CN106118135B - A kind of preparation method of hemispherical calcium carbonate structure - Google Patents
A kind of preparation method of hemispherical calcium carbonate structure Download PDFInfo
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- CN106118135B CN106118135B CN201610488769.1A CN201610488769A CN106118135B CN 106118135 B CN106118135 B CN 106118135B CN 201610488769 A CN201610488769 A CN 201610488769A CN 106118135 B CN106118135 B CN 106118135B
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- calcium carbonate
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 33
- 229920001353 Dextrin Polymers 0.000 claims abstract description 20
- 239000004375 Dextrin Substances 0.000 claims abstract description 20
- 235000019425 dextrin Nutrition 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012065 filter cake Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000001110 calcium chloride Substances 0.000 claims abstract description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 5
- 238000001694 spray drying Methods 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- QDYLMAYUEZBUFO-UHFFFAOYSA-N cetalkonium chloride Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 QDYLMAYUEZBUFO-UHFFFAOYSA-N 0.000 claims description 3
- MLGWTHRHHANFCC-UHFFFAOYSA-N prop-2-en-1-amine;hydrochloride Chemical compound Cl.NCC=C MLGWTHRHHANFCC-UHFFFAOYSA-N 0.000 claims description 2
- AVWKSSYTZYDQFG-UHFFFAOYSA-M dimethyl-octadecyl-prop-2-enylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC=C AVWKSSYTZYDQFG-UHFFFAOYSA-M 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 16
- 229920000620 organic polymer Polymers 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 9
- 239000011575 calcium Substances 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 235000013409 condiments Nutrition 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000001186 cumulative effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- FYHXNYLLNIKZMR-UHFFFAOYSA-N calcium;carbonic acid Chemical compound [Ca].OC(O)=O FYHXNYLLNIKZMR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- 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
- C09C1/02—Compounds of alkaline earth metals or magnesium
-
- 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
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Cosmetics (AREA)
Abstract
The present invention provides a kind of preparation method of hemispherical calcium carbonate, includes the following steps：1) one or more of calcirm-fluoride, calcium chloride, calcium nitrate are dissolved in water and are configured to Ca2+The solution of a concentration of 0.1~1mol/L, PH are adjusted to 4~5；2) dextrin, addition Ca are added in2+0.9~1.1 times of molal quantity stirs 10~30min at 50~70 DEG C；3) quaternary cationic surfactant is added in, 10~30min is stirred at 30~50 DEG C；4) it is passed through the NH of flowing3And CO2Mixed gas, flow be 0.05~0.5ml/min, NH3And CO2Volume ratio be 1:(0.8~1.2), reaction 4~for 24 hours；5) it filters, it is 6~7 that filter cake is washed to PH；6) alcohol is washed, spray drying.Present invention improves pearl filler to the compatibility of organic polymer, and improve the acid resistance and smoothness of filler.
Description
【Technical field】
The present invention relates to industrial filler field more particularly to a kind of preparation methods of hemispherical calcium carbonate.
【Background technology】
Calcium carbonate is the widest chemical products of current purposes, as the additive and reinforcing agent of a kind of function admirable, quilt
It is widely used in the industry such as rubber, plastics, papermaking, coating, weaving, ink, toothpaste, cosmetics, daily necessities, food, medicine, it can
To improve the heat resistance of product, wearability, dimensional stability, rigidity and machinability, improve the surface color degree of product, improve
The comprehensive mechanical property of product, and reduce the cost of product.But existing calcium carbonate surface has the stronger hydroxyl of hydrophily,
Stronger alkalinity is presented, the calcium carbonate and the compatibility of organic polymer that this hydrophilic and oleophobic property makes are poor, easily form aggregation
Body, cause high polymer inside points disperse it is uneven, so as to cause two kinds of storeroom boundary defects, direct application effect is bad；
Moreover, calcium carbonate, as filler, the performances such as acid resistance, smoothness need to be further improved.
Therefore, it develops new preparation method to be modified pearl filler, improves its compatibility to organic polymer,
Comprehensive performance of the calcium carbonate as additive or reinforcing agent will be improved, widens the application field of calcium carbonate.
【Invention content】
For the above problem of the prior art, the present invention provides a kind of preparation method of hemispherical calcium carbonate, improves
Pearl filler improves the acid resistance and smoothness of filler to the compatibility of organic polymer.
The technical scheme is that：
A kind of preparation method of hemispherical calcium carbonate structure, which is characterized in that include the following steps：
(1) one or more of calcirm-fluoride, calcium chloride, calcium nitrate are dissolved in water and are configured to Ca2+A concentration of 0.1~
The solution of 1mol/L adds nitric acid that the PH of solution is adjusted to 4~5；
(2) dextrin is added in the solution obtained by step (1), the addition of the dextrin is Ca2+The 0.9 of molal quantity~
1.1 times, under the conditions of 50~70 DEG C, stir 10~30min；
(3) quaternary cationic surfactant is added in the solution obtained by step (2), in 30~50 DEG C of conditions
Under, stir 10~30min；
(4) NH of flowing is passed through in the solution obtained by step (3)3And CO2Mixed gas, the stream of the mixed gas
It measures as 0.05~0.5ml/min, NH3And CO2Volume ratio be 1:(0.8~1.2), reaction 4~for 24 hours, generation has white crystals
Mixture；
(5) mixture obtained by step (4) is filtered, it is 6~7 that filter cake is washed to PH；
(6) the filter cake alcohol obtained by step (5) is washed, is spray-dried, obtains final products.
Specifically, the molal quantity of dextrin is equal to Ca in above-mentioned steps (2)2+Molal quantity, the addition of dextrin and its concentration determine
The pattern of product and its integrality of pattern.
Specifically, the quaternary cationic surfactant in above-mentioned steps (3) is hexadecyldimethyl benzyl ammonium pi-allyl
Ammonium chloride or solution property, the positively charged one end of this kind of modifying agent is by Electrostatic Absorption in carbonic acid
Calcium surface, the other end can be crosslinked with high polymer, realize the surface modification to calcium carbonate.
Specifically, the mixed gas flow of above-mentioned steps (4) is 0.1~0.2ml/min, air-flow is bigger, and product is averaged
Grain size is smaller.
Specifically, NH in above-mentioned mixed gas3And CO2Volume ratio be 1:1, NH3So that solution alkaline and keeping alkali
Property, make CO2Crystallization effect it is more preferable, while avoid excessive CO2The problem of making the dissolution of calcium carbonate crystallized.
Specifically, the alcohol of above-mentioned steps (6), which is washed, uses ethyl alcohol or propyl alcohol, and it is safe and non-toxic, be conducive to disperse and dry.
Specifically, the inlet temperature of the spray drying of above-mentioned steps (6) is 80~90 DEG C, outlet temperature is 30~50 DEG C.
Specifically, the product that above-mentioned steps (6) obtain is hemispherical calcium carbonate, hemispherical pattern, which exists, specifically preferentially to be taken
To, can improve the smoothness of condiment, and with the contact angle smaller of water, the moisture resistance and acid resistance of filler can be improved.
Specifically, the average grain diameter of product that above-mentioned steps (6) obtain is 100~500nm, the average grain diameter is accumulative
Size distribution percentage reaches grain size corresponding when 50%, dispersibility of the product in organic polymer in the range
Good, excessive or too small grain size is unfavorable for disperseing, thereby increases and it is possible to can reduce whiteness.
The present invention has technique effect beneficial below：
1) present invention obtains the hemispherical carbonic acid of 100~500nm of average grain diameter by appropriate raw material, proportioning and step
Calcium, good dispersion, and because of its special pattern, as filler when, can regulate and control its position of orientation, can improve the smooth of filler
Degree；2) present invention passes through hexadecyldimethyl benzyl ammonium allyl ammonium chloride or solution property lamp quaternary ammonium
Salt cationic surfactant improves compatibility of the pearl filler to organic polymer, is conducive to it organic high poly-
It is homodisperse in object；3) the hemispherical pattern of product of the present invention, the contact angle smaller with water, can improve the moisture-proof of filler
Property and acid resistance.
【Description of the drawings】
Fig. 1 is the stereoscan photograph of embodiment one.
【Specific embodiment】
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment provided below is not to limit the range that the utility model is covered, and described step is not yet
It is to limit its to perform sequence.Those skilled in the art the present invention is done with reference to existing common knowledge it is conspicuously improved,
Also fall into the present invention claims protection domain within.
Embodiment one
A kind of preparation method of hemispherical calcium carbonate structure, which is characterized in that include the following steps：
(1) calcirm-fluoride is dissolved in water and is configured to Ca2+The solution of a concentration of 0.5mol/L adds nitric acid that the PH of solution is adjusted to 4
~5；
(2) dextrin is added in the solution obtained by step (1), the addition of the dextrin is Ca2+1 times of molal quantity,
Under the conditions of 60 DEG C, 10~30min is stirred；The addition of dextrin and its concentration decide the pattern of product and its integrality of pattern；
(3) quaternary cationic surfactant is added in the solution obtained by step (2), under the conditions of 40 DEG C, stirred
Mix 10~30min；The positively charged one end of this kind of modifying agent by Electrostatic Absorption in calcium carbonate surface, the other end can and high polymer
It is crosslinked, realizes the surface modification to calcium carbonate；
(4) NH of flowing is passed through in the solution obtained by step (3)3And CO2Mixed gas, the stream of the mixed gas
It measures as 0.1ml/min, NH3And CO2Volume ratio be 1:1, reaction 4~for 24 hours, mixture of the generation with white crystals；Air-flow is got over
Greatly, the average grain diameter of product is smaller；NH3So that solution alkaline and keep alkalinity, make CO2Crystallization effect it is more preferable, avoid simultaneously
Excessive CO2The problem of making the dissolution of calcium carbonate crystallized, the mixed gas be successfully realized hemispherical calcium carbonate crystallization and
It is precipitated；
(5) mixture obtained by step (4) is filtered, it is 6~7 that filter cake is washed to PH；
(6) the filter cake ethyl alcohol obtained by step (5) is washed 3 times, be spray-dried, inlet temperature is 80~90 DEG C, outlet temperature
It is 30~50 DEG C, obtains final products.As shown in Figure 1, product is the hemispherical calcium carbonate of average grain diameter 150nm.Hemispherical shape
Looks can improve the smoothness of condiment there are specific preferred orientation, and with the contact angle smaller of water, filler can be improved
Moisture resistance and acid resistance.The average grain diameter is that cumulative particle sizes percentile reaches grain size corresponding when 50%, in the model
Good dispersion of the product in organic polymer in enclosing, excessive or too small grain size are unfavorable for disperseing, thereby increases and it is possible to can reduce
Whiteness.
Embodiment two
A kind of preparation method of hemispherical calcium carbonate structure, which is characterized in that include the following steps：
(1) calcium chloride is dissolved in water and is configured to Ca2+The solution of a concentration of 0.1mol/L adds nitric acid that the PH of solution is adjusted to 4
~5；
(2) dextrin is added in the solution obtained by step (1), the addition of the dextrin is Ca2+0.9 times of molal quantity,
Under the conditions of 50 DEG C, 10~30min is stirred；The addition of dextrin and its concentration decide product pattern and its pattern it is complete
Property；
(3) quaternary cationic surfactant is added in the solution obtained by step (2), under the conditions of 30 DEG C, stirred
Mix 10~30min；The positively charged one end of this kind of modifying agent by Electrostatic Absorption in calcium carbonate surface, the other end can and high polymer
It is crosslinked, realizes the surface modification to calcium carbonate；
(4) NH of flowing is passed through in the solution obtained by step (3)3And CO2Mixed gas, the stream of the mixed gas
It measures as 0.05ml/min, NH3And CO2Volume ratio be 1:0.8, reaction 4~for 24 hours, mixture of the generation with white crystals；Gas
Stream is bigger, and the average grain diameter of product is smaller；NH3So that solution alkaline and keep alkalinity, make CO2Crystallization effect it is more preferable, simultaneously
Avoid excessive CO2The problem of making the dissolution of calcium carbonate crystallized, the mixed gas are successfully realized the knot of hemispherical calcium carbonate
Brilliant and precipitation；
(5) mixture obtained by step (4) is filtered, it is 6~7 that filter cake is washed to PH；
(6) the filter cake propyl alcohol obtained by step (5) is washed 3 times, be spray-dried, inlet temperature is 80~90 DEG C, outlet temperature
It is 30~50 DEG C, obtains final products.Product is the hemispherical calcium carbonate of average grain diameter 500nm.There are specific for hemispherical pattern
Preferred orientation, can improve the smoothness of condiment, and with the contact angle smaller of water, the moisture resistance of filler and resistance to can be improved
It is acid.The average grain diameter is that cumulative particle sizes percentile reaches grain size corresponding when 50%, product in the range
Good dispersion in organic polymer, excessive or too small grain size are unfavorable for disperseing, thereby increases and it is possible to can reduce whiteness.
Embodiment three
A kind of preparation method of hemispherical calcium carbonate structure, which is characterized in that include the following steps：
(1) calcium nitrate is dissolved in water and is configured to Ca2+The solution of a concentration of 1mol/L, add nitric acid the PH of solution is adjusted to 4~
5；
(2) dextrin is added in the solution obtained by step (1), the addition of the dextrin is Ca2+1.1 times of molal quantity,
Under the conditions of 70 DEG C, 10~30min is stirred；The addition of dextrin and its concentration decide product pattern and its pattern it is complete
Property；
(3) quaternary cationic surfactant is added in the solution obtained by step (2), under the conditions of 50 DEG C, stirred
Mix 10~30min；The positively charged one end of this kind of modifying agent by Electrostatic Absorption in calcium carbonate surface, the other end can and high polymer
It is crosslinked, realizes the surface modification to calcium carbonate；
(4) NH of flowing is passed through in the solution obtained by step (3)3And CO2Mixed gas, the stream of the mixed gas
It measures as 0.5ml/min, NH3And CO2Volume ratio be 1:1.2, reaction 4~for 24 hours, mixture of the generation with white crystals；Air-flow
Bigger, the average grain diameter of product is smaller；NH3So that solution alkaline and keep alkalinity, make CO2Crystallization effect it is more preferable, keep away simultaneously
Excessive CO is exempted from2The problem of making the dissolution of calcium carbonate crystallized, the mixed gas are successfully realized the crystallization of hemispherical calcium carbonate
And precipitation；
(5) mixture obtained by step (4) is filtered, it is 6~7 that filter cake is washed to PH；
(6) the filter cake ethyl alcohol obtained by step (5) is washed 3 times, be spray-dried, inlet temperature is 80~90 DEG C, outlet temperature
It is 30~50 DEG C, obtains final products.Product is the hemispherical calcium carbonate of average grain diameter 100nm.There are specific for hemispherical pattern
Preferred orientation, can improve the smoothness of condiment, and with the contact angle smaller of water, the moisture resistance of filler and resistance to can be improved
It is acid.The average grain diameter is that cumulative particle sizes percentile reaches grain size corresponding when 50%, product in the range
Good dispersion in organic polymer, excessive or too small grain size are unfavorable for disperseing, thereby increases and it is possible to can reduce whiteness.
Example IV
A kind of preparation method of hemispherical calcium carbonate structure, which is characterized in that include the following steps：
(1) by calcirm-fluoride, calcium chloride, calcium nitrate according to 1:1:1, which is dissolved in water, is configured to Ca2+A concentration of 0.2mol/L's is molten
Liquid adds nitric acid that the PH of solution is adjusted to 4~5；
(2) dextrin is added in the solution obtained by step (1), the addition of the dextrin is Ca2+1 times of molal quantity,
Under the conditions of 70 DEG C, 10~30min is stirred；The addition of dextrin and its concentration decide the pattern of product and its integrality of pattern；
(3) quaternary cationic surfactant is added in the solution obtained by step (2), under the conditions of 50 DEG C, stirred
Mix 10~30min；The positively charged one end of this kind of modifying agent by Electrostatic Absorption in calcium carbonate surface, the other end can and high polymer
It is crosslinked, realizes the surface modification to calcium carbonate；
(4) NH of flowing is passed through in the solution obtained by step (3)3And CO2Mixed gas, the stream of the mixed gas
It measures as 0.2ml/min, NH3And CO2Volume ratio be 1:1, reaction 4~for 24 hours, mixture of the generation with white crystals；Air-flow is got over
Greatly, the average grain diameter of product is smaller；NH3So that solution alkaline and keep alkalinity, make CO2Crystallization effect it is more preferable, avoid simultaneously
Excessive CO2The problem of making the dissolution of calcium carbonate crystallized, the mixed gas be successfully realized hemispherical calcium carbonate crystallization and
It is precipitated；
(5) mixture obtained by step (4) is filtered, it is 6~7 that filter cake is washed to PH；
(6) the filter cake ethyl alcohol obtained by step (5) is washed 3 times, be spray-dried, inlet temperature is 80~90 DEG C, outlet temperature
It is 30~50 DEG C, obtains final products.As shown in Figure 1, product is the hemispherical calcium carbonate of average grain diameter 380nm.Hemispherical shape
Looks can improve the smoothness of condiment there are specific preferred orientation, and with the contact angle smaller of water, filler can be improved
Moisture resistance and acid resistance.The average grain diameter is that cumulative particle sizes percentile reaches grain size corresponding when 50%, in the model
Good dispersion of the product in organic polymer in enclosing, excessive or too small grain size are unfavorable for disperseing, thereby increases and it is possible to can reduce
Whiteness.
Claims (8)
1. a kind of preparation method of hemispherical calcium carbonate structure, which is characterized in that include the following steps：
(1) one or more of calcirm-fluoride, calcium chloride, calcium nitrate are dissolved in water and are configured to Ca2+A concentration of 0.1~1mol/L's
Solution adds nitric acid that the pH of solution is adjusted to 4~5；
(2) dextrin is added in the solution obtained by step (1), the addition of the dextrin is Ca2+0.9~1.1 times of molal quantity,
Under the conditions of 50~70 DEG C, 10~30min is stirred；
(3) quaternary cationic surfactant is added in the solution obtained by step (2), under the conditions of 30~50 DEG C, stirred
Mix 10~30min；
(4) NH of flowing is passed through in the solution obtained by step (3)3And CO2Mixed gas, the flow of the mixed gas is
0.1~0.2mL/min, NH3And CO2Volume ratio be 1:(0.8~1.2), reaction 4~for 24 hours, generation is mixed with white crystals
Close object；
(5) mixture obtained by step (4) is filtered, it is 6~7 that filter cake is washed to pH；
(6) the filter cake alcohol obtained by step (5) is washed, is spray-dried, obtains final products.
2. the preparation method of hemispherical calcium carbonate structure according to claim 1, which is characterized in that in the step (2)
The molal quantity of dextrin is equal to Ca2+Molal quantity.
3. the preparation method of hemispherical calcium carbonate structure according to claim 1, which is characterized in that in the step (3)
Quaternary cationic surfactant be hexadecyldimethyl benzyl ammonium allyl ammonium chloride or octadecyldimethyl allyl
Ammonium chloride.
4. the preparation method of hemispherical calcium carbonate structure according to claim 1, which is characterized in that in the mixed gas
NH3And CO2Volume ratio be 1:1.
5. the preparation method of hemispherical calcium carbonate structure according to claim 1, which is characterized in that the step (6)
Alcohol, which is washed, uses ethyl alcohol or propyl alcohol.
6. the preparation method of hemispherical calcium carbonate structure according to claim 1, which is characterized in that the step (6)
The inlet temperature of spray drying is 80~90 DEG C, and outlet temperature is 30~50 DEG C.
7. according to the preparation method of claim 1-6 any one of them hemispherical calcium carbonate structures, which is characterized in that the step
Suddenly the product that (6) obtain is hemispherical calcium carbonate.
8. according to the preparation method of claim 1-6 any one of them hemispherical calcium carbonate structures, which is characterized in that the step
Suddenly the average grain diameter for the product that (6) obtain is 100~500nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610488769.1A CN106118135B (en) | 2016-06-24 | 2016-06-24 | A kind of preparation method of hemispherical calcium carbonate structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610488769.1A CN106118135B (en) | 2016-06-24 | 2016-06-24 | A kind of preparation method of hemispherical calcium carbonate structure |
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| Publication Number | Publication Date |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1172073A (en) * | 1997-04-17 | 1998-02-04 | 王睛雁 | Production technique for ultramicrofine light calcium carbonate |
| CN1305956A (en) * | 2000-01-18 | 2001-08-01 | 北京化工大学 | Process for preparing calcium carbonate deposit by continuous method |
| CN102145910A (en) * | 2011-02-24 | 2011-08-10 | 四川大学 | Method for preparing calcium carbonate of different morphologies from ionic liquid |
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| AU2002359958A1 (en) * | 2001-12-31 | 2003-07-15 | Beijing University Of Chemical Technology | Calcium carbonate of different shapes and the preparing process thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1172073A (en) * | 1997-04-17 | 1998-02-04 | 王睛雁 | Production technique for ultramicrofine light calcium carbonate |
| CN1305956A (en) * | 2000-01-18 | 2001-08-01 | 北京化工大学 | Process for preparing calcium carbonate deposit by continuous method |
| CN102145910A (en) * | 2011-02-24 | 2011-08-10 | 四川大学 | Method for preparing calcium carbonate of different morphologies from ionic liquid |
Non-Patent Citations (1)
| Title |
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| 《环糊精与季铵盐表面活性剂的相互作用及其在碳纳米管分散和碳酸钙制备中的应用》;白燕;《中国博士学位论文全文数据库工程科技I辑》;20100515(第5期);第1.3节、第2节、第5.2.2节及第5.4节 * |
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