CN108217707A - A kind of calcium carbonate tiny balloon and preparation method thereof - Google Patents
A kind of calcium carbonate tiny balloon and preparation method thereof Download PDFInfo
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- CN108217707A CN108217707A CN201611270098.8A CN201611270098A CN108217707A CN 108217707 A CN108217707 A CN 108217707A CN 201611270098 A CN201611270098 A CN 201611270098A CN 108217707 A CN108217707 A CN 108217707A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Abstract
Disclose a kind of calcium carbonate tiny balloon and preparation method thereof.Preparation method includes：1st, configuration calcium chloride (CaCl2), sodium carbonate (Na2CO3), polyacrylic acid (PAA) and dodecyl sodium sulfate (SDS) solution；2nd, prepared PAA is added to Na in equal volume2CO3Solution and CaCl2In solution；3rd, the addition of SDS solution is contained only into Na2CO3In the mixed solution of PAA, CaCl is added it to2With the mixed solution of PAA；4th, reaction product is filtered, washed, dries the good calcium carbonate tiny balloon of monodispersity that can obtain white powder.The calcium carbonate tiny balloon obtained has calcite and the compound crystal form of vaterite, and particle diameter distribution is uniform, soilless sticking phenomenon, 5~8 μm of average grain diameter, and specific surface area is 30~60m2/g.This preparation method process is simple, of low cost, easily controllable, environmentally protective, it can be achieved that industrialized production；Gained calcium carbonate tiny balloon has very big application value in fields such as medicament slow releases.
Description
Technical field
The present invention relates to a kind of preparation methods of the calcium carbonate tiny balloon containing vaterite and calcite crystal form, belong to nothing
Machine powder body material field, can be applied to the filler of building materials, plastics, ink, rubber etc., have biocompatibility and the life of height
Biodegradable may be used as biomedical and new drug carrier.
Background technology
Calcium carbonate is important inorganic material and typical biogenic mineral, be widely used in plastics, papermaking, ink, coating,
The industries such as weaving, binding agent, cosmetics, food.In nature, calcium carbonate mainly has three kinds of calcite, aragonite and vaterite
Different crystal forms, wherein calcite are the most stable of crystal forms of thermodynamics, secondly aragonite, and vaterite is most unstable crystalline substance
Type is easily converted into thermodynamically stable calcite or aragonite.On surface structure, calcium carbonate has chain, aciculiform, sheet, stands
The different morphologies such as rectangular, spherical, spindle, and the calcium carbonate product of different crystal forms and pattern has different application field and work(
Can, therefore the crystal form of control calcium carbonate, appearance structure by various methods, to prepare the calcium carbonate of different structure and performance crystalline substance
Body can greatly expand its application prospect.Due to being inspired by biomineralization process, lived by adding in organic additive and surface
Property agent controls the nucleation of mineral crystal, growth and arrangement, regulates and controls the pattern of inorganic particulate and structure with this, is concerned.
In recent years, calcium carbonate tiny balloon, due to it with larger internal cavities, density is low, large specific surface area, good machinery
And thermal stability, have the advantages that biocompatibility and degradability concurrently, it can be used in the fields such as medicine, cosmetics, genophore,
And by the extensive concern of domestic and foreign scholars.
At present, the preparation of calcium carbonate tiny balloon mainly has CO2Gaseous diffusion process, double decomposition etc. pass through organic addition
Agent or the regulating and controlling effect of template obtain various crystal forms and the calcium carbonate tiny balloon of appearance structure.Chinese patent
CN102515236A discloses a kind of hyperbranched polymer molecule using parents' water type as template, passes through water-soluble Ca salt and carbon
Calcium carbonate tiny balloon is made in precipitation reaction between hydrochlorate.But the tiny balloon particle diameter distribution obtained by this method is uneven, than
Surface area is low, and the higher price of the dissaving polymer of this parents' water type, is not suitable for industrialized production use.Chinese patent
CN103864127A discloses one kind using calcium chloride water as reactant, adds in after ammonium hydroxide adjusts pH value of solution and is passed through titanium dioxide again
Carbon gas successfully prepares calcium carbonate tiny balloon.But the method is more demanding to equipment and reaction environment, complicated for operation, and
Reaction time is longer, and required expensive, economy is too poor, is unfavorable for industrializing.Chinese patent CN105692675A is disclosed
A kind of sodium bicarbonate aqueous solution and calcium chloride alcoholic solution are reactant, make its gel by the mixing concussion of two kinds of solution, then
It stands, centrifuge, can obtain calcium carbonate tiny balloon after high temperature drying.The method is cumbersome, and products therefrom is reunited seriously, grain size point
Cloth is uneven.
In conclusion there are following shortcomings for prior art：First, hollow microspheres amount is not high in product, and micro-
Spherolite diameter is unevenly distributed；Second is that using organic solution or more complicated dissaving polymer additive, and additive level
More, the cost is relatively high, is not suitable for industrialized production.Third, the reaction time is longer, and it is complex for operation step, cause calcium carbonate empty
The manufacturing cost of heart microballoon is relatively excessively high.
Invention content
Simple, reproducible the purpose of the present invention is to provide a kind of preparation method, particle diameter distribution is uniform, monodispersity is good
Calcium carbonate tiny balloon and preparation method thereof to solve the deficiencies in the prior art.
Technical solution：
Calcium carbonate tiny balloon prepared by the present invention, particle diameter distribution is uniform, and for particle size range at 5~8 μm, monodispersity is good,
Gained calcium carbonate tiny balloon has vaterite and the compound crystal form of calcite, 30~60m of specific surface area2/g。
The preparation method of the product of the present invention is deposited jointly in Sodium Polyacrylate (PAA) and dodecyl sodium sulfate (SDS)
Under the conditions, according to calcium ion and the difference of two kinds of additive electrostatic interaction abilities, so as to affect the aggregation row of calcium carbonate
For and appearance structure, generate micron order calcium carbonate tiny balloon on this condition.
The preparation method of calcium carbonate tiny balloon of the present invention, includes the following steps：
(1) certain density PAA solution is divided into two equal parts of volume, is added separately to certain density calcium chloride
In solution and sodium carbonate liquor；
A concentration of 0.3~1.0g/L of the PAA, a concentration of 0.1~1.0mol/L of calcium chloride, sodium carbonate it is a concentration of
0.1~1.0mol/L；
(2) certain density SDS solution is added to above-mentioned PAA and NaCO3In mixed solution；
A concentration of 10.0~25.0mmol/L SDS of the SDS and the mass ratio of products therefrom calcium carbonate are 2: 10~2:
3；
(3) by PAA and CaCl2Mixed solution be added in the sodium carbonate mixture prepared by (2), in certain temperature
0.5~1.5h is stirred to react under degree；And the molar ratio of calcium chloride and sodium carbonate is 1: 1；
(4) after product is filtered and wash 3 times with deionized water and absolute ethyl alcohol, 80 DEG C of dryings, you can obtain white powder
The good calcium carbonate tiny balloon of the monodispersity of last shape.
The relative molecular weight of PAA is 2000~5000 in the step (1), additive PAA and products therefrom calcium carbonate
Mass ratio be 3: 50~3: 35.
Reaction temperature is 60 DEG C~90 DEG C in the step (3).
By calcium carbonate product prepared by above-mentioned condition, there is vaterite and the compound crystal form of calcite, particle diameter distribution is in 5~8 μ
Between m, specific surface area is 30~60m2/ g is monodispersed calcium carbonate tiny balloon.
Advantageous effect of the invention
(1) present invention is using double decomposition, and preparation process is simple, inexpensive, easily controllable without adjusting pH, green
Environmental protection, mild condition, it is easy to accomplish industrialized production.
(2) the micron order calcium carbonate tiny balloon particle diameter distribution that the present invention synthesizes is uniform, and good dispersion is avoided by being carbonized
The phenomenon that particle agglomeration of calcium carbonate microspheres synthesized by method, can be applied to the filling of building materials, plastics, rubber etc., improve production
The properties such as mobility, the whiteness of product.
(3) present invention is additive using PAA and SDS, and the calcium carbonate tiny balloon large specific surface area of preparation has height
Biocompatibility and biodegradability, can be used in biomedical and new drug carrier.
Description of the drawings
The SEM photograph of 1 product of Fig. 1 embodiments.
The TEM photos of 1 product of Fig. 2 embodiments.
The SEM photograph of 2 product of Fig. 3 embodiments.
The XRD spectrum of 2 product of Fig. 4 embodiments.
The SEM photograph of 3 product of Fig. 5 embodiments.
The XRD spectrum of 3 product of Fig. 6 embodiments.
The SEM photograph of 4 product of Fig. 7 embodiments.
The XRD spectrum of 4 product of Fig. 8 embodiments.
The SEM photograph of 1 product of Fig. 9 comparative examples.
The TEM photos of 1 product of Figure 10 comparative examples.
The SEM photograph of 2 product of Figure 11 comparative examples.
The TEM photos of 2 product of Figure 12 comparative examples.
Specific embodiment
The specific embodiment of the present invention is described by the following examples, but embodiment is not intended to limit the present invention's
Protection domain.
Vaterite content is to measure collection of illustrative plates according to the XRD of product in product, and gained is calculated as follows：
X in formulaC、XVThe molar content of vaterite in sample, calcite, I are represented respectivelyV 110、IC 104Figure is represented respectively
The peak area of vaterite (110) crystal face, calcite (104) crystal face in spectrum.The specific surface area of product uses N2Absorption method is tested, root
It is calculated according to BET principles；Pore-size distribution is according to N2Isothermal adsorption-desorption data is calculated using BJH models.Product
Appearance structure and grain size are observed using scanning electron microscope (SEM) and transmission electron microscope (TEM).
Embodiment 1
By the use of water as solvent, the Na of 0.1mol/L is prepared2CO3The CaCl of solution, 0.1mol/L2The PAA of solution, 0.5g/L
The SDS solution of solution (relative molecular weight of PAA is 2000) and 10.0mmol/L.Two parts of PAA (each 25mL) solution are taken out, respectively
It is added to 100mLNa2CO3Solution and 100mL CaCl2In solution, 0.5h is stirred.50mL SDS solution is added to and is equipped with
Na2CO3In the three-necked flask of the mixed solution of PAA, then by CaCl2This three-necked flask is rapidly joined with PAA mixed solutions
In, under conditions of 80 DEG C, rotating speed is 200r/min, keep reaction 1h.The CaCO of gained3Suspension filters, and uses deionized water
It is respectively washed with absolute ethyl alcohol 3 times, filter cake is put into drying and dehydrating in 80 DEG C of drying box and obtains white powder product.
The SEM photograph and TEM photos of product are shown in attached drawing 1 and attached drawing 2, and Average Particle Diameters are 6.2 μm, and XRD tests its ball
Aragonite calcium carbonate molar content is 85.0% (calcite calcium carbonate molar content is 15.0%), specific surface area 59.6m2/
G, average pore size 20.44nm show the calcium carbonate tiny balloon that product is large specific surface area.Other tests and calculating data are shown in Table
1。
Embodiment 2
By the use of water as solvent, the Na of 1.0mol/L is prepared2CO3The CaCl of solution, 1.0mol/L2The PAA of solution, 1.0g/L
The SDS solution of solution (relative molecular weight of PAA is 5000) and 25.0mmol/L.Two parts of PAA (each 25mL) solution are taken out, respectively
It is added to 100mL Na2CO3Solution and 100mL CaCl2In solution, 0.5h.50mL SDS solution is added to equipped with Na2CO3With
In the three-necked flask of the mixed solution of PAA, then by CaCl2It is rapidly joined in this three-necked flask with PAA mixed solutions, 90
DEG C, rotating speed is under conditions of 200r/min, keeps reaction 1h.The CaCO of gained3Suspension filters, with deionized water and anhydrous second
Alcohol respectively washing 3 times, filter cake is put into drying and dehydrating in 80 DEG C of drying box, obtains white powder product.
The SEM photograph of product is shown in attached drawing 3, and Average Particle Diameters are 6.8 μm, and XRD spectrum is shown in attached drawing 4, vaterite carbonic acid
Calcium molar content is 68.0% (calcite calcium carbonate molar content is 32.0%), specific surface area 51.5m2/ g, average hole
Diameter 21.01nm shows the calcium carbonate tiny balloon that product is large specific surface area.Other tests and calculating data are shown in Table 1.
Embodiment 3
According to the identical method of embodiment 1, except that：Na2CO3Solution concentration is 0.5mol/L；CaCl2Solution is dense
It spends for 0.5mol/L；The molecular weight of PAA is 3000, a concentration of 0.8g/L；A concentration of 15.0mmol/L of SDS；Reaction temperature
It is 60 DEG C.
The SEM photograph of product is shown in attached drawing 5, and Average Particle Diameters are 5.2 μm, and XRD spectrum is shown in attached drawing 6, vaterite carbonic acid
Calcium molar content is 46.8% (calcite calcium carbonate molar content is 53.2%), specific surface area 40.6m2/ g, average hole
Diameter 18.49nm shows the calcium carbonate tiny balloon that product is large specific surface area.Other tests and calculating data are shown in Table 1.
Embodiment 4
According to the identical method of embodiment 2, except that：Na2CO3Solution concentration is 0.3mol/L；CaCl2Solution is dense
It spends for 0.3mol/L；The molecular weight of PAA is 4000, a concentration of 0.6g/L；A concentration of 20.0mmol/L of SDS；Reaction temperature
It is 70 DEG C.
The SEM photograph of product is shown in attached drawing 7, and Average Particle Diameters are 7.8 μm, and XRD spectrum is shown in attached drawing 8, vaterite carbonic acid
Calcium molar content is 34.5% (calcite calcium carbonate molar content is 65.5%), specific surface area 31.4m2/ g, average hole
Diameter 17.76nm, it is calcium carbonate tiny balloon to show product.Other tests and calculating data are shown in Table 1.
Comparative example 1
Keeping other reaction conditions and embodiment 1 under the same conditions, this comparative example is with polyvinylpyrrolidone (PVP)
Polyacrylic acid (PAA) is substituted as additive.
The SEM photograph and TEM photos of product are shown in attached drawing 9 and attached drawing 10, and Average Particle Diameters are 8.4 μm, and XRD tests its ball
Aragonite calcium carbonate molar content is 26.8% (calcite calcium carbonate molar content is 73.2%), specific surface area 21.8m2/
G, average pore size 15.33nm.Other tests and calculating data are shown in Table 1.
Comparative example 2
Keeping other reaction conditions and embodiment 1 under the same conditions, this comparative example polyethenoxy sorbitan
Monoleate (Tween-80) substitutes dodecyl sodium sulfate (SDS) as additive.
The SEM photograph and TEM photos of product are shown in attached drawing 11 and attached drawing 12.Average Particle Diameters are 5.6 μm, and XRD tests it
Vaterite calcium carbonate molar content is 13.1% (calcite calcium carbonate molar content is 86.9%), and specific surface area is
10.6m2/ g, average pore size 22.84nm.Other tests and calculating data are shown in Table 1.
The crystal form compositions and features of 1 product calcium carbonate of table
Claims (4)
1. a kind of calcium carbonate tiny balloon, which is characterized in that there is calcite and the compound crystal form of vaterite, 5~8 μ of average grain diameter
M, particle diameter distribution is uniform, and monodispersity is good, and specific surface area is 30~60m2/g。
2. the preparation method of calcium carbonate tiny balloon according to claim 1, which is characterized in that include the following steps：
(1) certain density polyacrylic acid aqueous solution is divided into isometric two parts, be added separately to calcium chloride water and
Calcium liquid and lye are made in aqueous sodium carbonate；
A concentration of 0.3~1.0g/L of described polyacrylic acid, 0.1~1.0mol/L of concentration of calcium chloride water, sodium carbonate
A concentration of 0.1~1.0mol/L of solution；
(2) certain density sodium dodecyl sulfate aqueous solution is added in above-mentioned lye and obtains alkaline mixed solution；Described ten
A concentration of 10.0~25.0mmol/L of dialkyl sulfonates solution；The quality of dodecyl sodium sulfate and products therefrom calcium carbonate
Than being 2: 10~2: 3；
(3) above-mentioned calcium liquid is added in into alkaline mixed solution, 0.5~1.5h of insulated and stirred；
(4) product is collected by filtration, then is washed respectively 3 times with water and absolute ethyl alcohol, filter cake is dry at 80 DEG C, obtains white powder
Shape product.
3. according to the method described in claim 2, it is characterized in that, the molar ratio of calcium chloride and sodium carbonate be 1.0, holding temperature
It is 60~90 DEG C.
4. according to 2 and 3 any one of them method of claim, which is characterized in that the molecular weight of polyacrylic acid for 2000~
5000, the mass ratio of polyacrylic acid and products therefrom calcium carbonate is 3: 50~3: 35.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110857220A (en) * | 2018-08-24 | 2020-03-03 | 中石化石油工程技术服务有限公司 | Method for mineralizing and depositing polymer carrying salt ions layer by layer |
| CN111718144A (en) * | 2020-06-05 | 2020-09-29 | 江苏科技大学 | Preparation method and application of cement-based material additive |
| CN112624171A (en) * | 2020-12-21 | 2021-04-09 | 广西华纳新材料科技有限公司 | Preparation method of stable hollow calcium carbonate particles with controllable particle size |
| CN112850767A (en) * | 2021-01-29 | 2021-05-28 | 湖北民族大学 | Low-temperature rapid preparation method of hollow capsule-shaped calcium carbonate |
| CN113663136A (en) * | 2021-09-29 | 2021-11-19 | 南京市中医院 | Degradable polymer-calcium carbonate composite bone repair material and preparation method thereof |
| CN114804176A (en) * | 2022-04-01 | 2022-07-29 | 广州大学 | Preparation method and application of porous calcium carbonate |
| CN115140755A (en) * | 2022-07-14 | 2022-10-04 | 桂林卓瑞食品原料有限公司 | Preparation method of porous calcium carbonate |
| CN115180644A (en) * | 2022-06-14 | 2022-10-14 | 广州大学 | Preparation method of porous calcium carbonate microspheres capable of loading regenerant to delay asphalt aging |
| CN115304303A (en) * | 2022-07-06 | 2022-11-08 | 广州大学 | Method for delaying asphalt aging by using porous calcium carbonate microsphere sustained-release regenerant |
| CN115520888A (en) * | 2022-10-18 | 2022-12-27 | 四川大学 | Application of carbon dioxide adduct of polyethyleneimine in preparation of calcium carbonate |
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| JP2013216545A (en) * | 2012-04-11 | 2013-10-24 | Nagoya Institute Of Technology | Hollow calcium carbonate particle and method for producing the same |
| CN107735527A (en) * | 2015-01-14 | 2018-02-23 | 英默里斯美国公司 | The controlled method of winnofil and the vaterite winnofil composition formed by methods described |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110857220A (en) * | 2018-08-24 | 2020-03-03 | 中石化石油工程技术服务有限公司 | Method for mineralizing and depositing polymer carrying salt ions layer by layer |
| CN111718144A (en) * | 2020-06-05 | 2020-09-29 | 江苏科技大学 | Preparation method and application of cement-based material additive |
| CN111718144B (en) * | 2020-06-05 | 2021-11-26 | 江苏科技大学 | Preparation method and application of cement-based material additive |
| CN112624171B (en) * | 2020-12-21 | 2023-03-28 | 广西华纳新材料股份有限公司 | Preparation method of stable hollow calcium carbonate particles with controllable particle size |
| CN112624171A (en) * | 2020-12-21 | 2021-04-09 | 广西华纳新材料科技有限公司 | Preparation method of stable hollow calcium carbonate particles with controllable particle size |
| CN112850767A (en) * | 2021-01-29 | 2021-05-28 | 湖北民族大学 | Low-temperature rapid preparation method of hollow capsule-shaped calcium carbonate |
| CN113663136A (en) * | 2021-09-29 | 2021-11-19 | 南京市中医院 | Degradable polymer-calcium carbonate composite bone repair material and preparation method thereof |
| CN114804176A (en) * | 2022-04-01 | 2022-07-29 | 广州大学 | Preparation method and application of porous calcium carbonate |
| CN115180644A (en) * | 2022-06-14 | 2022-10-14 | 广州大学 | Preparation method of porous calcium carbonate microspheres capable of loading regenerant to delay asphalt aging |
| CN115304303A (en) * | 2022-07-06 | 2022-11-08 | 广州大学 | Method for delaying asphalt aging by using porous calcium carbonate microsphere sustained-release regenerant |
| CN115140755A (en) * | 2022-07-14 | 2022-10-04 | 桂林卓瑞食品原料有限公司 | Preparation method of porous calcium carbonate |
| CN115140755B (en) * | 2022-07-14 | 2023-11-10 | 桂林卓瑞食品原料有限公司 | Preparation method of porous calcium carbonate |
| CN115520888A (en) * | 2022-10-18 | 2022-12-27 | 四川大学 | Application of carbon dioxide adduct of polyethyleneimine in preparation of calcium carbonate |
| CN115520888B (en) * | 2022-10-18 | 2023-08-29 | 四川大学 | Application of carbon dioxide adduct of polyethyleneimine in preparation of calcium carbonate |
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Application publication date: 20180629 |