composition for heat insulating coating material containing scaly silica particle and heat insulating cured product |
| JP2012025596A (en) * | 2010-07-20 | 2012-02-09 | Shin-Etsu Chemical Co Ltd | Method for producing agglomerated silica microparticle |
| CN103937293A (en) * | 2014-04-28 | 2014-07-23 | 北京化工大学 | Carbon-coated white carbon black |
| CN109354876A (en) * | 2018-10-09 | 2019-02-19 | 河南骏化发展股份有限公司 | A kind of preparation method of silicon rubber modified white carbon black |
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