CN107337810A - A kind of preparation method of hydrophobicity high-reinforcement white carbon black - Google Patents
A kind of preparation method of hydrophobicity high-reinforcement white carbon black Download PDFInfo
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- CN107337810A CN107337810A CN201710541084.3A CN201710541084A CN107337810A CN 107337810 A CN107337810 A CN 107337810A CN 201710541084 A CN201710541084 A CN 201710541084A CN 107337810 A CN107337810 A CN 107337810A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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Abstract
The present invention relates to a kind of preparation method of hydrophobicity high-reinforcement white carbon black, this method is with SiO2Wet gel is raw material, and A171 is modifying agent, prepares hydrophobicity high-reinforcement white carbon black.Modification temperature is 80 95 DEG C in this method, and modification time be 60 150min, and modified solution pH value is 2.2 3.1, and the dosage of modifying agent is 2.2% the 3.4% of reaction solution gross mass.It is more that the present invention solves traditional white carbon surface silanol groups, the problem of with rubber compatibility difference, improves the hydrophobicity of traditional white carbon.During applied to butadiene-styrene rubber, the processing characteristics of rubber is improved, reduces the cure time of rubber, the mechanical properties such as wearability and tensile strength, the stress at definite elongation of vulcanizate is improved, improves the reinforcing of traditional white carbon.And this technique is simple, product stability is good, is easy to industrialization, has good Technical Economy.
Description
Technical field
The present invention relates to white carbon technical field of modification, more particularly to a kind of preparation side of hydrophobicity high-reinforcement white carbon black
Method.
Background technology
White carbon is nano silicon, and molecular formula is：SiO2·nH2O, because of its microstructure and accumulation shape and carbon black
It is similar, and have similar reinforcing property in rubber, therefore it is referred to as white carbon.It has cheap, energy-conserving and environment-protective, processability
Can be good the advantages that.White carbon is applied to tire tread, the rolling resistance about 30% of tire can be reduced, at the same can keep compared with
Good anti-slippery and wearability.Therefore, tire manufacturer gradually substitutes carbon black using white carbon in recent years.But white carbon table
There is substantial amounts of hydrophilic silicone hydroxyl in face, hygroscopic reunion, cause compatibility and bad dispersibility in macromolecule matrix, largely effect on
The comprehensive mechanical property of vulcanizate, makes the reinforcing poor of white carbon.Therefore, it is necessary to select suitable modifying agent to white carbon
Surface modification is carried out, reduces the silicone hydroxyl number on white carbon surface, lifting white carbon is reinforcing in rubber tyre.
The content of the invention
It is an object of the invention to provide a kind of preparation method of hydrophobicity high-reinforcement white carbon black, asked with solving above-mentioned technology
Topic.So that by the white carbon that this method is prepared compared with existing white carbon, its surface hydroxyl number is reduced, reinforced rubber
Afterwards, vulcanizate comprehensive mechanical property improves.According to technical scheme provided by the invention, the system of the hydrophobicity high-reinforcement white carbon black
Preparation Method comprises the following steps：
By SiO2Wet gel is added in reactor, and it is 86% or so to control its moisture content, is stirred in a kettle, is heated
Heat up design temperature, adjusts pH value with dilute sulfuric acid, adds a certain proportion of modifier A 171, be modified reaction, last water
Wash, filter, drying, controlling the certain moisture content of white carbon, obtain hydrophobicity high-reinforcement white carbon black.
As limitation of the present invention, modified-reaction temperature is 80-95 DEG C, time 60-150min, pH value of solution 2.2-
3.1, amount of modifier is the 2.2%-3.4% of reaction solution gross mass, and filter type is press filtration or centrifugal filtration mode, drying side
Formula is oven drying or spray drying, and drying temperature is 100-115 DEG C, and the moisture content of white carbon is 3wt%-8wt% after drying.
As the further limitation to the present invention, in method of the present invention, modification temperature is 90 DEG C, and modification time is
120min, modified solution pH are 2.5, and amount of modifier is the 3.0% of reaction solution gross mass, and drying temperature is 105 DEG C, after drying
White carbon moisture content is 5.2wt%.
White carbon prepared by the present invention, obtained beneficial effect are：Compared to traditional precipitated silica, its surface hydroxyl
Number is reduced, hydrophobicity enhancing, adhesion with rubber molecule, wellability enhancing, so as to keep preferable anti-slippery and resistance to
Mill property.For white carbon activation grade up to 100%, hydroxyl value have dropped 60%, the hydrophobicity of traditional white carbon be improved, applied to butylbenzene
During rubber, the processing characteristics of rubber is improved, 300%, 500% stress at definite elongation is distinguished compared with the precipitated silica standards of HG/T 3061
31.3%, 26% is improved, preparing precipitated silica compared with traditional handicraft has been respectively increased 61.9%, 50.8%, under volume worn
14.4% has been dropped, has reduced the cure time of rubber, has improved the power such as wearability and tensile strength, the stress at definite elongation of vulcanizate
Performance is learned, improves the reinforcing property of traditional white carbon.
Brief description of the drawings
Fig. 1 is the embodiment of the present invention 6 and the gained XRD spectrum of comparative example 1, wherein 1 is before modified (comparative example 1)
Product XRD spectrum, 2 be modified (embodiment 6) product XRD spectrum；
Fig. 2 is the embodiment of the present invention 6 and the gained TG collection of illustrative plates of comparative example 1, wherein 1 is modified (embodiment 6) product
TG collection of illustrative plates, 2 be (comparative example 1) product TG collection of illustrative plates before modified；
Fig. 3 is the embodiment of the present invention 6 and the gained FT-IR collection of illustrative plates of comparative example 1, wherein 0% is (contrast implementation before modified
Example 1) product F T-IR collection of illustrative plates, 3% is modified (embodiment 6) product F T-IR collection of illustrative plates；
Fig. 4 is the embodiment of the present invention 6 and the gained TEM collection of illustrative plates of comparative example 1, and wherein A figures are (comparative example before modified
1) product TEM collection of illustrative plates, B figures are modified (embodiment 6) product TEM collection of illustrative plates.
Embodiment
The present invention will be described further in conjunction with the accompanying drawings and embodiments, and these embodiments are only to illustrate to be used, without
The limitation that the present invention is implemented should be interpreted.
The SiO used in all embodiments of the invention2Wet gel, its preparation method are：Pipette 30mL1.4mol/L water glass
Glass solution, 800mL water, is placed in four-hole boiling flask, with 250r/min uniform stirrings, adds a certain amount of dispersant, oil bath heating is anti-
Bottom liquid is answered to 83 DEG C, adds 32mL 98% concentrated sulfuric acid and 363mL with constant rate of speed in 100min using peristaltic pump
1.4mol/L water glass solution, reaction terminate, and stop adding water glass solution, continuously add the concentrated sulfuric acid, until reaction system
PH value reaches 4.0；Washing suction filtration is carried out using vavuum pump, until filtrate electrical conductivity is less than 100 μ S/cm, filter cake is taken out and adds water, it is molten
Slurry, to moisture content 85%-86%.
Method of testing
1) activation grade determines：
50mL distilled water is added in 100mL beakers, 1.0g precipitated silicas are accurately weighed in beaker, with certain
Rotating speed stirs 30min, is then transported in 250mL separatory funnels, stands 24h, by the white carbon filtering for sinking to bottom, dries
Do, weigh, activation grade is calculated further according to formula (1)：
2) lipophilic degree determines：
50mL distilled water is added in 100mL beakers, 1.0g precipitated silicas is accurately weighed in beaker, drips thereto
Add absolute ethyl alcohol until powder complete wetting, records the dripping quantity V (mL) of absolute ethyl alcohol, oleophylic is calculated further according to formula (2)
Degree：
3) specific surface area BET, X-ray diffraction XRD, thermogravimetric TG, infrared spectrum FTIR, transmission electron microscope TEM measure.
According to GB/T3073-2008《Measure N2 adsorption method of the precipitated hydrated silica than surface》Determine white carbon
Specific surface area.
XRD tests are carried out using Rigaku company D/Max 2500PC types powder x-ray diffraction；
TG tests are carried out using the resistance to company's T G 209F3 types thermogravimetric analyzer of speeding of Germany；
FTIR tests are carried out using Japanese Shimadzu Corporation IRAffinity-1 types infrared spectrometer；
TEM tests are carried out using Jeol Ltd. JEM-2100 types transmission electron microscope.
4) Mooney of sizing material, abrasion, curability and mechanics performance determining.
By HG/T2404-2008《Identification of the precipitated hydrated silica in butadiene-styrene rubber》Carry out refining glue experiment.
By GB/T1232《Half finished rubber is measured Part I with disk shearing viscosimeter：The measure of Mooney viscosity》
Test the Mooney viscosity of rubber.
By GB/T9867-2008《Vulcanize measure (the rotating roller cartridge type abrasion machine of rubber or thermoplastic elastomer anti-wear performance
Method》Test the anti-wear performance of rubber.
By GB/T9869-1997《The measure (oscillating disc curemeter method) of rubber size vulcanization characteristics》Test the sulphur of rubber
Change characteristic.
By GB/T528-2009《Vulcanize the measure of rubber or thermoplastic elastomer tensile stress-strain performance》Progress stress-should
Become the test of characteristic.
Embodiment 1
Pipette 460g SiO2Wet gel, it is added in 2L reactors, stirring (250rpm) is warming up to 80 DEG C, is added dropwise
2.5mol/L dilute sulfuric acid, reaction solution pH is down to 2.5, after acid adding terminates, add the mass 12.0g of silane coupling A 171 and carry out
Modified-reaction, modification time 60min, washed and filtered with distilled water, be less than 100 μ S/cm to water lotion electrical conductivity, at 105 DEG C
Dried in baking oven, be 5.2wt% to product moisture content, obtain the high reinforcement precipitated silica of hydrophobicity.
Embodiment 2
Pipette 460g SiO2Wet gel, it is added in 2L stirred autoclaves, stirring (250rpm) is warming up to 85 DEG C, is added dropwise
2.5mol/L dilute sulfuric acid, reaction solution pH is down to 2.5, after acid adding terminates, add the mass 12.0g of silane coupling A 171 and carry out
Modified-reaction, modification time 150min, washed and filtered with distilled water, be less than 100 μ S/cm to water lotion electrical conductivity, at 105 DEG C
Dried in baking oven, be 5.2wt% to product moisture content, obtain the high reinforcement precipitated silica of hydrophobicity.
Embodiment 3
Pipette 460g SiO2Wet gel, it is added in 2L stirred autoclaves, stirring (250rpm) is warming up to 90 DEG C, is added dropwise
2.5mol/L dilute sulfuric acid, reaction solution pH is down to 2.5, after acid adding terminates, add the mass 12.0g of silane coupling A 171 and carry out
Modified-reaction, modification time 120min, washed and filtered with distilled water, be less than 100 μ S/cm to water lotion electrical conductivity, at 105 DEG C
Dried in baking oven, be 5.2wt% to product moisture content, obtain the high reinforcement precipitated silica of hydrophobicity.
Embodiment 4
Pipette 460g SiO2Wet gel, it is added in 2L stirred autoclaves, stirring (250rpm) is warming up to 95 DEG C, is added dropwise
2.5mol/L dilute sulfuric acid, reaction solution pH is down to 2.5, after acid adding terminates, add the mass 12.0g of silane coupling A 171 and carry out
Modified-reaction, modification time 90min, washed and filtered with distilled water, be less than 100 μ S/cm to water lotion electrical conductivity, at 105 DEG C
Dried in baking oven, be 5.2wt% to product moisture content, obtain the high reinforcement precipitated silica of hydrophobicity.
Embodiment 5
Pipette 460g SiO2Wet gel, it is added in 2L stirred autoclaves, stirring (250rpm) is warming up to 90 DEG C, is added dropwise
2.5mol/L dilute sulfuric acid, reaction solution pH is down to 2.2, after acid adding terminates, add the mass 10.1g of silane coupling A 171 and carry out
Modified-reaction, modification time 120min, washed and filtered with distilled water, be less than 100 μ S/cm to water lotion electrical conductivity, at 105 DEG C
Dried in baking oven, be 5.2wt% to product moisture content, obtain the high reinforcement precipitated silica of hydrophobicity.
Embodiment 6
Pipette 460g SiO2Wet gel, it is added in 2L stirred autoclaves, stirring (250rpm) is warming up to 90 DEG C, is added dropwise
2.5mol/L dilute sulfuric acid, reaction solution pH is down to 2.5, after acid adding terminates, add the mass 13.8g of silane coupling A 171 and carry out
Modified-reaction, modification time 120min, washed and filtered with distilled water, be less than 100 μ S/cm to water lotion electrical conductivity, at 105 DEG C
Dried in baking oven, be 5.2wt% to product moisture content, obtain the high reinforcement precipitated silica of hydrophobicity.
Embodiment 7
Pipette 460g SiO2Wet gel, it is added in 2L stirred autoclaves, stirring (250rpm) is warming up to 90 DEG C, is added dropwise
2.5mol/L dilute sulfuric acid, reaction solution pH is down to 2.8, after acid adding terminates, add the mass 15.6g of silane coupling A 171 and carry out
Modified-reaction, modification time 120min, washed and filtered with distilled water, be less than 100 μ S/cm to water lotion electrical conductivity, at 105 DEG C
Dried in baking oven, be 5.2wt% to product moisture content, obtain the high reinforcement precipitated silica of hydrophobicity.
Embodiment 8
Pipette 460g SiO2Wet gel, it is added in 2L stirred autoclaves, stirring (250rpm) is warming up to 90 DEG C, is added dropwise
2.5mol/L dilute sulfuric acid, make reaction solution pH to 3.1, after acid adding terminates, add the mass 12.0g of silane coupling A 171 and changed
Property reaction, modification time 120min, with distilled water wash filter, be less than 100 μ S/cm to water lotion electrical conductivity, 105 DEG C dry
Dried in case, be 5.2wt% to product moisture content, obtain the high reinforcement precipitated silica of hydrophobicity.
Comparative example 1
Pipette 460g SiO2Wet gel, it is added in 2L stirred autoclaves, stirring (250rpm) is warming up to 90 DEG C, is added dropwise
2.5mol/L dilute sulfuric acid, reaction solution pH is down to 2.5, after acid adding terminates, be aged 30min, washed and filtered with distilled water, to water
Washing lotion electrical conductivity is less than 100 μ S/cm, is dried in 105 DEG C of baking ovens, is 5.2% to product moisture content, obtains precipitated silica.
Product prepared by above-described embodiment carries out performance test, and test result is shown in Table 1, table 2 and annex.
The performance indications of the product modified white carbon black of the present invention of table 1
The rubber mechanical performance index of the product modified white carbon black of the present invention of table 2
From above-mentioned data it can clearly be seen that product of the present invention is compared with comparative example 1, by silane coupling A 171
Modified white carbon surface hydroxyl number is reduced, and the activation grade and lipophilic degree of white carbon are obviously improved, and white carbon hydrophobicity increases
By force.Applied in rubber for tire, hence it is evident that improve the processing characteristics of rubber, reduce the cure time of rubber, improve vulcanization
The wearability and comprehensive mechanical property of glue.
It can be seen that by comparative example 1 and embodiment 6 (after before modified) XRD spectrum (accompanying drawing 1)：2 θ angles are 23 degree or so
There is a wider SiO2Diffraction maximum, this explanation before modified after white carbon sample be in amorphous state, modified white carbon structure
Do not change, be unformed non-crystal structure.
It can be seen that by comparative example 1 and embodiment 6 (after before modified) TG collection of illustrative plates (accompanying drawing 2)：With the rise of temperature,
Between 50-120 DEG C, rear quality has loss before modified, and the loss of this part is due to that the desorption release for adsorbing water causes；Change
White carbon is slower in 120-800 DEG C of weightlessness before property, and this is due to that white carbon surface adjacent hydroxyl groups are gradually condensed caused by dehydration.It is modified
White carbon is flatter in 120-300 DEG C of weightlessness afterwards, and 300-800 DEG C of weightlessness is gradually accelerated, this be due in this section of heating process not
Dehydration is only condensed, the decomposition of organic carbochain, A171 boiling point is 122 DEG C, still there is larger mass loss explanation at high temperature
There occurs stronger bonding action, A171 to be successfully grafted to white carbon surface for A171 and white carbon surface-active silicone hydroxyl.
It can be seen that by comparative example 1 and embodiment 6 (after before modified) FT-IR collection of illustrative plates (accompanying drawing 3)：It is modified through A171
Afterwards, in 964cm-1The flexural vibrations absworption peak of the Si-OH keys at place substantially dies down, and absorption peak strength is only before modified 30%, these
Show that modified white carbon the adsorbed hydroxyl content is reduced.In 3066cm-1Nearby occur that the C-H stretching vibrations on alkene absorb
Peak, surface white carbon is after modification, surface grafting vinyl-functional.It is white that these all illustrate that A171 has successfully been grafted to
Carbon black particle surface.
It can be seen that by comparative example 1 and embodiment 6 (after before modified) TEM collection of illustrative plates (accompanying drawing 4)：White carbon group before modified
Poly- phenomenon is more serious, and modified dispersiveness is preferably, it can be seen that white carbon primary particle is spherical in shape, is connected with each other between particle in connection
Branch network structure, its particle diameter about 20nm.
It is complete by above-mentioned description, relevant staff using the above-mentioned desirable embodiment according to the present invention as enlightenment
Various change and modification can be carried out without departing from the scope of the technological thought of the present invention' entirely.This invention it is technical
Scope is not limited to the content on specification, it is necessary to determines its technical scope according to right.
Claims (4)
- A kind of 1. preparation method of hydrophobicity high-reinforcement white carbon black, it is characterised in that：By SiO2Wet gel is added in reactor, It is 86% or so to control its moisture content, stirs in a kettle, is heated to setting modification temperature, is adjusted with dilute sulfuric acid to setting Surely pH value is modified, a certain proportion of modifying agent silane coupling A 171 is added, is modified reaction, finally washes, filter, be dry It is dry, obtain hydrophobicity high-reinforcement white carbon black.
- A kind of 2. preparation method of hydrophobicity high-reinforcement white carbon black according to claim 1, it is characterised in that：Modification temperature For 80-95 DEG C, modification time 60-150min, modified pH value is 2.2-3.1.
- A kind of 3. preparation method of hydrophobicity high-reinforcement white carbon black according to claim 1, it is characterised in that：The modification The dosage of agent silane coupling A 171 is the 2.2%-3.4% of reaction solution gross mass.
- A kind of 4. preparation method of hydrophobicity high-reinforcement white carbon black according to Claims 2 or 3, it is characterised in that：It is modified Temperature is 90 DEG C, modification time 120min, pH value 2.5, and the dosage of silane coupling A 171 is reaction solution gross mass 3.0%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107686564A (en) * | 2017-10-30 | 2018-02-13 | 无锡恒诚硅业有限公司 | A kind of preparation method of hydrophabic silica |
| CN110387145A (en) * | 2019-07-18 | 2019-10-29 | 常州大学 | A kind of preparation method of the high abrasion white carbon black for butadiene-styrene rubber reinforcement |
| CN111019400A (en) * | 2019-12-25 | 2020-04-17 | 烟台大学 | Silicon dioxide surface modification method based on homogeneous reaction system |
| CN114014326A (en) * | 2021-10-12 | 2022-02-08 | 华东理工大学 | White carbon black modification method and modified white carbon black |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102220036A (en) * | 2011-06-02 | 2011-10-19 | 北京化工大学 | Method for preparing white carbon black modified by silane coupling agent |
| CN105060304A (en) * | 2015-07-25 | 2015-11-18 | 常州大学 | Preparation method for hydrophobic high-dispersion white carbon black |
| CN105694236A (en) * | 2016-02-18 | 2016-06-22 | 繁昌县菲德通讯材料设计有限公司 | Oil-proof high-and low-temperature resistant cable |
-
2017
- 2017-07-05 CN CN201710541084.3A patent/CN107337810A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102220036A (en) * | 2011-06-02 | 2011-10-19 | 北京化工大学 | Method for preparing white carbon black modified by silane coupling agent |
| CN105060304A (en) * | 2015-07-25 | 2015-11-18 | 常州大学 | Preparation method for hydrophobic high-dispersion white carbon black |
| CN105694236A (en) * | 2016-02-18 | 2016-06-22 | 繁昌县菲德通讯材料设计有限公司 | Oil-proof high-and low-temperature resistant cable |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107686564A (en) * | 2017-10-30 | 2018-02-13 | 无锡恒诚硅业有限公司 | A kind of preparation method of hydrophabic silica |
| CN107686564B (en) * | 2017-10-30 | 2020-07-28 | 无锡恒诚硅业有限公司 | Preparation method of hydrophobic white carbon black |
| CN110387145A (en) * | 2019-07-18 | 2019-10-29 | 常州大学 | A kind of preparation method of the high abrasion white carbon black for butadiene-styrene rubber reinforcement |
| CN111019400A (en) * | 2019-12-25 | 2020-04-17 | 烟台大学 | Silicon dioxide surface modification method based on homogeneous reaction system |
| CN114014326A (en) * | 2021-10-12 | 2022-02-08 | 华东理工大学 | White carbon black modification method and modified white carbon black |
| CN114014326B (en) * | 2021-10-12 | 2023-09-01 | 华东理工大学 | White carbon black modification method and modified white carbon black |
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