CN107697920A - A kind of method that hydrophobic nano white carbon is prepared using sol-gal process - Google Patents

A kind of method that hydrophobic nano white carbon is prepared using sol-gal process Download PDF

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Publication number
CN107697920A
CN107697920A CN201711164387.4A CN201711164387A CN107697920A CN 107697920 A CN107697920 A CN 107697920A CN 201711164387 A CN201711164387 A CN 201711164387A CN 107697920 A CN107697920 A CN 107697920A
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white carbon
sol
bentonite
prepared
microwave
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戴文忠
吴钰娟
戴超
戴文秉
戴章
戴冕
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Anhui Yifala Electrical Co Ltd
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Anhui Yifala Electrical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/16—Preparation of silica xerogels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/32—Alkali metal silicates
    • 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
    • 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
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of method that hydrophobic nano white carbon is prepared using sol-gal process, using rice hull ash, bentonite as raw material in the present invention, by rice hull ash pickling impurity removal, bentonite is after pickling under microwave action, using microwave reaction mode, reacted with sodium hydroxide and obtain water glass solution, using obtained water glass solution as silicon source, ammoniacal liquor is catalyst, the white carbon particle size of preparation is small, specific surface area is big, and purity is high, has excellent physical and chemical properties；Using vinyl silanes as modifying agent, by sol-gal process successfully by the surface of hydrophobic grouping vinyl graft copolymer to white carbon, improve the hydrophobicity of white carbon, strengthen the interaction between white carbon and silicon rubber, the fields such as the rubber at basic, normal, high end, the coating of special purpose, silastic product are can be widely used for, especially in electrically insulating silicone rubber arts.

Description

A kind of method that hydrophobic nano white carbon is prepared using sol-gel process
Technical field
The invention belongs to white carbon preparing technical field, and in particular to one kind prepares hydrophobic type using sol-gel process and received The method of off-white carbon black.
Background technology
The production method of traditional white carbon mainly has using halosilanes as the vapor phase method of raw material, using waterglass and inorganic acid as original The precipitation method of material.The white carbon that distinct methods are prepared, its structure and performance also difference.Precipitated silica particle size Larger, specific surface area is smaller, less to the adsorption layer of rubber, and its reinforcing property to silicon rubber is relatively poor；Vapor phase method hard charcoal Black track producing particle size is small, and specific surface area is big, and substantial amounts of adsorption layer is easily formed to rubber, strengthens mutual between white carbon and silicon rubber Effect, its reinforcing property to rubber are excellent.Collosol and gel fado is using TEOS as silicon source, and acid or alkali are catalyst, preparation White carbon particle size is small, and specific surface area is big, and purity is high, has excellent physical and chemical properties.
There are a large amount of activity hydroxies in white carbon surface, these surface hydroxyls also play in white carbon is to the reinforcement of silicon rubber Positive effect.Because hard charcoal black track producing particle is small, specific surface area is big, and substantial amounts of interface, the table of white carbon are formd in silicon rubber The strand of face hydroxyl and silicon rubber forms hydrogen bond, enhances the interface binding power between white carbon and silicon rubber.But this effect It is weaker, and stability is bad.The surface hydroxyl of white carbon is reduced, although improving the hydrophobicity of white carbon, is reduced Interaction between white carbon and silicon rubber.White carbon is grafted using with hydrophobic functional group, white carbon can not only be improved Hydrophobicity, the strand of functional group and silicon rubber can also be made to chemically react, strengthen white carbon and the phase between silicon rubber Interaction.
The content of the invention
In view of the shortcomings of the prior art, hydrophobic nano hard charcoal is prepared using sol-gel process the invention provides one kind Black method, improve the hydrophobic of white carbon while realize effective control of dialogue particle size carbon black.
The present invention is achieved by the following technical solutions：
A kind of method that hydrophobic nano white carbon is prepared using sol-gel process, using rice hull ash, bentonite as raw material, by rice Shell ash pickling impurity removal, bentonite, using microwave reaction mode, react with sodium hydroxide after pickling under microwave action and obtain water glass Glass solution, using vinyl silanes as modifying agent, hydrophobic nano white carbon is obtained through sol-gel transition.
The vinyl silanes include vinyltrimethoxy silane, VTES or vinyl triacetyl TMOS.
Specifically include following processing step：
（1）Pretreatment of raw material：
100 mesh sieves are crushed after rice hull ash is cleaned, after washing 40-70min under 55-65 DEG C of stirring, by the rice husk after washing Ash soaks 2-2.5 hours under 55-65 DEG C of stirring under the conditions of pH is 1-1.5, centrifugation washing, is neutrality to eluate, will The rice hull ash arrived is dried, standby；
100-200 mesh sieves are crushed after bentonite is cleaned, after washing, according to liquid-solid ratio 4-5:1 adds the bentonite after washing In the sulfuric acid solution for entering 30-50%, microwave treatment 35-55min, it is then centrifuged for washing, is neutrality to eluate, then will obtain Bentonite dry, it is standby；
（2）The preparation of water glass solution：
, will be according to 1 according to 13-17g/100mL solid-liquid ratio：The 0.5-3 above-mentioned bentonite of mass ratio, rice hull ash mixing add dense Spend 2-3mol/L sodium hydroxide solution, be sufficiently mixed, be placed in microwave chemical reactor, microwave reaction for a period of time after, take out Filter, filter residue is washed with boiling water, filtrate concentration, obtains water glass solution；
（3）The preparation of acidic hydrolysis solution：
Vinyl silanes, distilled water and absolute ethyl alcohol are measured respectively according to 1:7-10:6-12 volume ratio mixing, adds 8-15% 0.1mL/L hydrochloric acid solutions, be placed in after being mixed in 36-45 DEG C of water bath with thermostatic control, per 5min vibrate 1 time, hydrolyze 15-25min, system It is standby into vinyl silanes acidic hydrolysis solution；
（4）Prepare graft modification white carbon：
Compound concentration is 0.25-0.5mol/L ammoniacal liquor, according to 3-5:1 volume ratio mixes ammoniacal liquor, ethanol, is placed in water-bath It is interior, when temperature reaches 48-53 DEG C, the step of being slowly added to 2 times of ammoniacal liquor volumes（2）Water glass solution, charging terminate 10- After 15min, step is added into reaction solution（3）Vinyl silanes acidic hydrolysis liquid, is placed in 45-55 DEG C of water bath with thermostatic control, carries out Modified-reaction, after the still aging 50-65min of precipitation system, centrifuge precipitation is filtered, dry after obtain Nano carbon white.
Wherein, the step（1）Microwave treatment is 400-500W using microwave irradiation intensity.
Wherein, the step（2）The irradiation intensity of microwave reaction is 650-800W, and the time is in 25-60min.
Wherein, the usage amount of the vinyl silanes is the 10-20% of water glass solution.
The present invention has the beneficial effect that：
（1）Using rice hull ash, bentonite as raw material in the present invention, by rice hull ash pickling impurity removal, bentonite pickling under microwave action, H+Mg in the gradual dissolution octahedron of meeting2+, but the silicon atom in raw material is not had an effect substantially, heated and improved using microwave Mg2+Leaching rate, the amorphous silica that silicon becomes active is stayed in solid product, afterwards using microwave reaction side Formula, rice hull ash, bentonite and sodium hydroxide reaction obtain water glass solution, reach acceleration reaction, contracting by microwave irradiation heating The purpose of short reaction time, then the water glass solution to obtain is silicon source, ammoniacal liquor are catalyst, the white carbon particle size of preparation Small, specific surface area is big, and purity is high, has an excellent physical and chemical properties, while can be with recycling trade waste, greatly Amplitude reduction white carbon black production cost of material.
（2）The present invention is successfully connect hydrophobic grouping vinyl by sol-gel process using vinyl silanes as modifying agent Branch arrives the surface of white carbon, on the one hand improves the hydrophobicity of white carbon, and the vinyl on another aspect white carbon surface can join With the cross-linking reaction during silicon rubber vulcanization, strengthen the interaction between white carbon and silicon rubber, trigger silicon rubber and hard charcoal The formation of the vinyl cross-linked network on black surface, promotes the sulfidation of silicon rubber, product of the present invention can be widely used for it is low, in, The fields such as high-end rubber, the coating of special purpose, silastic product, especially in electrically insulating silicone rubber arts.
Embodiment
Embodiment 1
A kind of method that hydrophobic nano white carbon is prepared using sol-gel process, using rice hull ash, bentonite as raw material, by rice Shell ash pickling impurity removal, bentonite, using microwave reaction mode, react with sodium hydroxide after pickling under microwave action and obtain water glass Glass solution, using vinyl silanes as modifying agent, hydrophobic nano white carbon is obtained through sol-gel transition.
Specifically include following processing step：
（1）Pretreatment of raw material：
100 mesh sieves are crushed after rice hull ash is cleaned, after washing 50min under 60 DEG C of stirrings, by the rice hull ash after washing 60 DEG C stirring under pH be 1 under the conditions of soak 2 hours, centrifugation washing, to eluate for neutrality, by obtained rice hull ash drying, it is standby With；
100 mesh sieves are crushed after bentonite is cleaned, after washing, according to liquid-solid ratio 4:Bentonite after washing is added 50% by 1 In sulfuric acid solution, microwave treatment 50min, it is then centrifuged for washing, is neutrality to eluate, then dries obtained bentonite, It is standby；
（2）The preparation of water glass solution：
, will be according to 1 according to 15g/100mL solid-liquid ratio：The 2 above-mentioned bentonite of mass ratio, rice hull ash mixing add concentration 2mol/ L sodium hydroxide solution, is sufficiently mixed, and is placed in microwave chemical reactor, microwave reaction for a period of time after, filter, use boiling water Filter residue is washed, filtrate concentration, obtains water glass solution；
（3）The preparation of acidic hydrolysis solution：
Vinyltrimethoxy silane, distilled water and absolute ethyl alcohol are measured respectively according to 1:8:10 volume ratio mixing, adds 15% 0.1mL/L hydrochloric acid solutions, be placed in after being mixed in 40 DEG C of water bath with thermostatic control, per 5min vibrate 1 time, hydrolyze 20min, ethene is made Base silane acidic hydrolysis solution, it is standby；
（4）Prepare graft modification white carbon：
Compound concentration is 0.5mol/L ammoniacal liquor, according to 3:1 volume ratio mixes ammoniacal liquor, ethanol, is placed in water-bath, treats temperature Degree is when reaching 50 DEG C, the step of being slowly added to 2 times of ammoniacal liquor volumes（2）Water glass solution, after charging terminates 10min, to reaction solution Middle addition step（3）Vinyl silanes acidic hydrolysis liquid, it is placed in 50 DEG C of waters bath with thermostatic control, is modified reaction, precipitation system is quiet After putting ageing 65min, centrifuge and obtain Nano carbon white after precipitating filtered, drying.
Wherein, the step（1）Microwave treatment is 465W using microwave irradiation intensity.
Wherein, the step（2）The irradiation intensity of microwave reaction is 650W, and the time is in 30min.
Wherein, the usage amount of the vinyl silanes is the 10% of water glass solution.

Claims (6)

  1. A kind of 1. method that hydrophobic nano white carbon is prepared using sol-gel process, it is characterised in that with rice hull ash, swelling Soil is raw material, and by rice hull ash pickling impurity removal, bentonite is after pickling under microwave action, using microwave reaction mode, with hydroxide Sodium reaction obtains water glass solution, and using vinyl silanes as modifying agent, hydrophobic nano hard charcoal is obtained through sol-gel transition It is black.
  2. 2. a kind of method that hydrophobic nano white carbon is prepared using sol-gel process, its feature are existed according to claim 1 In the vinyl silanes include vinyltrimethoxy silane, VTES or vinyl triacetoxy Silane.
  3. 3. a kind of method that hydrophobic nano white carbon is prepared using sol-gel process, its feature are existed according to claim 1 In specifically including following processing step：
    （1）Pretreatment of raw material：
    100 mesh sieves are crushed after rice hull ash is cleaned, after washing 40-70min under 55-65 DEG C of stirring, by the rice husk after washing Ash soaks 2-2.5 hours under 55-65 DEG C of stirring under the conditions of pH is 1-1.5, centrifugation washing, is neutrality to eluate, will The rice hull ash arrived is dried, standby；
    100-200 mesh sieves are crushed after bentonite is cleaned, after washing, according to liquid-solid ratio 4-5:1 adds the bentonite after washing In the sulfuric acid solution for entering 30-50%, microwave treatment 35-55min, it is then centrifuged for washing, is neutrality to eluate, then will obtain Bentonite dry, it is standby；
    （2）The preparation of water glass solution：
    , will be according to 1 according to 13-17g/100mL solid-liquid ratio：The 0.5-3 above-mentioned bentonite of mass ratio, rice hull ash mixing add dense Spend 2-3mol/L sodium hydroxide solution, be sufficiently mixed, be placed in microwave chemical reactor, microwave reaction for a period of time after, take out Filter, filter residue is washed with boiling water, filtrate concentration, obtains water glass solution；
    （3）The preparation of acidic hydrolysis solution：
    Vinyl silanes, distilled water and absolute ethyl alcohol are measured respectively according to 1:7-10:6-12 volume ratio mixing, adds 8-15% 0.1mL/L hydrochloric acid solutions, be placed in after being mixed in 36-45 DEG C of water bath with thermostatic control, per 5min vibrate 1 time, hydrolyze 15-25min, system It is standby into vinyl silanes acidic hydrolysis solution；
    （4）Prepare graft modification white carbon：
    Compound concentration is 0.25-0.5mol/L ammoniacal liquor, according to 3-5:1 volume ratio mixes ammoniacal liquor, ethanol, is placed in water-bath It is interior, when temperature reaches 48-53 DEG C, the step of being slowly added to 2 times of ammoniacal liquor volumes（2）Water glass solution, charging terminate 10- After 15min, step is added into reaction solution（3）Vinyl silanes acidic hydrolysis liquid, is placed in 45-55 DEG C of water bath with thermostatic control, carries out Modified-reaction, after the still aging 50-65min of precipitation system, centrifuge precipitation is filtered, dry after obtain Nano carbon white.
  4. 4. a kind of method that hydrophobic nano white carbon is prepared using sol-gel process, its feature are existed according to claim 3 In the step（1）Microwave treatment is 400-500W using microwave irradiation intensity.
  5. 5. a kind of method that hydrophobic nano white carbon is prepared using sol-gel process, its feature are existed according to claim 3 In the step（2）The irradiation intensity of microwave reaction is 650-800W, and the time is in 25-60min.
  6. 6. a kind of method that hydrophobic nano white carbon is prepared using sol-gel process, its feature are existed according to claim 3 In the usage amount of the vinyl silanes is the 10-20% of water glass solution.
CN201711164387.4A 2017-11-21 2017-11-21 A kind of method that hydrophobic nano white carbon is prepared using sol-gal process Pending CN107697920A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020029019A1 (en) * 2018-08-06 2020-02-13 湖州五爻硅基材料研究院有限公司 Novel precipitated silica and preparation method therefor
CN112143259A (en) * 2020-10-16 2020-12-29 安徽锦华氧化锌有限公司 Treatment process for improving reinforcing effect of white carbon black
CN113636564A (en) * 2021-09-09 2021-11-12 无锡恒诚硅业有限公司 Green preparation method of white carbon black
WO2023009065A3 (en) * 2021-07-27 2023-04-13 Singapore Polytechnic Method for making silica aerogel blanket

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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
CN103130228A (en) * 2011-11-28 2013-06-05 陈昆先 Preparation method of high dispersion white carbon black from bentonite by making use of non-metallic mine dissociation method
CN103803559A (en) * 2014-01-17 2014-05-21 江西恒隆实业有限公司 Processing technology for white carbon black with low water content
CN104340982A (en) * 2014-10-17 2015-02-11 江西恒隆实业有限公司 Production technique for preparing silica white from rice hull ash
CN104445221A (en) * 2014-12-02 2015-03-25 铜仁学院 New microwave-assisted method for preparing white carbon black from rice hull ash

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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
CN103130228A (en) * 2011-11-28 2013-06-05 陈昆先 Preparation method of high dispersion white carbon black from bentonite by making use of non-metallic mine dissociation method
CN103803559A (en) * 2014-01-17 2014-05-21 江西恒隆实业有限公司 Processing technology for white carbon black with low water content
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CN104445221A (en) * 2014-12-02 2015-03-25 铜仁学院 New microwave-assisted method for preparing white carbon black from rice hull ash

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020029019A1 (en) * 2018-08-06 2020-02-13 湖州五爻硅基材料研究院有限公司 Novel precipitated silica and preparation method therefor
CN111867974A (en) * 2018-08-06 2020-10-30 浙江三时纪新材科技有限公司 Novel precipitated white carbon black and preparation method thereof
CN111867974B (en) * 2018-08-06 2022-11-01 浙江三时纪新材科技有限公司 Precipitated white carbon black and preparation method thereof
CN112143259A (en) * 2020-10-16 2020-12-29 安徽锦华氧化锌有限公司 Treatment process for improving reinforcing effect of white carbon black
WO2023009065A3 (en) * 2021-07-27 2023-04-13 Singapore Polytechnic Method for making silica aerogel blanket
CN113636564A (en) * 2021-09-09 2021-11-12 无锡恒诚硅业有限公司 Green preparation method of white carbon black
CN113636564B (en) * 2021-09-09 2022-11-22 无锡恒诚硅业有限公司 Green preparation method of white carbon black

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