CN107778529A - The method of liquid phase Ozone modified Nano carbon black - Google Patents
The method of liquid phase Ozone modified Nano carbon black Download PDFInfo
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- CN107778529A CN107778529A CN201711225849.9A CN201711225849A CN107778529A CN 107778529 A CN107778529 A CN 107778529A CN 201711225849 A CN201711225849 A CN 201711225849A CN 107778529 A CN107778529 A CN 107778529A
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- carbon black
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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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
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Abstract
A kind of method of liquid phase Ozone modified Nano carbon black, belongs to field of chemical raw material preparation, it is characterised in that：Take carbon black sample to be added in the oxidation unit containing zirconium pearl, then add deionized water, and be uniformly mixed with glass bar；Stirred with electric device, while toward being passed through ozone in dispersion liquid；After ozone oxidation, pH value is adjusted with the NaOH solution of saturation, is then further continued for aoxidizing；After oxidation terminates, oxidized black dispersion liquid is poured out, and adds concentrated hydrochloric acid regulation pH；It is then centrifuged for separating, is washed with deionized, separates repeatedly, be finally baked to.Utilize the strong oxidation of ozone, Surface Oxidation Modification is carried out to carbon black in water, to introduce the hydrophily oxy radicals such as carboxyl, hydroxyl in carbon blacksurface, so as to improve the wettability of carbon black, its dispersion stabilization in aqueous is improved, is it basic using feasibility is provided in the industry fields such as pigment printing.
Description
Technical field
The invention belongs to field of chemical raw material preparation, more particularly to a kind of method of liquid phase Ozone modified Nano carbon black.
Background technology
Carbon black is the tiny black powder material generated by the imperfect combustion or cracking of hydrocarbons, mainly by carbon
Element forms, phosphorus content about more than 90%, while also containing elements such as a small amount of oxygen, hydrogen, sulphur and nitrogen.Its crystallite has quasi- stone
Ink structure, and be in concentric orientation.Its particle is intimate spherical colloidal particle, and all clinkerings of these particles are into aggregation, and with
The form of aggregation is present in applied system.Therefore, the morphological character of carbon black directly affects the application performance of carbon black.
As people are increasingly taken seriously to environmental issue growing interest, the research of water-based carbon black dispersion system, into
One of focus for carbon black dispersion Journal of Sex Research.Therefore, carbon black is modified, enhancing carbon black hydrophily, improves carbon black in water
Dispersion stabilization turn into industry make great efforts target.At present, researcher's method hydrophilically modified to carbon black mainly includes：Oxygen
Change modified, Polymer adsorption modification, polymer graft modification and polymer overmold modification etc..Carbon black can be increased by oxidation modification
The oxygen-containing functional group on surface, so as to increase the hydrophily of carbon black；And polymer modification is then by using physical absorption and chemistry
The method of modifying of key even arrives carbon blacksurface by polymer-modified, realizes the Coulomb repulsion between carbon black particle or physical isolation, solves
The certainly agglomeration traits of carbon black in the base.
Although carbon black is a kind of important black pigment colouring agent, the primary particle diameter of carbon black only has tens nanometer, phase
Powder is easily reunited extremely strong Van der Waals force, while the polar group of carbon blacksurface is seldom, is not easy to soak, so as to be difficult
Relatively stable is dispersed in water-based system, thus limits carbon black to a certain extent as the application of black pigment and make
Use effect.And surface is modified the dispersive property that can then improve carbon black, wherein, oxidation modification method is the basic of carbon blacksurface modification
Method.Oxidation modification method mainly includes vapour phase oxidation process, liquid phase oxidation, plasma oxidation method.Wherein, vapour phase oxidation process is
Oxidation processes are carried out to carbon black using oxygen, ozone, nitrogen oxide etc., and liquid phase oxidation is then mainly using nitric acid, hydrogen peroxide, over cure
Sour ammonium etc. carries out oxidation processes to carbon black.In general, the positive effect of liquid phase oxidation is better than gaseous oxidation.But use nitric acid
More spent acid and waste water can be produced to carbon black progress oxidation modification Deng acid solution, it is seriously polluted, and also modifying process compares
It is cumbersome, it is not easy to operate.
The content of the invention
This law aims to provide a kind of method of liquid phase Ozone modified Nano carbon black.
The method of liquid phase Ozone modified Nano carbon black of the present invention, bag following steps：（1）Take 5.32g carbon black samples
It is added in the oxidation unit containing zirconium pearl, then adds 100g deionized waters, and be uniformly mixed with glass bar；（2）With
Electric device stirs, while toward being passed through ozone in dispersion liquid；（3）After ozone oxidation 1h, adjusted with the NaOH solution of saturation scattered
Then the pH value of liquid is further continued for aoxidizing 7h to 13-14；（4）After oxidation terminates, oxidized black dispersion liquid is poured out, and add dense salt
Acid for adjusting pH is to less than 4；（5）It is then centrifuged for separating, is washed with deionized, separates repeatedly, be finally baked to.
The method of liquid phase Ozone modified Nano carbon black of the present invention, step（2）The rotating speed of the electric device is
240r/min。
The method of liquid phase Ozone modified Nano carbon black of the present invention, step（2）The flow of the ozone is 3L/
min。
The method of liquid phase Ozone modified Nano carbon black of the present invention, step（5）The drying temperature is 100 DEG C.
The method of liquid phase Ozone modified Nano carbon black of the present invention, step（5）It is described centrifuge use for
Table model high speed centrifuge H1850.
The method of liquid phase Ozone modified Nano carbon black of the present invention, step（2）The electric mixer is IKA-
RW20。
The method of liquid phase Ozone modified Nano carbon black of the present invention, using the strong oxidation of ozone, in water
Surface Oxidation Modification is carried out to carbon black, to introduce the hydrophily oxy radicals such as carboxyl, hydroxyl in carbon blacksurface, so as to improve charcoal
Black wettability, its dispersion stabilization in aqueous is improved, carried for its application in the industry fields such as pigment printing
For feasibility basis.
Embodiment
The method of liquid phase Ozone modified Nano carbon black of the present invention, bag following steps：（1）Take 5.32g carbon black samples
It is added in the oxidation unit containing zirconium pearl, then adds 100g deionized waters, and be uniformly mixed with glass bar；（2）With
Electric device stirs, while toward being passed through ozone in dispersion liquid；（3）After ozone oxidation 1h, adjusted with the NaOH solution of saturation scattered
Then the pH value of liquid is further continued for aoxidizing 7h to 13-14；（4）After oxidation terminates, oxidized black dispersion liquid is poured out, and add dense salt
Acid for adjusting pH is to less than 4；（5）It is then centrifuged for separating, is washed with deionized, separates repeatedly, be finally baked to.
The method of liquid phase Ozone modified Nano carbon black of the present invention, step（2）The rotating speed of the electric device is
240r/min.Step（2）The flow of the ozone is 3L/min.Step（5）The drying temperature is 100 DEG C.Step（5）It is described
Centrifuge use for table model high speed centrifuge H1850.Step（2）The electric mixer is IKA-RW20.In the aqueous solution
In, the reaction path of ozone and carbon black mainly has 2 kinds, and one kind is that ozone molecule is anti-directly with carbon black by nucleophilic or electrophilic effect
Should, or addition reaction occurs with the double bond of carbon blacksurface.Wherein, 1,3- cycloaddition reactions are ozone and alkene or aromatics
Important mechanism when thing reacts.First, C=C double bonds disconnect, and are connected with the O at ozone both ends, produce five-membered ring intermediate structure.
Then one of O-O singly-bounds disconnect, and generate a zwitterionic intermediate.The C -- C single bond of the intermediate can be further broken,
And the products such as alcohol, aldehyde, acid are generated in H2O presence.Another is that ozone molecule selfdecomposition produces hydroxyl radical free radical, then
Reacted again with carbon black.Ozone is soluble in water first, and react in the basic conditions with OH- produce superoxide radical and
The superoxide radical of protonation；Then the ozone in water again with superoxide radical occur electron transfer reaction, generation oxygen with it is smelly
Oxygen radical；Subsequent ozone free radical is protonated, and and then sloughs a molecule oxygen, generates hydroxyl radical free radical.Then hydroxyl
With carbon black addition reaction occurs for free radical, produces the products such as phenolic hydroxyl group, aldehyde.
After ozone oxidation, the quantity of its surface oxygen functional group substantially increases carbon black, generates substantial amounts of carboxyl, hydroxyl
Base, while also add the content of acid anhydrides and lactone group；And the quinonyl content of carbon blacksurface is then reduced, this is mainly due to quinonyl
Lactone group is generated with neighbouring caused carboxyl reaction.First, it is being carbon blacksurface Free water and knot corresponding to 30 DEG C to 200 DEG C
The desorption process of Heshui, it is mainly that carboxyl decomposes the process for producing carbon dioxide, in this stage, CB- mono- at 200 DEG C to 400 DEG C
The weight-loss ratio that carbonoxide OH weight-loss ratio is 2.03%, CB is 0.81%；And acid anhydrides and lactone group are then in 400 DEG C to 600 DEG C progress
Decompose and produce carbon monoxide and carbon dioxide, wherein CB- carbon monoxide OH weight-loss ratio is that 4.58%, CB weight-loss ratio is
1.53%；In addition, phenolic hydroxyl group then starts to decompose at 600 DEG C produces carbon monoxide, in this process, CB- carbon monoxide OH weight-loss ratio
Weight-loss ratio for 5.22%, CB is 3.93%, and quinones and metal carbonyl then decompose more than 700 DEG C and produce an oxidation
Carbon, wherein CB- carbon monoxide OH weight-loss ratio are 12.43%, and CB weight-loss ratio is 15.81%.
Carbon black is after ozone oxidation, and its carbon content is reduced to 87.44% from 92.32%, and carbon black hydrogen content adds
0.18%, and the oxygen content of oxidizing carbon black through ozone then increases to 11.29% by 6.63%, about adds 4.66%, and H and O members
The mol ratio of plain variable quantity is 0.618.For this explanation after ozone oxidation, carbon blacksurface not only increases the content of carboxyl, and
And the content of hydroxyl is also add, and this also explains the carbon black original that the reduction of pH value and its dispersiveness improve in oxidizing process
Cause.The dispersion liquid of different pH value is configured, and is separately added into 1.3mg oxidized blacks in 40ml dispersion liquid, it is then ultrasonic
30min, then after standing 12h, the particle diameter of oxidized black dispersion liquid is tested, when the pH value of dispersion liquid is between 4.0-10.0, oxidation
The particle diameter of carbon black is with the increase of pH value and in the trend reduced, and pH value is 4.0 to 6.0, and the particle diameter of oxidized black is from 451.5nm
159.4nm is quickly decreased to, but the pH value of dispersion liquid, in 7-10, the particle diameter of oxidized black is held essentially constant.
During by carbon black dispersion in water, due to gravity or centrifugal force, it can be settled in system.If carbon black is scattered
Stability is good, then sinking speed is slow in water, causes in supernatant liquid that contained amounts of carbon black is more, and the absorption to light is more,
So that the light transmittance of supernatant liquid is lower；Conversely, then make it that the light transmittance of supernatant liquid is higher.So can basis
The situation of change of the light transmittance of dispersion liquid, dispersion stabilization of the reflection carbon black in water.With the increase of centrifugation time, former state charcoal
Black and oxidized black light transmittance all increases.Wherein when centrifuging 10min, its light transmittance is just increased to former state carbon black by 13.6%
78.6%, then as the extension of time, its light transmittance is just slowly increased to 96.7%；But oxidized black is in centrifugation 10min
When, its light transmittance just increases to 3.4% from 2%, then then slowly progressively increases to 26.1%.This explanation carbon black is through superoxidized modified
Afterwards, its dispersed stability in sodium bicarbonate solution has obtained very big improvement, and reason is probably that carbon blacksurface adds acidity
Oxygen-containing functional group.Carbon black is modified by ozone oxidation, and its dispersed stability in sodium bicarbonate solution has obtained greatly changing
It is kind.This be due to carbon black after ozone oxidation, more acid oxygen-containing functional groups are introduced on its surface so that its hydrophily
Increase；Be introduced into simultaneously-carbon monoxide OH is easier to be ionized into carbon monoxide O- in sodium bicarbonate solution, make electric double layer electric
Position increase, electrostatic repulsion increase, so as to more make it that oxidized black dispersiveness is more stable.Relative to former state carbon black, oxidized black
After being scattered in water, its average grain diameter is obviously reduced.When pH value is 8-9, particle diameter is about 150nm or so, and under equal conditions,
The average grain diameter of former state carbon black is then 750nm or so.
Claims (6)
- A kind of 1. method of liquid phase Ozone modified Nano carbon black, it is characterised in that bag following steps：（1）Take 5.32g carbon black samples to be added in the oxidation unit containing zirconium pearl, then add 100g deionized waters, and use glass Glass rod is uniformly mixed；（2）Stirred with electric device, while toward being passed through ozone in dispersion liquid；（3）After ozone oxidation 1h, then the pH value for adjusting dispersion liquid with the NaOH solution of saturation is further continued for aoxidizing to 13-14 7h；（4）After oxidation terminates, oxidized black dispersion liquid is poured out, and adds concentrated hydrochloric acid regulation pH to less than 4；（5）It is then centrifuged for separating, is washed with deionized, separates repeatedly, be finally baked to.
- 2. the method for liquid phase Ozone modified Nano carbon black according to claim 1, it is characterised in that：Step（2）It is described The rotating speed of electric device is 240r/min.
- 3. the method for liquid phase Ozone modified Nano carbon black according to claim 2, it is characterised in that：Step（2）It is described The flow of ozone is 3L/min.
- 4. the method for liquid phase Ozone modified Nano carbon black according to claim 3, it is characterised in that：Step（5）It is described Drying temperature is 100 DEG C.
- 5. the method for liquid phase Ozone modified Nano carbon black according to claim 4, it is characterised in that：Step（5）It is described Centrifuge use for table model high speed centrifuge H1850.
- 6. the method for liquid phase Ozone modified Nano carbon black according to claim 5, it is characterised in that：Step（2）It is described Electric mixer is IKA-RW20.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110538651A (en) * | 2019-09-10 | 2019-12-06 | 沈阳化工研究院有限公司 | Platinum-carbon catalyst and preparation method thereof |
| CN110591419A (en) * | 2019-09-10 | 2019-12-20 | 沈阳化工研究院有限公司 | Modified superfine carbon black catalyst and application thereof |
| CN111269590A (en) * | 2020-03-04 | 2020-06-12 | 焦作市和兴化学工业有限公司 | Preparation method of easily-dispersible acetylene black |
| CN111564632A (en) * | 2020-05-20 | 2020-08-21 | 苏州柔能纳米科技有限公司 | Preparation method of electrode slurry for flexible battery |
| CN111808445A (en) * | 2020-05-07 | 2020-10-23 | 安徽省克林泰迩再生资源科技有限公司 | Process method for preparing hydrophilic pyrolysis carbon black by using pressure difference |
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2017
- 2017-11-29 CN CN201711225849.9A patent/CN107778529A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110538651A (en) * | 2019-09-10 | 2019-12-06 | 沈阳化工研究院有限公司 | Platinum-carbon catalyst and preparation method thereof |
| CN110591419A (en) * | 2019-09-10 | 2019-12-20 | 沈阳化工研究院有限公司 | Modified superfine carbon black catalyst and application thereof |
| CN110591419B (en) * | 2019-09-10 | 2021-06-01 | 沈阳化工研究院有限公司 | Modified superfine carbon black catalyst and application thereof |
| CN111269590A (en) * | 2020-03-04 | 2020-06-12 | 焦作市和兴化学工业有限公司 | Preparation method of easily-dispersible acetylene black |
| CN111269590B (en) * | 2020-03-04 | 2021-10-22 | 焦作市和兴化学工业有限公司 | Preparation method of easily-dispersible acetylene black |
| CN111808445A (en) * | 2020-05-07 | 2020-10-23 | 安徽省克林泰迩再生资源科技有限公司 | Process method for preparing hydrophilic pyrolysis carbon black by using pressure difference |
| CN111564632A (en) * | 2020-05-20 | 2020-08-21 | 苏州柔能纳米科技有限公司 | Preparation method of electrode slurry for flexible battery |
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Application publication date: 20180309 |