CN110065960A - A kind of preparation method of the spherical calcium carbonate powder of nanometer - Google Patents
A kind of preparation method of the spherical calcium carbonate powder of nanometer Download PDFInfo
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- C01F11/00—Compounds of calcium, strontium, or barium
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- C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
- C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
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Abstract
The invention discloses a kind of preparation methods of the spherical calcium carbonate powder of nanometer, belong to technical field of nanometer material preparation.Modified microballoon is mixed with sodium hydroxide solution 1:10~1:15 in mass ratio that mass fraction is 10~18%, and carbon dioxide is passed through with the rate of 10~30mL/min into the mixture of microballoon and sodium hydroxide solution, in temperature be 30~40 DEG C, under conditions of revolving speed is 300~400r/min, after being stirred to react 4~6h, filtering, obtain spherical nanometer calcium carbonate blank, under conditions of being 80~90 DEG C in temperature by spherical nanometer calcium carbonate blank after dry 1~2h, and 20~30min is calcined under air atmosphere, obtain the spherical calcium carbonate powder of nanometer.The spherical calcium carbonate powder of nanometer of technical solution of the present invention preparation has the characteristics that preferable pattern and particle size uniformity and easily disperse are good, has broad prospects in the development of nano material preparation technology industry.
Description
Technical field
The invention discloses a kind of preparation methods of the spherical calcium carbonate powder of nanometer, belong to nano material preparation technology neck
Domain.
Background technique
Nanometer calcium carbonate is also known as super fine calcium carbonate.Title, that is, calcium carbonate superfine powder of standard.Nanometer calcium carbonate application most at
Ripe industry is that plastics industry is mainly used in high-grade plastic products.The rheological characteristic that plastic matrix can be improved improves its mouldability.
Have the function of as plastic filler toughened and reinforced, improve the bending strength and bending elastic modulus of plastics, heat distortion temperature and
Dimensional stability, while it is stagnant hot also to assign plastics.Nanometer calcium carbonate is for having embodied excellent dispersibility in ink product
With the transparency and fabulous gloss and excellent ink absorption and high drying property.Nanometer calcium carbonate is made in resin type ink
The advantages that ink filler has stability good, and glossiness is high, does not influence the drying property for printing ink, adaptable.
The production technology of nanometer calcium carbonate mainly uses charring, mainly has interval carbonizatin method, continuous multilevel spray carbonization, surpasses
The production methods such as gravity carbonizatin method.The production technology of powdered whiting is mainly that crushing, ultra-fine grinding, classification and surface are modified.
The production technology of precipitated calcium carbonate is generally using lime stone as raw material, through calcining, digestion, carbonization, separation, drying, classification, packaging etc.
Process prepares winnofil product.It is good with resin compatible due to active nano-calcium carbonate surface oleophilic drainage, it can effectively mention
High or adjusting the rigid of product, toughness, finish and bending strength；Improve processing performance, improves rheological property, the size of product
Stability, heat-resistant stability have the function of filling and enhance, toughening, can replace the expensive filler material in part and help
Ji, reduces the dosage of resin, to reduce production cost, nanometer calcium carbonate is applied in feedstuff industry, can be used as calcium supplement,
Increase feed calcium content.It is used in cosmetics, due to its purity is high, whiteness is good, and granularity is small, titanium dioxide can be partially substituted,
Nanometer calcium carbonate is added in toothpaste can improve its extrusion performance.
The rapid development of the industry such as rubber, plastics, papermaking, coating, ink, product quality and professional standard constantly mention
Height, nanometer calcium carbonate will be widely used in every profession and trade, substitute import similar product.
And the spherical calcium carbonate powder of traditional nanometer is poor there is also pattern and particle size uniformity and dispersibility can not be into one
Therefore the problem of step is promoted the shortcomings that how improving Conventional nano spherical calcium carbonate powder, is developed in the hope of exploring with good
The spherical calcium carbonate powder of nanometer of good comprehensive performance is problem to be solved.
Summary of the invention
The present invention solves the technical problem of: it is directed to the spherical calcium carbonate powder pattern difference of Conventional nano and partial size is equal
The shortcomings that even property and dispersibility can not be promoted further provides a kind of preparation method of spherical calcium carbonate powder of nanometer.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
A kind of preparation method of the spherical calcium carbonate powder of nanometer, it is specific the preparation method comprises the following steps:
(1) pretreatment kaolin is mixed with sodium hydroxide solution 1:2~1:3 in mass ratio, after being stirred to react, filtering must be filtered
Liquid is to get inclined sodium aluminosilicate solution；
(2) by inclined sodium aluminosilicate solution, in dehydrated alcohol, 10:1 is mixed by volume, mixed solution is obtained, by mixed solution and poly- second
Glycol 80:1~100:1 in mass ratio mixing, and after being stirred to react under carbon dioxide atmosphere, it is aged, filters, wash, it is dry,
Obtain white carbon black；
(3) white carbon black is mixed with calcium chloride solution 1:10~1:12 in mass ratio, after being stirred to react, is filtered, it is dry, obtain pre- place
White carbon black is managed, γ-methacryloxypropyl trimethoxy silane is mixed with water 1:20~1:30 in mass ratio, adjusts pH
To 3.5~4.5, it is stirred, obtains treatment fluid, pretreatment white carbon black is mixed with treatment fluid 1:8~1:15 in mass ratio, is stirred
After reaction, filter, it is dry, obtain modified white carbon black；
(4) modified white carbon black is mixed with surfactant 1:20~1:22 in mass ratio, and modified white carbon black quality 0.2 is added
~0.3 times of initiator and 150~200 times of modified white carbon black quality of water after being stirred, obtain modified white carbon black mixture,
Modified white carbon black mixture is mixed with styrene 3:1~4:1 in mass ratio, and under nitrogen atmosphere, after being stirred to react, is obtained pre-
Polystyrene blends are handled, pretreatment polystyrene blends are mixed with methanol 2:1~4:1 in mass ratio, filters, does
It is dry, obtain polystyrene microsphere；
(5) polystyrene microsphere is mixed with water 1:10~1:20 in mass ratio, ultrasonic disperse obtains microballoon dispersion liquid, by microballoon
Dispersion liquid is mixed with chitosan solution 1:1 in mass ratio, and centrifuge separation removes upper liquid, must pre-process microballoon dispersion liquid, will be pre-
Processing microballoon dispersion liquid is mixed with water 1:1~1:2 in mass ratio, and the seaweed of 1~2 times of microballoon dispersion liquid quality of pretreatment is added
Acid sodium solution after being stirred, filters, dry, obtains pre- modified microballoon, by pre- modified microballoon and glutaraldehyde solution in mass ratio 1:
5~1:6 mixing after being stirred to react, is filtered, is washed, dry, obtains modified microballoon blank, by modified microballoon blank and tetrahydrofuran
The mixing of 1:8~1:10 in mass ratio is impregnated, and is filtered, and is washed, dry, obtains modified microballoon；
(6) modified microballoon is mixed with sodium hydroxide solution 1:10~1:15 in mass ratio, and is passed through carbon dioxide, be stirred to react
Afterwards, it filters, dry, calcining obtains the spherical calcium carbonate powder of nanometer.
Step (1) the pretreatment kaolin is to crush kaolin, is sieved, and heating roasting obtains pretreatment kaolin.
Step (2) described polyethylene glycol is the polyethylene glycol that molecular weight is 2000~2500.
Step (4) surfactant is neopelex, lauryl sodium sulfate or fatty alcohol polyoxy second
Any one in alkene ether.
Step (4) initiator is azodiisobutyronitrile, any one in potassium peroxydisulfate or sodium peroxydisulfate.
Step (5) described chitosan solution is the vinegar for being 3~8% by the chitosan of deacetylation 70~95% and mass fraction
Acid solution 1:8~1:10 in mass ratio mixing, obtains chitosan solution.
Step (4) calcination temperature is 100~200 DEG C.
The beneficial effects of the present invention are:
(1) present invention adsorbs calcium ion in the spherical calcium carbonate powder Shi Xianyong white carbon black of preparation nanometer, keeps calcium ion absorption solid
Due to white carbon black surface, so as to make calcium ion is quantitative in product preparation process to be fixed in the core of modified microballoon, and
Once having calcium carbonate crystal to be formed can be fixed by effective absorption, further growing up and reuniting for calcium carbonate crystal is avoided, is had
Effect controls the partial size after the spherical calcium carbonate powder of nanometer is formed and appearance structure, to make product with more uniform partial size point
Cloth；
(2) secondly technical solution of the present invention carries out the white carbon black after absorption calcium ion with polystyrene in product preparation process
Cladding avoids having adsorbed the mutual reunion of white carbon black after calcium ion, and in subsequent processing in polystyrene surface
The compound coating layer of chitosan and sodium alginate is formed, while removing polystyrene layer, on the one hand, chitosan and sodium alginate are multiple
The constituent of chitosan closed in clad can be after polystyrene removal, the fixed free calcium when silica is dissolved in lye
Ion, and the calcium carbonate for deposition provides protective layer, prevents the reunion of calcium carbonate, and then improve the particle size uniformity of product, separately
On the one hand, the composite protection layer of chitosan and sodium alginate can be removed in product calcination process, and generate gas, be prevented
Product is reunited again in calcination process, and then improves the dispersibility of product；
(3) technical solution of the present invention is by introducing many kinds of substance such as white carbon black, polystyrene, chitosan and sodium alginate entire
It is realized in the preparation and reaction process of product to the Effective Regulation of calcium carbonate crystal and pattern, and above-mentioned substance is finally all can quilt
Removal can't cause adverse effect that can leave hollow kernel after removal, protect product to the purity of calcium carbonate crystal
Hold good spherical structure.
Specific embodiment
Kaolin is crushed, 150 meshes is crossed, obtains refinement kaolin, will refine kaolin in temperature be 950~960 DEG C
Under the conditions of roast 1~2h after, obtain pretreatment kaolin；The sodium hydroxide that kaolin and mass fraction are 20~22% will be pre-processed
Solution 1:2~1:3 in mass ratio mixing is 90~95 DEG C in temperature, and under conditions of revolving speed is 200~250r/min, stirring is anti-
After answering 60~70min, filtering obtains filtrate to get inclined sodium aluminosilicate solution；Inclined sodium aluminosilicate solution is pressed into volume in dehydrated alcohol
Than 10:1 mix, in temperature be 40~60 DEG C, revolving speed be 300~400r/min under conditions of, after being stirred 20~30min,
Mixed solution is obtained, mixed solution and polyethylene glycol 80:1~100:1 in mass ratio are mixed in three-necked flask, and is burnt to three mouthfuls
Carbon dioxide is passed through with the rate of 18~30mL/min in bottle, is 90~95 DEG C in temperature, revolving speed is the item of 200~280r/min
Under part, after being stirred to react 90~100min, and it is aged 90~120min under conditions of being 30~50 DEG C in temperature, filtering must filter
Cake after filter cake is washed with deionized 8~10 times, and dries 1~2h under conditions of being 80~100 DEG C in temperature, obtains hard charcoal
It is black；Calcium chloride solution 1:10~1:12 in mass ratio that white carbon black and mass fraction are 18~25% mix, in temperature for 40~
60 DEG C, under conditions of revolving speed is 300~350r/min, after being stirred to react 1~3h, filtering must pre-process white carbon black blank, will be pre-
Under conditions of processing white carbon black blank is 60~80 DEG C in temperature after dry 1~2h, pretreatment white carbon black is obtained, by γ-methyl-prop
Alkene acryloxypropylethoxysilane trimethoxy silane and water 1:20~1:30 in mass ratio are mixed in beaker, and with mass fraction for 10~
15% acetic acid adjusts the pH to 3.5~4.5 of material in beaker, is 30~60 DEG C in temperature, revolving speed is 300~400r/min's
Under the conditions of, after being stirred 30~40min, treatment fluid is obtained, pretreatment white carbon black is mixed with treatment fluid 1:8~1:15 in mass ratio
It closes, is 30~40 DEG C in temperature, under conditions of revolving speed is 300~400r/min, after being stirred to react 30~60min, filtering must change
Property white carbon black blank, under conditions of being 120~130 DEG C in temperature by modified white carbon black blank after dry 40~60min, obtain modification
White carbon black；Modified white carbon black is mixed with surfactant 1:20~1:22 in mass ratio, and living to modified white carbon black and surface
Property agent mixture in be added 0.2~0.3 times of modified white carbon black quality initiator and 150~200 times of modified white carbon black quality
Water, in temperature be 30~45 DEG C, revolving speed be 300~400r/min under conditions of, after being stirred 30~50min, obtain modification
Modified white carbon black mixture and styrene 3:1~4:1 in mass ratio are mixed in four-hole boiling flask by white carbon black mixture, and to
Nitrogen is passed through with the rate of 20~30mL/min in four-hole boiling flask, is 70~75 DEG C in temperature, revolving speed is 300~400r/min's
Under the conditions of, after being stirred to react after 1~3h, pretreatment polystyrene blends are obtained, by pretreatment polystyrene blends and methanol
The mixing of 2:1~4:1 in mass ratio is 30~45 DEG C in temperature, under conditions of revolving speed is 280~350r/min, is stirred 40
After~60min, filtering obtains polystyrene microsphere blank, by polystyrene microsphere blank under conditions of temperature is 70~80 DEG C
After dry 1~2h, polystyrene microsphere is obtained；Polystyrene microsphere is mixed with water 1:10~1:20 in mass ratio, is in frequency
Under conditions of 45~55kHz after 30~40min of ultrasonic disperse, microballoon dispersion liquid is obtained, microballoon dispersion liquid is pressed with chitosan solution
Mass ratio 1:1 mixing is 30~40 DEG C in temperature, under conditions of revolving speed is 300~400r/min, is stirred 30~40min
Afterwards, and under conditions of revolving speed is 2000~300r/min it is centrifugated 10~15min, removes upper liquid, obtains pretreatment microballoon
Dispersion liquid mixes with water 1:1~1:2 in mass ratio pretreatment microballoon dispersion liquid, and to pre-processing microballoon dispersion liquid and water
The sodium alginate soln that the mass fraction of 1~2 times of microballoon dispersion liquid quality of pretreatment is 10~15%, Yu Wen are added in mixture
Degree is 30~50 DEG C, and under conditions of revolving speed is 300~400r/min, after being stirred 40~60min, it is micro- to obtain pre- modification for filtering
Ball blank obtains pre- modified microballoon under conditions of being 80~90 DEG C in temperature by pre- modified microballoon blank after dry 1~2h, will be pre-
Modified microballoon is mixed with glutaraldehyde solution 1:5~1:6 in mass ratio that mass fraction is 2~8%, is 30~40 DEG C in temperature, is turned
Under conditions of speed is 300~350r/min, after being stirred to react 2~3h, filtering obtains filter residue, filter residue is washed with deionized 5~
After 8 times, and 2~3h is dried under conditions of being 80~90 DEG C in temperature, obtains modified microballoon blank, it will modified microballoon blank and tetrahydro
Furans 1:8~1:10 in mass ratio mixing, after impregnating 2~3h under room temperature, filtering obtains pretreatment modification microballoon blank,
After pretreatment modification microballoon blank is washed with water 4~8 times, dry 1~2h under conditions of being 80~90 DEG C in temperature obtains modification
Microballoon；Modified microballoon is mixed with mass fraction for 10~18% sodium hydroxide solution 1:10~1:15 in mass ratio, and to micro-
Carbon dioxide is passed through with the rate of 10~30mL/min in the mixture of ball and sodium hydroxide solution, in temperature be 30~40 DEG C,
Under conditions of revolving speed is 300~400r/min, after being stirred to react 4~6h, filtering obtains the spherical calcium carbonate powder blank of nanometer,
Under conditions of being 80~90 DEG C in temperature by the spherical calcium carbonate powder blank of nanometer after dry 1~2h, and under air atmosphere
20~30min is calcined, the spherical calcium carbonate powder of nanometer is obtained.The polyethylene glycol is the poly- second two that molecular weight is 2000~2500
Alcohol.The surfactant is neopelex, any one in lauryl sodium sulfate or fatty alcohol polyoxyethylene ether
Kind.The initiator is azodiisobutyronitrile, any one in potassium peroxydisulfate or sodium peroxydisulfate.The chitosan solution is that will take off
The chitosan of acetyl degree 70~95% is mixed with acetum 1:8~1:10 in mass ratio that mass fraction is 3~8%, and it is poly- to obtain shell
Sugar juice.The calcination temperature is 100~200 DEG C.
Example 1
Kaolin is crushed, 150 meshes is crossed, obtains refinement kaolin, is roasted under conditions of being 960 DEG C in temperature by refinement kaolin
After 2h, pretreatment kaolin is obtained；The sodium hydroxide solution 1:3 in mass ratio that kaolin is 22% with mass fraction will be pre-processed to mix
It closes, is 95 DEG C in temperature, under conditions of revolving speed is 250r/min, after being stirred to react 70min, filtering obtains filtrate to get inclined sial
Acid sodium solution；By inclined sodium aluminosilicate solution in dehydrated alcohol by volume 10:1 mix, in temperature be 60 DEG C, revolving speed 400r/
Under conditions of min, after being stirred 30min, mixed solution is obtained, mixed solution is mixed with polyethylene glycol 100:1 in mass ratio
Carbon dioxide is passed through with the rate of 30mL/min in three-necked flask, and into three-necked flask, is 95 DEG C in temperature, revolving speed is
Under conditions of 280r/min, after being stirred to react 100min, and it is aged 120min under conditions of being 50 DEG C in temperature, filters, must filter
Cake after filter cake is washed with deionized 10 times, and dries 2h under conditions of being 100 DEG C in temperature, obtains white carbon black；By white carbon black
The calcium chloride solution 1:12 in mass ratio for being 25% with mass fraction is mixed, and is 60 DEG C in temperature, revolving speed is the condition of 350r/min
Under, after being stirred to react 3h, filtering must pre-process white carbon black blank, the condition for being 80 DEG C in temperature by pretreatment white carbon black blank
After lower dry 2h, pretreatment white carbon black is obtained, by γ-methacryloxypropyl trimethoxy silane and water 1:30 in mass ratio
Be mixed in beaker, and with mass fraction be 15% acetic acid adjust beaker in material pH to 4.5, in temperature be 60 DEG C, revolving speed
Under conditions of 400r/min, after being stirred 40min, treatment fluid is obtained, white carbon black and treatment fluid in mass ratio 1 will be pre-processed:
15 mixing are 40 DEG C in temperature, and under conditions of revolving speed is 400r/min, after being stirred to react 60min, filtering obtains modified white carbon black
Blank obtains modified white carbon black under conditions of being 130 DEG C in temperature by modified white carbon black blank after dry 60min；It will modified hard charcoal
It is black to be mixed with surfactant 1:22 in mass ratio, and addition modification is white into the mixture of modified white carbon black and surfactant
The initiator and 200 times of modified white carbon black quality of water that 0.3 times of carbon black mass are 45 DEG C in temperature, and revolving speed is 400r/min's
Under the conditions of, after being stirred 50min, modified white carbon black mixture is obtained, in mass ratio with styrene by modified white carbon black mixture
4:1 is mixed in four-hole boiling flask, and is passed through nitrogen into four-hole boiling flask with the rate of 30mL/min, in temperature be 75 DEG C, revolving speed
Under conditions of 400r/min, after being stirred to react rear 3h, pretreatment polystyrene blends are obtained, pretreatment polystyrene is mixed
Object is mixed with methanol 4:1 in mass ratio, in temperature be 45 DEG C, revolving speed be 350r/min under conditions of, after being stirred 60min,
Filtering, obtains polystyrene microsphere blank, under conditions of being 80 DEG C in temperature by polystyrene microsphere blank after dry 2h, obtains polyphenyl
Ethylene microballoon；Polystyrene microsphere is mixed with water 1:20 in mass ratio, the ultrasonic disperse under conditions of frequency is 55kHz
After 40min, microballoon dispersion liquid is obtained, microballoon dispersion liquid is mixed with chitosan solution 1:1 in mass ratio, is 40 DEG C in temperature, turns
Under conditions of speed is 400r/min, after being stirred 40min, and it is centrifugated 15min under conditions of revolving speed is 300r/min,
Upper liquid is removed, microballoon dispersion liquid must be pre-processed, pretreatment microballoon dispersion liquid is mixed with water 1:2 in mass ratio, and locates to pre-
Manage the alginic acid for being added that the mass fraction of 2 times of microballoon dispersion liquid quality of pretreatment is 15% in the mixture of microballoon dispersion liquid and water
Sodium solution is 50 DEG C in temperature, and under conditions of revolving speed is 400r/min, after being stirred 60min, filtering obtains pre- modified microballoon
Pre- modified microballoon blank after dry 2h, is obtained pre- modified microballoon under the conditions of at a temperature of 90 °C by blank, by pre- modified microballoon with
Mass fraction be 8% glutaraldehyde solution 1:6 in mass ratio mix, in temperature be 40 DEG C, revolving speed be 350r/min under conditions of,
After being stirred to react 3h, filtering obtains filter residue, after filter residue is washed with deionized 8 times, and it is dry under the conditions of at a temperature of 90 °C
3h obtains modified microballoon blank, and modified microballoon blank is mixed with tetrahydrofuran 1:10 in mass ratio, in impregnating 3h under room temperature
Afterwards, it filters, pretreatment modification microballoon blank is obtained, after pretreatment modification microballoon blank is washed with water 8 times, at a temperature of 90 °C
Under the conditions of dry 2h, obtain modified microballoon；The sodium hydroxide solution 1:15 in mass ratio that modified microballoon is 18% with mass fraction is mixed
Close, and carbon dioxide be passed through with the rate of 30mL/min into the mixture of microballoon and sodium hydroxide solution, in temperature be 40 DEG C,
Under conditions of revolving speed is 400r/min, after being stirred to react 6h, filtering obtains the spherical calcium carbonate powder blank of nanometer, by nanometer class
After spherical calcium carbonate powder blank dries 2h under the conditions of at a temperature of 90 °C, and 30min is calcined under air atmosphere, obtains nanometer
Spherical calcium carbonate powder.The polyethylene glycol is the polyethylene glycol that molecular weight is 2500.The surfactant is dodecane
Base benzene sulfonic acid sodium salt.The initiator is azodiisobutyronitrile.The chitosan solution is by the chitosan and matter of deacetylation 95%
It measures the acetum 1:10 in mass ratio that score is 8% to mix, obtains chitosan solution.The calcination temperature is 200 DEG C.
Example 2
Nano silica is mixed with surfactant 1:22 in mass ratio, and to nano silica and surfactant
0.3 times of nano silica quality of initiator and 200 times of nano silica quality of water are added in mixture, is in temperature
45 DEG C, under conditions of revolving speed is 400r/min, after being stirred 50min, nano silica mixture is obtained, by nanometer titanium dioxide
Silicon mixture and styrene 4:1 in mass ratio are mixed in four-hole boiling flask, and logical with the rate of 30mL/min into four-hole boiling flask
Enter nitrogen, is 75 DEG C in temperature, under conditions of revolving speed is 400r/min, after being stirred to react rear 3h, it is mixed that polystyrene must be pre-processed
Close object, pretreatment polystyrene blends mixed with methanol 4:1 in mass ratio, in temperature be 45 DEG C, revolving speed 350r/min
Under conditions of, after being stirred 60min, filtering, obtain polystyrene microsphere blank, by polystyrene microsphere blank in temperature be 80
Under conditions of DEG C after dry 2h, polystyrene microsphere is obtained；Polystyrene microsphere is mixed with water 1:20 in mass ratio, is in frequency
Under conditions of 55kHz after ultrasonic disperse 40min, microballoon dispersion liquid is obtained, by microballoon dispersion liquid and chitosan solution 1:1 in mass ratio
Mixing, in temperature be 40 DEG C, under conditions of revolving speed is 400r/min, after being stirred 40min, and in revolving speed be 300r/min
Under the conditions of be centrifugated 15min, remove upper liquid, must pre-process microballoon dispersion liquid, will pretreatment microballoon dispersion liquid and water by matter
Amount is mixed than 1:2, and the matter of 2 times of microballoon dispersion liquid quality of pretreatment is added into the mixture of pretreatment microballoon dispersion liquid and water
The sodium alginate soln that score is 15% is measured, is 50 DEG C in temperature, under conditions of revolving speed is 400r/min, is stirred 60min
Afterwards, it filters, obtains pre- modified microballoon blank, pre- modified microballoon blank after dry 2h, is obtained into pre- change under the conditions of at a temperature of 90 °C
Property microballoon, the glutaraldehyde solution 1:6 in mass ratio that pre- modified microballoon and mass fraction are 8% mix, in temperature be 40 DEG C, turn
Under conditions of speed is 350r/min, after being stirred to react 3h, filtering obtains filter residue, after filter residue is washed with deionized 8 times, and in
Dry 3h, obtains modified microballoon blank under the conditions of at a temperature of 90 °C, by modified microballoon blank and tetrahydrofuran 1:10 in mass ratio
Mixing, after impregnating 3h under room temperature, filtering obtains pretreatment modification microballoon blank, by pretreatment modification microballoon blank water
After washing 8 times, dry 2h, obtains modified microballoon under the conditions of at a temperature of 90 °C；The hydrogen for being 18% by modified microballoon and mass fraction
Sodium hydroxide solution 1:15 in mass ratio mixing, and it is logical with the rate of 30mL/min into the mixture of microballoon and sodium hydroxide solution
Enter carbon dioxide, is 40 DEG C in temperature, under conditions of revolving speed is 400r/min, after being stirred to react 6h, it is spherical to obtain nanometer for filtering
Calcium carbonate powder blank, by the spherical calcium carbonate powder blank of nanometer under the conditions of at a temperature of 90 °C after dry 2h, and in sky
Atmosphere encloses lower calcining 30min, obtains the spherical calcium carbonate powder of nanometer.The surfactant is neopelex.Institute
Stating initiator is azodiisobutyronitrile.It is 8% that the chitosan solution, which is by the chitosan of deacetylation 95% and mass fraction,
Acetum 1:10 in mass ratio mixing, obtains chitosan solution.The calcination temperature is 200 DEG C.
Example 3
Kaolin is crushed, 150 meshes is crossed, obtains refinement kaolin, is roasted under conditions of being 960 DEG C in temperature by refinement kaolin
After 2h, pretreatment kaolin is obtained；The sodium hydroxide solution 1:3 in mass ratio that kaolin is 22% with mass fraction will be pre-processed to mix
It closes, is 95 DEG C in temperature, under conditions of revolving speed is 250r/min, after being stirred to react 70min, filtering obtains filtrate to get inclined sial
Acid sodium solution；By inclined sodium aluminosilicate solution in dehydrated alcohol by volume 10:1 mix, in temperature be 60 DEG C, revolving speed 400r/
Under conditions of min, after being stirred 30min, mixed solution is obtained, mixed solution is mixed with polyethylene glycol 100:1 in mass ratio
Carbon dioxide is passed through with the rate of 30mL/min in three-necked flask, and into three-necked flask, is 95 DEG C in temperature, revolving speed is
Under conditions of 280r/min, after being stirred to react 100min, and it is aged 120min under conditions of being 50 DEG C in temperature, filters, must filter
Cake after filter cake is washed with deionized 10 times, and dries 2h under conditions of being 100 DEG C in temperature, obtains white carbon black；By white carbon black
The calcium chloride solution 1:12 in mass ratio for being 25% with mass fraction is mixed, and is 60 DEG C in temperature, revolving speed is the condition of 350r/min
Under, after being stirred to react 3h, filtering must pre-process white carbon black blank, the condition for being 80 DEG C in temperature by pretreatment white carbon black blank
After lower dry 2h, pretreatment white carbon black is obtained, by γ-methacryloxypropyl trimethoxy silane and water 1:30 in mass ratio
Be mixed in beaker, and with mass fraction be 15% acetic acid adjust beaker in material pH to 4.5, in temperature be 60 DEG C, revolving speed
Under conditions of 400r/min, after being stirred 40min, treatment fluid is obtained, white carbon black and treatment fluid in mass ratio 1 will be pre-processed:
15 mixing are 40 DEG C in temperature, and under conditions of revolving speed is 400r/min, after being stirred to react 60min, filtering obtains modified white carbon black
Blank obtains modified white carbon black under conditions of being 130 DEG C in temperature by modified white carbon black blank after dry 60min；It will modified hard charcoal
It is black to be mixed with surfactant 1:22 in mass ratio, and addition modification is white into the mixture of modified white carbon black and surfactant
The initiator and 200 times of modified white carbon black quality of water that 0.3 times of carbon black mass are 45 DEG C in temperature, and revolving speed is 400r/min's
Under the conditions of, after being stirred 50min, modified white carbon black mixture is obtained, in mass ratio with styrene by modified white carbon black mixture
4:1 is mixed in four-hole boiling flask, and is passed through nitrogen into four-hole boiling flask with the rate of 30mL/min, in temperature be 75 DEG C, revolving speed
Under conditions of 400r/min, after being stirred to react rear 3h, pretreatment polystyrene blends are obtained, pretreatment polystyrene is mixed
Object is mixed with methanol 4:1 in mass ratio, in temperature be 45 DEG C, revolving speed be 350r/min under conditions of, after being stirred 60min,
Filtering, obtains polystyrene microsphere blank, under conditions of being 80 DEG C in temperature by polystyrene microsphere blank after dry 2h, obtains polyphenyl
Ethylene microballoon；Polystyrene microsphere is mixed with water 1:20 in mass ratio, the ultrasonic disperse under conditions of frequency is 55kHz
After 40min, obtain microballoon dispersion liquid, by microballoon dispersion liquid in temperature be 40 DEG C, revolving speed be 400r/min under conditions of, be stirred
After 40min, and it is centrifugated 15min under conditions of revolving speed is 300r/min, removes upper liquid, microballoon dispersion must be pre-processed
Pretreatment microballoon dispersion liquid is mixed with water 1:2 in mass ratio, and added into the mixture of pretreatment microballoon dispersion liquid and water by liquid
Enter to pre-process the sodium alginate soln that the mass fraction of 2 times of microballoon dispersion liquid quality is 15%, is 50 DEG C in temperature, revolving speed is
Under conditions of 400r/min, after being stirred 60min, filtering obtains pre- modified microballoon blank, by pre- modified microballoon blank in temperature
Under conditions of being 90 DEG C after dry 2h, pre- modified microballoon is obtained, the glutaraldehyde solution that pre- modified microballoon is 8% with mass fraction is pressed
Mass ratio 1:6 mixing is 40 DEG C in temperature, and under conditions of revolving speed is 350r/min, after being stirred to react 3h, filtering obtains filter residue, will
After filter residue is washed with deionized 8 times, and the dry 3h under the conditions of at a temperature of 90 °C, modified microballoon blank is obtained, modification is micro-
Ball blank is mixed with tetrahydrofuran 1:10 in mass ratio, and after impregnating 3h under room temperature, filtering obtains pretreatment modification microballoon base
Material, after pretreatment modification microballoon blank is washed with water 8 times, dry 2h, obtains modified microballoon under the conditions of at a temperature of 90 °C；It will
Modified microballoon is mixed with mass fraction for 18% sodium hydroxide solution 1:15 in mass ratio, and to microballoon and sodium hydroxide solution
Mixture in carbon dioxide is passed through with the rate of 30mL/min, be 40 DEG C in temperature, under conditions of revolving speed is 400r/min, stir
After mixing reaction 6h, filtering obtains the spherical calcium carbonate powder blank of nanometer, is in temperature by the spherical calcium carbonate powder blank of nanometer
Under conditions of 90 DEG C after dry 2h, and 30min is calcined under air atmosphere, obtains the spherical calcium carbonate powder of nanometer.The poly- second
Glycol is the polyethylene glycol that molecular weight is 2500.The surfactant is neopelex.The initiator is even
Nitrogen bis-isobutyronitrile.The calcination temperature is 200 DEG C.
Example 4
Kaolin is crushed, 150 meshes is crossed, obtains refinement kaolin, is roasted under conditions of being 960 DEG C in temperature by refinement kaolin
After 2h, pretreatment kaolin is obtained；The sodium hydroxide solution 1:3 in mass ratio that kaolin is 22% with mass fraction will be pre-processed to mix
It closes, is 95 DEG C in temperature, under conditions of revolving speed is 250r/min, after being stirred to react 70min, filtering obtains filtrate to get inclined sial
Acid sodium solution；By inclined sodium aluminosilicate solution in dehydrated alcohol by volume 10:1 mix, in temperature be 60 DEG C, revolving speed 400r/
Under conditions of min, after being stirred 30min, mixed solution is obtained, mixed solution is mixed with polyethylene glycol 100:1 in mass ratio
Carbon dioxide is passed through with the rate of 30mL/min in three-necked flask, and into three-necked flask, is 95 DEG C in temperature, revolving speed is
Under conditions of 280r/min, after being stirred to react 100min, and it is aged 120min under conditions of being 50 DEG C in temperature, filters, must filter
Cake after filter cake is washed with deionized 10 times, and dries 2h under conditions of being 100 DEG C in temperature, obtains white carbon black；By white carbon black
The calcium chloride solution 1:12 in mass ratio for being 25% with mass fraction is mixed, and is 60 DEG C in temperature, revolving speed is the condition of 350r/min
Under, after being stirred to react 3h, filtering must pre-process white carbon black blank, the condition for being 80 DEG C in temperature by pretreatment white carbon black blank
After lower dry 2h, pretreatment white carbon black is obtained, by γ-methacryloxypropyl trimethoxy silane and water 1:30 in mass ratio
Be mixed in beaker, and with mass fraction be 15% acetic acid adjust beaker in material pH to 4.5, in temperature be 60 DEG C, revolving speed
Under conditions of 400r/min, after being stirred 40min, treatment fluid is obtained, white carbon black and treatment fluid in mass ratio 1 will be pre-processed:
15 mixing are 40 DEG C in temperature, and under conditions of revolving speed is 400r/min, after being stirred to react 60min, filtering obtains modified white carbon black
Blank obtains modified white carbon black under conditions of being 130 DEG C in temperature by modified white carbon black blank after dry 60min；It will modified hard charcoal
It is black to be mixed with surfactant 1:22 in mass ratio, and addition modification is white into the mixture of modified white carbon black and surfactant
The initiator and 200 times of modified white carbon black quality of water that 0.3 times of carbon black mass are 45 DEG C in temperature, and revolving speed is 400r/min's
Under the conditions of, after being stirred 50min, modified white carbon black mixture is obtained, in mass ratio with styrene by modified white carbon black mixture
4:1 is mixed in four-hole boiling flask, and is passed through nitrogen into four-hole boiling flask with the rate of 30mL/min, in temperature be 75 DEG C, revolving speed
Under conditions of 400r/min, after being stirred to react rear 3h, pretreatment polystyrene blends are obtained, pretreatment polystyrene is mixed
Object is mixed with methanol 4:1 in mass ratio, in temperature be 45 DEG C, revolving speed be 350r/min under conditions of, after being stirred 60min,
Filtering, obtains polystyrene microsphere blank, under conditions of being 80 DEG C in temperature by polystyrene microsphere blank after dry 2h, obtains polyphenyl
Ethylene microballoon；Polystyrene microsphere is mixed with water 1:20 in mass ratio, the ultrasonic disperse under conditions of frequency is 55kHz
After 40min, microballoon dispersion liquid is obtained, microballoon dispersion liquid is mixed with chitosan solution 1:1 in mass ratio, is 40 DEG C in temperature, turns
Under conditions of speed is 400r/min, after being stirred 40min, and it is centrifugated 15min under conditions of revolving speed is 300r/min,
Upper liquid is removed, microballoon dispersion liquid must be pre-processed, pretreatment microballoon dispersion liquid is mixed with water 1:2 in mass ratio, is in temperature
50 DEG C, under conditions of revolving speed is 400r/min, after being stirred 60min, filtering obtains pre- modified microballoon blank, and pre- modification is micro-
Ball blank after dry 2h, obtains pre- modified microballoon under the conditions of at a temperature of 90 °C, is 8% by pre- modified microballoon and mass fraction
Glutaraldehyde solution 1:6 in mass ratio mixing, in temperature be 40 DEG C, revolving speed be 350r/min under conditions of, after being stirred to react 3h, mistake
Filter, obtains filter residue, after filter residue is washed with deionized 8 times, and the dry 3h under the conditions of at a temperature of 90 °C, obtain modified microballoon base
Material mixes modified microballoon blank with tetrahydrofuran 1:10 in mass ratio, and after impregnating 3h under room temperature, filtering obtains pre- place
Modified microballoon blank is managed, after pretreatment modification microballoon blank is washed with water 8 times, the dry 2h under the conditions of at a temperature of 90 °C,
Microballoon must be modified；Modified microballoon is mixed with the sodium hydroxide solution 1:15 in mass ratio that mass fraction is 18%, and to microballoon and
Carbon dioxide is passed through with the rate of 30mL/min in the mixture of sodium hydroxide solution, in temperature be 40 DEG C, revolving speed 400r/
Under conditions of min, after being stirred to react 6h, filtering obtains the spherical calcium carbonate powder blank of nanometer, by the spherical Paris white of nanometer
After body blank dries 2h under the conditions of at a temperature of 90 °C, and 30min is calcined under air atmosphere, obtains the spherical calcium carbonate of nanometer
Powder.The polyethylene glycol is the polyethylene glycol that molecular weight is 2500.The surfactant is neopelex.Institute
Stating initiator is azodiisobutyronitrile.It is 8% that the chitosan solution, which is by the chitosan of deacetylation 95% and mass fraction,
Acetum 1:10 in mass ratio mixing, obtains chitosan solution.The calcination temperature is 200 DEG C.
Comparative example: the spherical calcium carbonate powder of nanometer of Wuxi material production Co., Ltd production.
Example 1 to the spherical calcium carbonate powder of the resulting nanometer of example 4 and comparative example product are subjected to performance detection, specifically
Detection method is as follows:
1. particle diameter: using D/ma-rB type rotating anode target polycrystal X ray diffractometer measurement nanoparticle crystal structure and
Average Particle Diameters calculate the average grain diameter of nanoparticle according to the crystallite dimension calculation formula of Scherrer.
Shape characteristic: with the pattern of Hitachi's H-600 transmission electron microscope observation characterization nanoparticle.
Specific testing result is as shown in table 1:
1 nanometer of table spherical calcium carbonate powder performance test results
| Detection project | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example |
| Average grain diameter (nm) | 9.2~9.6 | 9.6~13.2 | 9.5~23.4 | 9.2~25.3 | 9.8~33.6 |
| Shape characteristic | It is spherical | Near-spherical | It is irregular | It is irregular | Near-spherical |
By 1 testing result of table it is found that the spherical calcium carbonate powder of nanometer of technical solution of the present invention preparation has preferable pattern
And particle size uniformity and the good feature of easily disperse, it has broad prospects in the development of nano material preparation technology industry.
Claims (7)
1. a kind of preparation method of the spherical calcium carbonate powder of nanometer, which is characterized in that it is specific the preparation method comprises the following steps:
(1) pretreatment kaolin is mixed with sodium hydroxide solution 1:2~1:3 in mass ratio, after being stirred to react, filtering must be filtered
Liquid is to get inclined sodium aluminosilicate solution；
(2) by inclined sodium aluminosilicate solution, in dehydrated alcohol, 10:1 is mixed by volume, mixed solution is obtained, by mixed solution and poly- second
Glycol 80:1~100:1 in mass ratio mixing, and after being stirred to react under carbon dioxide atmosphere, it is aged, filters, wash, it is dry,
Obtain white carbon black；
(3) white carbon black is mixed with calcium chloride solution 1:10~1:12 in mass ratio, after being stirred to react, is filtered, it is dry, obtain pre- place
White carbon black is managed, γ-methacryloxypropyl trimethoxy silane is mixed with water 1:20~1:30 in mass ratio, adjusts pH
To 3.5~4.5, it is stirred, obtains treatment fluid, pretreatment white carbon black is mixed with treatment fluid 1:8~1:15 in mass ratio, is stirred
After reaction, filter, it is dry, obtain modified white carbon black；
(4) modified white carbon black is mixed with surfactant 1:20~1:22 in mass ratio, and modified white carbon black quality 0.2 is added
~0.3 times of initiator and 150~200 times of modified white carbon black quality of water after being stirred, obtain modified white carbon black mixture,
Modified white carbon black mixture is mixed with styrene 3:1~4:1 in mass ratio, and under nitrogen atmosphere, after being stirred to react, is obtained pre-
Polystyrene blends are handled, pretreatment polystyrene blends are mixed with methanol 2:1~4:1 in mass ratio, filters, does
It is dry, obtain polystyrene microsphere；
(5) polystyrene microsphere is mixed with water 1:10~1:20 in mass ratio, ultrasonic disperse obtains microballoon dispersion liquid, by microballoon
Dispersion liquid is mixed with chitosan solution 1:1 in mass ratio, and centrifuge separation removes upper liquid, must pre-process microballoon dispersion liquid, will be pre-
Processing microballoon dispersion liquid is mixed with water 1:1~1:2 in mass ratio, and the seaweed of 1~2 times of microballoon dispersion liquid quality of pretreatment is added
Acid sodium solution after being stirred, filters, dry, obtains pre- modified microballoon, by pre- modified microballoon and glutaraldehyde solution in mass ratio 1:
5~1:6 mixing after being stirred to react, is filtered, is washed, dry, obtains modified microballoon blank, by modified microballoon blank and tetrahydrofuran
The mixing of 1:8~1:10 in mass ratio is impregnated, and is filtered, and is washed, dry, obtains modified microballoon；
(6) modified microballoon is mixed with sodium hydroxide solution 1:10~1:15 in mass ratio, and is passed through carbon dioxide, be stirred to react
Afterwards, it filters, dry, calcining obtains the spherical calcium carbonate powder of nanometer.
2. a kind of preparation method of the spherical calcium carbonate powder of nanometer according to claim 1, it is characterised in that: step
(1) the pretreatment kaolin is to crush kaolin, is sieved, and heating roasting obtains pretreatment kaolin.
3. a kind of preparation method of the spherical calcium carbonate powder of nanometer according to claim 1, it is characterised in that: step
(2) polyethylene glycol is the polyethylene glycol that molecular weight is 2000~2500.
4. a kind of preparation method of the spherical calcium carbonate powder of nanometer according to claim 1, it is characterised in that: step
(4) surfactant is neopelex, any one in lauryl sodium sulfate or fatty alcohol polyoxyethylene ether
Kind.
5. a kind of preparation method of the spherical calcium carbonate powder of nanometer according to claim 1, it is characterised in that: step
(4) initiator is azodiisobutyronitrile, any one in potassium peroxydisulfate or sodium peroxydisulfate.
6. a kind of preparation method of the spherical calcium carbonate powder of nanometer according to claim 1, it is characterised in that: step
(5) chitosan solution be by the chitosan of deacetylation 70~95% and mass fraction be 3~8% acetum by quality
It is mixed than 1:8~1:10, obtains chitosan solution.
7. a kind of preparation method of the spherical calcium carbonate powder of nanometer according to claim 1, it is characterised in that: step
(4) calcination temperature is 100~200 DEG C.
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