CN108165054A - A kind of preparation method of cation carbon black - Google Patents
A kind of preparation method of cation carbon black Download PDFInfo
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- CN108165054A CN108165054A CN201711439891.0A CN201711439891A CN108165054A CN 108165054 A CN108165054 A CN 108165054A CN 201711439891 A CN201711439891 A CN 201711439891A CN 108165054 A CN108165054 A CN 108165054A
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- carbon black
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- epoxychloropropane
- tetraethyl orthosilicate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
Abstract
The present invention relates to a kind of preparation methods of cationic carbon black.Using nano carbon black as raw material, tetraethyl orthosilicate is presoma, concentrated ammonia liquor makees catalyst, ethanol water makees solvent, epoxychloropropane and tertiary amine are modifying agent, certain condition quaternization reaction, centrifuge washing, it is redispersed in aqueous solution and obtains cationic carbon black dispersion liquid, it is dry to obtain cationic carbon black powder.The present invention in carbon blacksurface covalence graft cationic quaternary ammonium functional group by preparing cationic carbon black, and granularity is small, and surface carries positive charge, has dispersibility well, can be used as the production fields such as fabric, chromotrichia, ink-jet paint, rubber plastic filling.
Description
Technical field
The present invention relates to a kind of preparation methods of the nano carbon black of surface covalence graft cation group.
Background technology
Black dyes and pigment are widely used in the fields such as weaving, cosmetics, coating.At present in field of printing and dyeing extensively
The black dyes used is mostly azo dyes, has good chemical stability, preferable color fastness, but reductive cleavage can produce
Raw carcinogen endangers human health.
Carbon black is a kind of amorphous carbon, light, pine and superfine black powder, and grain size is from tens nanometers to hundreds of nanometers
It differs, there is excellent reinforcing, coloring, light resistance etc., be widely used in ink, paint, the fields such as plastics and coating.
Carbon black has natural black simultaneously, and alternative azo dyes is as ideal black pigment.Multiselect grain size is sufficiently small at present
Carbon black pellet, using dispersant handle or Surface Oxidation Modification prepare dispersion charcoal blacks, the carbon black of these modifications
Dispersion liquid has good dispersibility, depends on intermolecular force and reaches coloring effect, but carbon black own face specific functional groups
Then less, intermolecular force is weaker, limits its tinctorial property to a certain extent.
Quarternary ammonium salt is also known as quaternary ammonium salt, is all replaced the compound generated by alkyl for four hydrogen atoms in ammonium ion,
There are one positive charges for band on central nitrogen atom.It in textile printing and dyeing industry, can be used as softening agent, antistatic agent, have excellent soft
Soft, antistatic, sterilization, yellowing resistance energy, dosage is few, and effect is good, and it is convenient to prepare, and compatibility is good, has high cost performance；
Water treatment field, as flocculant, demulsifier, as a kind of quaternary ammonium salt of inorganic flocculating agent synergist；It, can in petroleum industry
As drilling fluid, VES fracturing fluids, drag reducer, thickener；And antiseptic, anion synergist etc..
With reference to cation quaternary ammonium salt excellent properties, the present invention passes through the quaternary ammonium function in carbon blacksurface covalence graft cation
Group, cation group can improve the chemism and water solubility of carbon black, electronegative substance can be adsorbed in by electrostatic interaction
Surface, such as acrylic fibers, blended fabric.And hydrophobic long-chain fat hydrocarbon can increase carbon blacksurface steric hindrance in its quaternary ammonium component, reduce charcoal
It is black from agglomeration, improve the performance of carbon black.In addition, covalence graft has the amino acid of weak cationic in the table of carbon black
Face can improve the bio-compatibility of carbon black, can be as the colorant of daily cosmetics.
Invention content
A kind of preparation method of cationic carbon black is provided the purpose of the invention is to improve the deficiencies in the prior art,
Carbon blacksurface covalence graft quaternary ammonium functional group improves the surface property of carbon black.
The technical solution adopted in the present invention is：A kind of preparation method of cation nanometer carbon black, is as follows：
A) a certain amount of nano carbon black, catalyst, solvent are mixed evenly, tetraethyl orthosilicate ethyl alcohol is added dropwise in heating
Solution reacts certain time；
B) to A) in mixed liquor, epoxychloropropane is added in, after keeping thermotonus, add tertiary amine or amino acid and its spread out
Biology, temperature control carry out quaternization reaction；
C step B) is taken) the cationic carbon black mixed liquor centrifuge washing that is prepared is in neutrality to pH, is redispersed in water, obtains
Modified cation carbon black dispersion liquid is obtained, cationic carbon black is obtained after dry.
Preferred steps A) in nano carbon black grain size be 15~50nm.Preferred steps A) in solvent be volumetric concentration be 80~
100% ethanol water.
Preferred steps A) described in tetraethyl orthosilicate ethanol solution in the volume ratio of tetraethyl orthosilicate and ethyl alcohol be
1：(2.5~5).
Preferred steps A) described in catalyst for concentrated ammonia liquor, the mass concentration of concentration is 25~28%；Nano carbon black powder
The mass volume ratio of body and catalyst is 1：(1~4) g/mL.
Preferred steps A) described in nano carbon black powder and tetraethyl orthosilicate mass volume ratio be 1：(2~4) g/
mL。
Preferred steps A) in heating be added dropwise tetraethyl orthosilicate ethanol solution temperature be 40 DEG C~60 DEG C；One timing of reaction
Between be 1~3h.
Preferred steps B) described in tertiary amine be dodeca-tertiary amine, 12 tertiary amines, 16 tertiary amines or 3- dimethylaminos third
One kind in amine；Tertiary amine is 1 with the molar ratio of epoxychloropropane：(1~1.1).
Preferred steps B) described in amino acid and its derivative be arginine, arginine monohydrochloride or arginine ethyl ester salt
The molar ratio of one kind of hydrochlorate, amino acid and its derivative and epoxychloropropane is 1：(1~1.1).
Preferred steps B) in keep thermotonus 40 DEG C~60 DEG C of temperature, the reaction time be 1~3h；Quaternization reaction temperature
Spend is 50~70 DEG C；Reaction time is 1~3h.
Preferred steps A) in tetraethyl orthosilicate and step B) in epoxychloropropane molar ratio be 1：(0.5~3).
Advantageous effect：
1st, the cationic carbon black pellet average grain diameter that prepared by the present invention is small (30~70nm), surface covalence graft cation official
It can roll into a ball, can have certain characteristic of quaternary ammonium salt and good dispersibility, zeta current potentials display surface carries positive charge.
2nd, cationic carbon black can be used as colour carbon black that can save the pretreatment to fabric, and it for fabric coloring
Color performance is better than the tinctorial property of pure carbon black.
3rd, amino-acid modified cationic carbon black improves the bio-compatibility of carbon black, can as the black of daily cosmetics
Toner.
4th, the coloring process safety of cationic charcoal blacks will not generate harmful substance as organic dyestuff decomposes.
Description of the drawings
Fig. 1 is CB@SiO2 composite material of core-shell structure, the covalent modified CB@SiO2 of epoxychloropropane prepared by embodiment 1
The infrared spectrogram of composite material, cationic carbon black.
Fig. 2 is the TEM figures of the cationic carbon black prepared by embodiment 18.
Fig. 3 is embodiment 1, example 17, example 18, the thermogravimetric analysis figure of cationic carbon black prepared by example 19.
Fig. 4 is the comparison diagram that embodiment 18 colours wool fabric with pure carbon black.
Specific embodiment
The embodiment of the present invention is described in detail below, the present embodiment is carried out lower premised on inventive technique scheme
Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following realities
Apply example.The experimental program of actual conditions is not specified in embodiment, the condition usually according to normal condition or proposed by manufacturer
Implement.
Embodiment 1
A kind of cation carbon black, specific preparation process are as follows：
The first step：1g nano carbon blacks (average grain diameter 24nm), 3ml concentrated ammonia liquors (mass concentration 28%) are taken in 40ml95%
In ethanol water, 1h is sufficiently stirred, is warming up to 50 DEG C after mixing.3ml tetraethyl orthosilicates is taken to be dissolved in 8ml95% ethyl alcohol
Solution, oscillation is uniformly mixed, then above-mentioned carbon black suspension is added dropwise, and reacts 2h.
Second step：A certain amount of epoxychloropropane is added in into above-mentioned reaction solution, 50 DEG C are stirred to react 2h, add 12
Tertiary amine stops heating after 50 DEG C of quaternization reaction 2h, obtains cationic carbon black suspension.Tetraethyl orthosilicate, epoxychloropropane
Molar ratio with dodeca-tertiary amine is 1:2:2.
Third walks：By above-mentioned suspension, centrifuge washing to pH is in neutrality, and is redispersed in water and is obtained cationic carbon black dispersion
Liquid is dried to obtain cationic carbon black powder.The zeta current potentials of cationic carbon black dispersion liquid are+40.0mv.
Fig. 1 is intermediate product CB@SiO2 compounds prepared by the example 1, and the covalent modified CB@SiO2 of epoxychloropropane are answered
The infrared spectrum of object and final product cation carbon black is closed, comparison is as can be seen that compound after epoxychloropropane modified
Do not occur the characteristic peak of three-membered ring in infrared but the characteristic peak of-CH2- occur, while hydroxyl peak is strengthened, and illustrates epoxychloropropane
Open loop anti-ization occurs and answers covalence graft in composite surface.- CH2- the peaks of cationic carbon black are strengthened, while C-N peaks, explanation occur
Tertiary amine participates in quaternization reaction.
Fig. 3 b are the thermogravimetric curve of the cationic carbon black of embodiment 1, be cationic carbon blacksurface sun between 120-530 DEG C from
The weightlessness of subgroup point, it can be seen that the accounting of cationic components is bigger.
Embodiment 2
A kind of cation carbon black, specific preparation process are as follows：
The first step：1g nano carbon blacks (average grain diameter 24nm), 3ml concentrated ammonia liquors (mass concentration 28%) are taken in 40ml95%
In ethanol water, 1h is sufficiently stirred, is warming up to 50 DEG C after mixing.3ml tetraethyl orthosilicates is taken to be dissolved in 8ml95% ethyl alcohol
Solution, oscillation is uniformly mixed, then above-mentioned carbon black suspension is added dropwise, and reacts 2h.
Second step：Epoxychloropropane is added in into above-mentioned reaction solution, 50 DEG C are stirred to react 2h, add 3- dimethylaminos third
Amine stops heating after 50 DEG C of quaternization reaction 2h, obtains cationic carbon black suspension.Tetraethyl orthosilicate, epoxychloropropane, 3-
The molar ratio of dimethylaminopropylamine is 1:2:2.
Third walks：By above-mentioned suspension, centrifuge washing to pH is in neutrality, and is redispersed in water and is obtained cationic carbon black dispersion
Liquid is dried to obtain cationic carbon black powder.The zeta current potentials of cationic carbon black dispersion liquid are+52.0mv.
Embodiment 3
A kind of cation carbon black, specific preparation process are as follows：
The first step：1g nano carbon blacks (average grain diameter 24nm), 3ml concentrated ammonia liquors (mass concentration 25%) are taken in 40ml95%
In ethanol water, 1h is sufficiently stirred, is warming up to 50 DEG C after mixing.3ml tetraethyl orthosilicates is taken to be dissolved in 8ml95% ethyl alcohol
Solution, oscillation is uniformly mixed, then above-mentioned carbon black suspension is added dropwise, and reacts 2h.
Second step：Epoxychloropropane is added in into above-mentioned reaction solution, 50o is stirred to react 2h, adds 12 tertiary amines,
Stop heating after 50 DEG C of quaternization reaction 2h, obtain cationic carbon black suspension.Tetraethyl orthosilicate, epoxychloropropane, 12
The molar ratio of 14 tertiary amines is 1:2:2.
Third walks：By above-mentioned suspension, centrifuge washing to pH is in neutrality, and is redispersed in water and is obtained cationic carbon black dispersion
Liquid is dried to obtain cationic carbon black powder.The zeta current potentials of cationic carbon black dispersion liquid are+46.4mv.
Embodiment 4
A kind of cation carbon black, specific preparation process are as follows：
One step：1g nano carbon blacks (average grain diameter 24nm), 3ml concentrated ammonia liquors (mass concentration 28%) are taken in 40ml95% second
In alcohol solution, 1h is sufficiently stirred, is warming up to 50 DEG C after mixing.3ml tetraethyl orthosilicates is taken to be dissolved in 8ml95% ethyl alcohol molten
Liquid, oscillation is uniformly mixed, then above-mentioned carbon black suspension is added dropwise, and reacts 2h.
Second step：Add in epoxychloropropane into above-mentioned reaction solution, 50o2h is stirred to react, adds 16 tertiary amines, 50 DEG C
Stop heating after quaternization reaction 2h, obtain cationic carbon black suspension.Tetraethyl orthosilicate, epoxychloropropane, 16 tertiary amines
Molar ratio be 1:2:2.
Third walks：By above-mentioned suspension, centrifuge washing to pH is in neutrality, and redisperse obtains cationic carbon black dispersion liquid, is done
It is dry to obtain cationic carbon black powder.The zeta current potentials of cationic carbon black dispersion liquid are+43.8mv.
Embodiment 5
A kind of cation carbon black, specific preparation process are as follows：
The first step：Take 1g nano carbon blacks (average grain diameter 16nm), 3ml concentrated ammonia liquors (mass concentration 28%) anhydrous in 40ml
In ethyl alcohol, 1h is sufficiently stirred, is warming up to 50 DEG C after mixing.3ml tetraethyl orthosilicates is taken to be dissolved in 10ml ethanol solutions,
Oscillation is uniformly mixed, then above-mentioned carbon black suspension is added dropwise, and reacts 2h.
Second step：Epoxychloropropane is added in into above-mentioned reaction solution, 50 DEG C are stirred to react 2h, add 12 uncles
Amine stops heating after 50 DEG C of quaternization reaction 2h, obtains cationic carbon black suspension.Tetraethyl orthosilicate, epoxychloropropane, ten
The molar ratio of 24 tertiary amines is 1:2:2.
Third walks：By above-mentioned suspension, centrifuge washing to pH is in neutrality, and is redispersed in water and is obtained cationic carbon black dispersion
Liquid is dried to obtain cationic carbon black powder.The zeta current potentials of cationic carbon black dispersion liquid are+47.9mv.
Embodiment 6
A kind of cation carbon black, specific preparation process are as follows：
The first step：Take 1g nano carbon blacks (average grain diameter 30nm), 3ml concentrated ammonia liquors (mass concentration 28%) anhydrous in 40ml
In ethyl alcohol, 1h is sufficiently stirred, is warming up to 50 DEG C after mixing.3ml tetraethyl orthosilicates is taken to be dissolved in 8ml ethanol solutions,
Oscillation is uniformly mixed, then above-mentioned carbon black suspension is added dropwise, and reacts 2h.
Second step：Epoxychloropropane is added in into above-mentioned reaction solution, 50 DEG C are stirred to react 2h, add 12 uncles
Amine stops heating after 50 DEG C of quaternization reaction 2h, obtains cationic carbon black suspension.Tetraethyl orthosilicate, epoxychloropropane, ten
The molar ratio of 24 tertiary amines is 1:2:2.
Third walks：By above-mentioned suspension, centrifuge washing to pH is in neutrality, and redisperse obtains cationic carbon black dispersion liquid, is done
It is dry to obtain cationic carbon black powder.The zeta current potentials of cationic carbon black dispersion liquid are+41.4mv.
Embodiment 7
A kind of cation carbon black, specific preparation process are as follows：
The first step：Take 1g nano carbon blacks (average grain diameter 45nm), 3ml concentrated ammonia liquors (mass concentration 28%) anhydrous in 40ml
In ethyl alcohol, 1h is sufficiently stirred, is warming up to 50 DEG C after mixing.4ml tetraethyl orthosilicates is taken to be dissolved in 10ml ethanol solutions,
Oscillation is uniformly mixed, then above-mentioned carbon black suspension is added dropwise, and reacts 2h.
Second step：Epoxychloropropane is added in into above-mentioned reaction solution, 50 DEG C are stirred to react 2h, add 12 uncles
Amine stops heating after 50 DEG C of quaternization reaction 2h, obtains cationic carbon black suspension.Tetraethyl orthosilicate, epoxychloropropane, ten
The molar ratio of 24 tertiary amines is 1:2:2.
Third walks：By above-mentioned suspension, centrifuge washing to pH is in neutrality, and redisperse obtains cationic carbon black dispersion liquid, is done
It is dry to obtain cationic carbon black powder.The zeta current potentials of cationic carbon black dispersion liquid are+56.2mv.
Embodiment 8
A kind of cation carbon black, specific preparation process are as follows：
The first step：1g nano carbon blacks (average grain diameter 24nm), 4ml concentrated ammonia liquors (mass concentration 25%) are taken in 40ml80%
In ethanol water, 1h is sufficiently stirred, is warming up to 50 DEG C after mixing.3ml tetraethyl orthosilicates is taken to be dissolved in 8ml absolute ethyl alcohols
Solution, oscillation is uniformly mixed, then above-mentioned carbon black suspension is added dropwise, and reacts 1h.
Second step：Epoxychloropropane is added in into above-mentioned reaction solution, 50 DEG C are stirred to react 2h, add 12 uncles
Amine stops heating after 60 DEG C of quaternization reaction 2h, obtains cationic carbon black suspension.Tetraethyl orthosilicate, epoxychloropropane, ten
The molar ratio of 24 tertiary amines is 1:2:2.
Third walks：By above-mentioned suspension, centrifuge washing to pH is in neutrality, and is redispersed in water and is obtained cationic carbon black dispersion
Liquid is dried to obtain cationic carbon black powder.The zeta current potentials of cationic carbon black dispersion liquid are+37.0mv.
Embodiment 9
A kind of cation carbon black, specific preparation process are as follows：
The first step：1g nano carbon blacks (average grain diameter 24nm), 1ml concentrated ammonia liquors (mass concentration 28%) are taken in 40ml95%
In ethanol water, 1h is sufficiently stirred, is warming up to 50 DEG C after mixing.2ml tetraethyl orthosilicates is taken to be dissolved in the anhydrous second of 10ml
Alcoholic solution, oscillation is uniformly mixed, then above-mentioned carbon black suspension is added dropwise, and reacts 3h.
Second step：Epoxychloropropane is added in into above-mentioned reaction solution, 50 DEG C are stirred to react 2h, add dodeca-tertiary amine amine,
Stop heating after 70 DEG C of quaternization reaction 1h, obtain cationic carbon black suspension.Tetraethyl orthosilicate, epoxychloropropane, 12
The molar ratio of tertiary amine is 1:2:2.
Third walks：By above-mentioned suspension, centrifuge washing to pH is in neutrality, and is redispersed in water and is obtained cationic carbon black dispersion
Liquid is dried to obtain cationic carbon black powder.The zeta current potentials of cationic carbon black dispersion liquid are+48.0mv.
Embodiment 10
A kind of cation carbon black, specific preparation process are as follows：
The first step：Take 1g nano carbon blacks (average grain diameter 24nm), 3ml concentrated ammonia liquors (mass concentration 28%) anhydrous in 40ml
In ethyl alcohol, 1h is sufficiently stirred, is warming up to 50 DEG C after mixing.3ml tetraethyl orthosilicates is taken to be dissolved in 8ml ethanol solutions,
Oscillation is uniformly mixed, then above-mentioned carbon black suspension is added dropwise, and reacts 2h.
Second step：Epoxychloropropane is added in into above-mentioned reaction solution, 50 DEG C are stirred to react 1h, add dodeca-tertiary amine, and 50
Stop heating after DEG C quaternization reaction 1h, obtain cationic carbon black suspension.Tetraethyl orthosilicate, epoxychloropropane, 12 uncles
The molar ratio of amine is 1:1.5:1.5.
Third walks：By above-mentioned suspension, centrifuge washing to pH is in neutrality, and is redispersed in water and is obtained cationic carbon black dispersion
Liquid is dried to obtain cationic carbon black powder.The zeta current potentials of cationic carbon black dispersion liquid are+35.5mv.
Embodiment 11
A kind of cation carbon black, specific preparation process are as follows：
The first step：1g nano carbon blacks (average grain diameter 16nm), 3ml concentrated ammonia liquors (mass concentration 27%) are taken in 40ml95%
In ethanol water, 1h is sufficiently stirred, is warming up to 50 DEG C after mixing.4ml tetraethyl orthosilicates is taken to be dissolved in 10ml95% second
Alcohol solution, oscillation is uniformly mixed, then above-mentioned carbon black suspension is added dropwise, and reacts 2h.
Second step：Epoxychloropropane is added in into above-mentioned reaction solution, 50 DEG C are stirred to react 3h, add 12 uncles
Amine stops heating after 50 DEG C of quaternization reaction 3h, obtains cationic carbon black suspension.Tetraethyl orthosilicate, epoxychloropropane, ten
The molar ratio of 24 tertiary amines is 1:1.1:1.
Third walks：By above-mentioned suspension, centrifuge washing to pH is in neutrality, and redisperse obtains cationic carbon black dispersion liquid, is done
It is dry to obtain cationic carbon black powder.The zeta current potentials of cationic carbon black dispersion liquid are+24.6mv.
Embodiment 12
The first step：1g nano carbon blacks (average grain diameter 24nm), 3ml concentrated ammonia liquors (mass concentration 28%) are taken in 40ml95%
In ethanol water, 1h is sufficiently stirred, is warming up to 50 DEG C after mixing.3ml tetraethyl orthosilicates is taken to be dissolved in 8ml95% ethyl alcohol
Aqueous solution, oscillation is uniformly mixed, then above-mentioned carbon black suspension is added dropwise, and reacts 2h.
Second step：A certain amount of epoxychloropropane is added in into above-mentioned reaction solution, 50 DEG C are stirred to react 2h, add smart ammonia
Acid ethyl ester hydrochloride salt, 50 DEG C are reacted stopping heating after 3h, obtain cationic carbon black suspension.Tetraethyl orthosilicate, epoxy chloropropionate
Alkane, arginine ethyl ester hydrochloride molar ratio be 1:1.1:1.
Third walks：By above-mentioned suspension, centrifuge washing to pH is in neutrality, and is redispersed in water and is adjusted pH value of solution to 4-5, obtains
Cationic carbon black dispersion liquid is dried to obtain cationic carbon black powder.Cationic carbon black dispersion has weak cationic, zeta
Current potential is+23.4mv.
Embodiment 13
The first step：1g nano carbon blacks (average grain diameter 24nm), 3ml concentrated ammonia liquors (mass concentration 28%) are taken in 40ml95%
In ethanol water, 1h is sufficiently stirred, is warming up to 50 DEG C after mixing.3ml tetraethyl orthosilicates is taken to be dissolved in 8ml95% ethyl alcohol
Aqueous solution, oscillation is uniformly mixed, then above-mentioned carbon black suspension is added dropwise, and reacts 2h.
Second step：A certain amount of epoxychloropropane is added in into above-mentioned reaction solution, 50 DEG C are stirred to react 2h, add smart ammonia
Acid, 50 DEG C are reacted stopping heating after 3h, obtain cationic carbon black suspension.It is tetraethyl orthosilicate, epoxychloropropane, arginic
Molar ratio is 1:1.1:1.
Third walks：By above-mentioned suspension, centrifuge washing to pH is in neutrality, and is redispersed in water and is adjusted pH value of solution to 4-5, obtains
Cationic carbon black dispersion liquid is dried to obtain cationic carbon black powder.Cationic carbon black dispersion has weak cationic, zeta
Current potential is+26.8mv.
Embodiment 14
The first step：1g nano carbon blacks (average grain diameter 24nm), 3ml concentrated ammonia liquors (mass concentration 28%) are taken in 40ml95%
In ethanol water, 1h is sufficiently stirred, is warming up to 50 DEG C after mixing.3ml tetraethyl orthosilicates is taken to be dissolved in 8ml95% ethyl alcohol
Aqueous solution, oscillation is uniformly mixed, then above-mentioned carbon black suspension is added dropwise, and reacts 2h.
Second step：A certain amount of epoxychloropropane is added in into above-mentioned reaction solution, 50 DEG C are stirred to react 2h, add smart ammonia
Acid hydrochloride, 50 DEG C are reacted stopping heating after 3h, obtain cationic carbon black suspension.Tetraethyl orthosilicate, epoxychloropropane, essence
The molar ratio of propylhomoserin is 1:1.1:1.
Third walks：By above-mentioned suspension, centrifuge washing to pH is in neutrality, and is redispersed in water and is adjusted pH value of solution to 4-5, obtains
Cationic carbon black dispersion liquid is dried to obtain cationic carbon black powder.Cationic carbon black dispersion has weak cationic, zeta
Current potential is+25.3mv.
Embodiment 15
The first step：1g nano carbon blacks (average grain diameter 24nm), 3ml concentrated ammonia liquors (mass concentration 25%) are taken in 40ml95%
In ethanol water, 1h is sufficiently stirred, is warming up to 50 DEG C after mixing.3ml tetraethyl orthosilicates is taken to be dissolved in 8ml95% ethyl alcohol
Aqueous solution, oscillation is uniformly mixed, then above-mentioned carbon black suspension is added dropwise, and reacts 2h.
Second step：A certain amount of epoxychloropropane is added in into above-mentioned reaction solution, is stirred to react 2h, adds 12
Tertiary amine stops heating after reacting 2h, obtains cationic carbon black suspension.Tetraethyl orthosilicate, epoxychloropropane, 12 uncles
The molar ratio of amine is 1:0.55:0.5.
Third walks：By above-mentioned suspension, centrifuge washing to pH is in neutrality, and redisperse obtains cationic carbon black dispersion liquid, is done
It is dry to obtain cationic carbon black powder.The zeta current potentials of cationic carbon black dispersion liquid are+18.1mv.
Embodiment 16
The first step：1g nano carbon blacks (average grain diameter 24nm), 3ml concentrated ammonia liquors (mass concentration 28%) are taken in 40ml95%
In ethanol water, 1h is sufficiently stirred, is warming up to 50 DEG C after mixing.3ml tetraethyl orthosilicates is taken to be dissolved in 8ml95% ethyl alcohol
Aqueous solution, oscillation is uniformly mixed, then above-mentioned carbon black suspension is added dropwise, and reacts 2h.
Second step：A certain amount of epoxychloropropane is added in into above-mentioned reaction solution, is stirred to react 2h, adds 12 uncles
Amine stops heating after reacting 2h, obtains cationic carbon black suspension.Tetraethyl orthosilicate, epoxychloropropane, dodeca-tertiary amine rub
You are than being 1:1.1:1.
Third walks：By above-mentioned suspension, centrifuge washing to pH is in neutrality, and redisperse obtains cationic carbon black dispersion liquid, is done
It is dry to obtain cationic carbon black powder.The zeta current potentials of cationic carbon black dispersion liquid are+23.5mv.
Embodiment 17
The first step：1g nano carbon blacks (average grain diameter 24nm), 3ml concentrated ammonia liquors (mass concentration 28%) are taken in 40ml95%
In ethanol water, 1h is sufficiently stirred, is warming up to 50 DEG C after mixing.3ml tetraethyl orthosilicates is taken to be dissolved in 8ml95% ethyl alcohol
Aqueous solution, oscillation is uniformly mixed, then above-mentioned carbon black suspension is added dropwise, and reacts 2h.
Second step：A certain amount of epoxychloropropane is added in into above-mentioned reaction solution, is stirred to react 2h, adds 12 uncles
Amine stops heating after reacting 2h, obtains cationic carbon black suspension.Tetraethyl orthosilicate, epoxychloropropane, dodeca-tertiary amine rub
You are than being 1:1.5:1.5.
Third walks：By above-mentioned suspension, centrifuge washing to pH is in neutrality, and redisperse obtains cationic carbon black dispersion liquid, is done
It is dry to obtain cationic carbon black powder.The zeta current potentials of cationic carbon black dispersion liquid are+30.5mv.
Fig. 3 a are the thermogravimetric curve of the cationic carbon black of the embodiment, are cationic carbon blacksurface sun between 120-530 DEG C
The weightlessness of ion component, it can be seen that the accounting of cationic components is bigger.
Embodiment 18
The first step：1g nano carbon blacks (average grain diameter 24nm), 3ml concentrated ammonia liquors (mass concentration 28%) are taken in 40ml95%
In ethanol water, 1h is sufficiently stirred, is warming up to 50 DEG C after mixing.3ml tetraethyl orthosilicates is taken to be dissolved in 8ml95% ethyl alcohol
Aqueous solution, oscillation is uniformly mixed, then above-mentioned carbon black suspension is added dropwise, and reacts 2h.
Second step：A certain amount of epoxychloropropane is added in into above-mentioned reaction solution, is stirred to react 2h, adds 12 uncles
Amine stops heating after reacting 2h, obtains cationic carbon black suspension.Tetraethyl orthosilicate, epoxychloropropane molar ratio be 1:
2.5:2.5。
Third walks：By above-mentioned suspension, centrifuge washing to pH is in neutrality, and redisperse obtains cationic carbon black dispersion liquid, is done
It is dry to obtain cationic carbon black powder.The zeta current potentials of cationic carbon black dispersion liquid are+60.2mv.
Fig. 2 is that the cationic carbon black TEM of the embodiment schemes, it can be seen that cationic average grain diameter is 45nm.
Fig. 3 c are the thermogravimetric curve of the cationic carbon black of the embodiment, are cationic carbon blacksurface sun between 120-530 DEG C
The weightlessness of ion component, it can be seen that the accounting of cationic components is bigger.
The tinctorial property of cationic carbon black and pure carbon black synthesized under Optimizing Technical is compared：
The cationic carbon black of synthesis and unmodified pure carbon black are made into the black pigment of mass fraction 2% respectively, respectively
Wool fabric is coloured.Dye bath is than 1:50, amount of pigment 10%owf., ammonium hydroxide adjust dye liquor pH as 9,45 DEG C of colorings
30min, which is warming up to 80 DEG C, to be continued to colour 30min.Cooling washs drying for several times respectively with tap water, and the soap lye for reusing 5% is washed
Drying is washed, observes color change.
Fig. 4 illustrates that the tinctorial property of cationic carbon black is better than the tinctorial property of unmodified pure carbon black.A is cationic carbon black
The wool of dyeing, B be pure carbon black dyeing wool, wherein A (a-b) be respectively pure wool, the wool coloured by cationic carbon black,
Wool sample after washed several times with water, the wool sample after soaping；B (a-b) is respectively pure wool, the sheep coloured by pure carbon black
Hair, the wool sample after washed several times with water, the wool sample after soaping.
Embodiment 19
The first step：1g nano carbon blacks (average grain diameter 24nm), 3ml concentrated ammonia liquors (mass concentration 28%) are taken in 40ml95%
In ethanol water, 1h is sufficiently stirred, is warming up to 50 DEG C after mixing.3ml tetraethyl orthosilicates is taken to be dissolved in 8ml95% ethyl alcohol
Aqueous solution, oscillation is uniformly mixed, then above-mentioned carbon black suspension is added dropwise, and reacts 2h.
Second step：A certain amount of epoxychloropropane is added in into above-mentioned reaction solution, is stirred to react 2h, adds 12 uncles
Amine stops heating after reacting 2h, obtains cationic carbon black suspension.Tetraethyl orthosilicate, epoxychloropropane molar ratio be 1:
3:3。
Third walks：By above-mentioned suspension, centrifuge washing to pH is in neutrality, and redisperse obtains cationic carbon black dispersion liquid, is done
It is dry to obtain cationic carbon black powder.The zeta current potentials of cationic carbon black dispersion liquid are+46.0mv.
Fig. 3 d are the thermogravimetric curve of the cationic carbon black of the embodiment, are cationic carbon blacksurface sun between 120-530 DEG C
The weightlessness of ion component, it can be seen that the accounting of cationic components is bigger.
More than content is only the better embodiment of the present invention, for those of ordinary skill in the art, according to the present invention
Thought, there will be changes, the content of the present specification should not be construed as to this hair in specific embodiments and applications
Bright limitation.
Claims (10)
1. a kind of preparation method of cation nanometer carbon black, is as follows：
A) a certain amount of nano carbon black, catalyst, solvent are mixed evenly, it is molten that tetraethyl orthosilicate ethyl alcohol is added dropwise in heating
Liquid reacts certain time；
B) to A) in mixed liquor, epoxychloropropane is added in, after keeping thermotonus, add tertiary amine or amino acid and its derivative
Object, temperature control carry out quaternization reaction；
C step B) is taken) the cationic carbon black mixed liquor centrifuge washing that is prepared is in neutrality to pH, is redispersed in water, changed
Property cation carbon black dispersion liquid, it is dry after cationic carbon black.
2. preparation method according to claim 1, it is characterised in that step A) in nano carbon black grain size be 15~50nm；
Step A) in solvent be ethanol water that volumetric concentration is 80~100%.
3. preparation method according to claim 1, it is characterised in that step A) described in tetraethyl orthosilicate ethyl alcohol it is molten
The volume ratio of tetraethyl orthosilicate and ethyl alcohol is 1 in liquid：(2.5~5).
4. preparation method according to claim 1, it is characterised in that step A) described in catalyst for concentrated ammonia liquor, dense ammonia
The mass concentration of water is 25~28%；The mass volume ratio of nano carbon black powder and catalyst is 1：(1~4) g/mL.
5. preparation method according to claim 1, it is characterised in that step A) described in nano carbon black powder and positive silicon
The mass volume ratio of sour tetra-ethyl ester is 1：(2~4) g/mL.
6. preparation method according to claim 1, it is characterised in that step A) in heating be added dropwise tetraethyl orthosilicate ethyl alcohol
The temperature of solution is 40 DEG C~60 DEG C；Reaction certain time is 1~3h.
7. preparation method according to claim 1, it is characterised in that step B) described in tertiary amine be dodeca-tertiary amine, 12
One kind in 14 tertiary amines, 16 tertiary amines or 3- dimethylaminopropylamines；Tertiary amine is 1 with the molar ratio of epoxychloropropane：(1~
1.1)。
8. preparation method according to claim 1, it is characterised in that step B) described in amino acid and its derivative be
One kind of arginine, arginine monohydrochloride or arginine ethyl ester hydrochloride, amino acid and its derivative and epoxychloropropane rub
You are than being 1：(1~1.1).
9. preparation method according to claim 1, it is characterised in that step B) in keep thermotonus 40 DEG C of temperature~
60 DEG C, the reaction time is 1~3h；Quaternization reaction temperature is 50~70 DEG C；Reaction time is 1~3h.
10. according to the method described in claim 1, it is characterized in that step A) in tetraethyl orthosilicate and step B) in epoxy chlorine
The molar ratio of propane is 1：(0.5~3).
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