CN115259197A - Method for preparing disc-shaped nano calcium carbonate by using polyamidine type guiding agent - Google Patents
Method for preparing disc-shaped nano calcium carbonate by using polyamidine type guiding agent Download PDFInfo
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 84
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000012544 monitoring process Methods 0.000 claims abstract description 9
- 239000011575 calcium Substances 0.000 claims abstract description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 17
- 239000000920 calcium hydroxide Substances 0.000 claims description 17
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 4
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000003763 carbonization Methods 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- ARBPOEAGKXLZHI-UHFFFAOYSA-N 2-benzylprop-2-enenitrile Chemical compound N#CC(=C)CC1=CC=CC=C1 ARBPOEAGKXLZHI-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- 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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or 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
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Geology (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a method for preparing disc-shaped nano calcium carbonate by using a polyamidine type guiding agent, which comprises the steps of mixing a polyamidine aqueous solution with the concentration of 0.05 to 5 percent and Ca (OH) with the concentration of 6 to 12 percent 2 After mixing the aqueous solutions, CO was introduced 2 Reacting gas at 5 to 30 ℃, monitoring the pH of the system in the reaction process, and continuously introducing CO when the pH reaches 6.8 to 7.2 2 Stopping the reaction after the gas is used for 10 to 30 min; and after the reaction is finished, filtering and washing the system, and drying to obtain the disc-shaped nano calcium carbonate. The invention can realize large-scale high-efficiency production, and the obtained disc-shaped nano calcium carbonate has the characteristics of uniform crystal grain appearance, narrow size distribution and the like, can be used as an additive of high-quality paper and coating materials, and can improve the surface smoothness and the glossiness.
Description
Technical Field
The invention relates to the field of inorganic material synthesis, in particular to a method for preparing disc-shaped nano calcium carbonate by using a polyamidine type guiding agent.
Background
The superfine calcium carbonate is used as a functional inorganic material and has wide application in the fields of papermaking, paint, rubber, cables, coatings, food, clothing and the like. Under the global carbon neutralization large background, the limestone which is cheap and easy to obtain is digested and cured, and then is combined with rich and renewable carbon dioxide to generate nano calcium carbonate, so that the fine utilization from carbon dioxide molecules to high-end functional materials can be realized to a certain extent. However, the application performance and the price of the calcium carbonate powder greatly depend on the particle size, morphology, dispersibility and the like of the calcium carbonate. As the outstanding calcium carbonate in the calcium carbonate industry, the nano calcium carbonate with uniform particle size distribution and uniform morphology drives the professional application of the whole calcium carbonate industry in the chemical industry. In the production process, the carbonization step is an important process influencing the appearance and the particle size of the crystal. Therefore, the method needs to find suitable carbonization process conditions to synthesize the nano calcium carbonate with a specific morphology in a large scale, and has important significance.
At present, CO is utilized 2 The system for synthesizing nano calcium carbonate with calcium hydroxide aqueous solution is widely reported, and the carbonization process mainly focuses on the technologies of low-temperature intermittent bubbling carbonization, normal-temperature continuous spraying carbonization, low-temperature stirring reaction kettle carbonization, supergravity reaction crystallization and the like. Among them, the crystal form directing agent is essential to control the growth of crystal grains. Such as sulfate, sodium polyphosphate and the like, and the cubic nano calcium carbonate is generated by induction, and the particle size distribution is 5 to 100 nm; the binary compound of sodium salicylate and ammonium nitrate is used as a crystal form control agent to produce whisker-shaped nano calcium carbonate (Chinese patent CN 104975339A); polyethylene glycol is used for inducing and producing spindle-shaped nano calcium carbonate (Chinese patent CN 111268712A) and the like.
The flaky/disc-shaped nano calcium carbonate has the characteristics of strong surface coating force, good printing performance, high smoothness, high glossiness and the like, and is used for the production of high-end paper, coating pigments and the like by foreign researchers. Relatively, the preparation of the flaky nano calcium carbonate in China just starts, and a new regulation and control means is urgently needed to realize the high-efficiency production of the flaky/disc-shaped calcium carbonate.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing disc-shaped nano calcium carbonate by using a polyamidine type guiding agent, which can be used for large-scale high-efficiency production.
In order to solve the problems, the invention provides a method for preparing disc-shaped nano calcium carbonate by using a polyamidine type guiding agent, which is characterized by comprising the following steps: the method is to mix 0.05 to 5 percent of amidine aqueous solution with 6 to 12 percent of Ca (OH) 2 After mixing the aqueous solutions, CO was introduced 2 Reacting gas at 5-30 ℃, monitoring the pH of the system in the reaction process, and continuously introducing CO when the pH reaches 6.8-7.2 2 Stopping the reaction after the gas is used for 10 to 30 min; and after the reaction is finished, filtering and washing the system, and drying to obtain the disc-shaped nano calcium carbonate.
The polyamidine powder in the polyamidine aqueous solution contains five-membered ring amidino units, the surface of the polyamidine powder has positive charges, and the polyamidine aqueous solution has a structural general formula as follows:
in the formula: r 1 、R 2 Is one of H, C1-C8 alkane or aryl, and R 1 、R 2 At least one is an aryl group; n =40 to 110; x = Cl - 、Br - Or HSO 4 - One kind of (1).
The aqueous polyamidine solution is mixed with the Ca (OH) 2 The volume ratio of the aqueous solution is 0.05 to 10 percent.
The CO is 2 The flow rate is controlled to be 0.8 to 2.5L/h per gram of calcium hydroxide.
The CO is 2 The concentration is more than 28 percent.
The drying temperature is 45-105 ℃, and the time is 8-20 h.
Compared with the prior art, the invention has the following advantages:
1. the invention takes the polyamidine containing the five-membered ring structural unit as the structure directing agent, and utilizes the surface charge of the polyamidine and the CO pair thereof 2 With an affinity of aqueous calcium hydroxide with CO 2 The disc-shaped nano calcium carbonate is successfully prepared as a raw material.
2. The method has mild synthesis conditions, has no high requirements on equipment and control means, and is beneficial to large-scale and efficient production of the disc-shaped nano calcium carbonate.
3. The disc-shaped nano calcium carbonate obtained by the invention has the characteristics of uniform crystal grain appearance, narrow size distribution (as shown in figure 2) and the like, can be used as an additive of high-quality paper and coating materials, and can improve the surface smoothness and the glossiness.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows an infrared spectrum of a cyclic polyamidine according to example 1 of the invention.
FIG. 2 is a transmission electron microscope image of the disc-shaped nano calcium carbonate prepared in example 1 of the present invention.
Detailed Description
A method for preparing disk-shaped nano calcium carbonate by using a polyamidine type guiding agent is characterized in that a polyamidine aqueous solution with the concentration of 0.05 to 5 percent and Ca (OH) with the concentration of 6 to 12 percent are used 2 Mixing the aqueous solution, the aqueous solution of polyamidine and Ca (OH) 2 The volume ratio of the aqueous solution is 0.05 to 10%. After mixing, introducing CO with the concentration of more than 28 percent at the flow rate of 0.8 to 2.5L/h per gram of calcium hydroxide 2 Reacting gas at 5 to 30 ℃, monitoring the pH of the system in the reaction process, and continuously introducing CO when the pH reaches 6.8 to 7.2 2 Stopping the reaction after the gas is used for 10 to 30 min; and after the reaction is finished, filtering and washing the system, and drying at 45 to 105 ℃ for 8 to 20 hours to obtain the disc-shaped nano calcium carbonate.
Preferably: the concentration of the polyamidine aqueous solution is 0.25 to 4 percent; CO 2 2 The flow rate is 1 to 1.8L/h per gram of calcium hydroxide; CO 2 2 The concentration of (a) is more than 95%; the synthesis temperature is 10 to 20 ℃.
Wherein: the polyamidine powder in the polyamidine aqueous solution contains five-membered ring amidino units, the surface of the polyamidine powder has positive charges, and the structural general formula of the polyamidine powder is as follows:
in the formula: r 1 、R 2 Is one of H, C1-C8 alkane or aryl, and R 1 、R 2 At least one is an aryl group; n =40 to 110; x = Cl - 、Br - Or HSO 4 - To (3) is provided.
The polyamidine-type directing agents used in the present invention can be synthesized using strategies and methods known in the art (Polymer Science, 2015, 57, 61-70).
The invention adopts calcium hydroxide, carbon dioxide and deionized water which are sold in the market for preparation.
Example 1
Synthesis of R 1 、R 2 Are respectively hydrogen and C 6 H 5 X is Cl - The polyamidine of (a):
8.8 g of N-vinylformamide, 16.0 g of 2-phenylacetonitrile and 20 ml of H are weighed out 2 In O, N 2 15 ml of initiator 2-2' -azoacetamidinylpropane dihydrochloride (1 g/L) was added under protection, and the temperature was raised to 45 ℃ and held for 4 hours. Then 30 ml of 0.5 g/ml aqueous hydrochloric acid were added and the temperature was further raised to 106 ℃ for 4 h. And after the reaction is finished, adding acetone to obtain a precipitated white precipitate, and precipitating, filtering, washing and drying to obtain the target polyamidine.
Infrared spectrum characterization of the target polyamidine is carried out, and as shown in figure 1, 3465 cm can be known -1 The N-H vibration absorption peak of amidino at the vicinity of 2900 to 3050 cm -1 The vibration absorption peak of benzene ring C-H is 1650 to 1450 cm -1 1326 cm as the peak of vibration of the aromatic ring skeleton -2 Is the infrared absorption of the C-N bond.
By the use of R 1 、R 2 Are respectively hydrogen and C 6 H 5 X is Cl - Preparing an aqueous solution of 0.05 percent of the polyamidine and 8 percent of the calcium hydroxide, stirring and mixing the two according to the volume ratio of 10 percent, and introducing CO 2 The gas flow rate is 1.2L/h per gram of calcium hydroxide, and the reaction temperature is 16 ℃. Monitoring the pH value of the system in the reaction process, and continuously introducing CO after the pH value reaches 7 2 And (5) stopping the reaction after the gas is used for 10 min. And after the reaction is finished, filtering, washing and drying at the drying temperature of 60 ℃ to obtain the disc-shaped nano calcium carbonate.
The morphology and the particle size of the obtained disc-shaped nano calcium carbonate are analyzed by a transmission electron microscope, and the result is shown in fig. 2. As can be seen from the figure, the average diameter of the particles is 75 nm, the crystal grains are uniform in appearance and narrow in size distribution.
Example 2
R from example 1 was used 1 、R 2 Are respectively hydrogen and C 6 H 5 X is Cl - Of a polyamidine in a concentration of polyamidine0.08% and 10% calcium hydroxide aqueous solution, stirring and mixing the two according to the volume ratio of 10%, and introducing CO 2 The gas flow rate is 1.2L/h per gram of calcium hydroxide, and the reaction temperature is 16 ℃. Monitoring the pH value of the system in the reaction process, and continuously introducing CO after the pH value reaches 7 2 And (5) stopping the reaction after the gas is used for 10 min. And after the reaction is finished, filtering, washing and drying at the drying temperature of 60 ℃ to obtain the disc-shaped nano calcium carbonate.
Example 3
Synthesis of R 1 、R 2 Are respectively hydrogen and C 7 H 7 X is Cl - The polyamidine of (a):
8.8 g of N-vinylformamide, 17.8 g of 2-benzylacrylonitrile and 20 ml of H are weighed 2 In O, N 2 15 ml of initiator 2-2' -azoacetamidinylpropane dihydrochloride (concentration 1 g/L) was added under protection and the temperature was raised to 45 ℃ and held for 4 h. Then 30 ml of 0.5 g/ml aqueous hydrochloric acid were added and the temperature was further raised to 106 ℃ for 4 h. And after the reaction is finished, adding acetone to obtain a precipitated white precipitate, and precipitating, filtering, washing and drying to obtain the target polyamidine.
By the use of R 1 、R 2 Are respectively hydrogen and C 7 H 7 X is Cl - Preparing an aqueous solution of 0.05 percent of the polyamidine and 7 percent of the calcium hydroxide, stirring and mixing the two according to the volume ratio of 10 percent, and introducing CO 2 The gas flow rate is 1.2L/h per gram of calcium hydroxide, and the reaction temperature is 16 ℃. Monitoring the pH value of the system in the reaction process, and continuously introducing CO after the pH value reaches 7 2 And (5) stopping the reaction after the gas is used for 10 min. And after the reaction is finished, filtering, washing and drying at the drying temperature of 60 ℃ to obtain the disc-shaped nano calcium carbonate.
Comparative example 1
Synthesis of R 1 、R 2 Are respectively hydrogen and X is Cl - The polyamidine of (a):
8.81 g of N-vinylformamide and 6.58 g of acrylonitrile are weighed out in 20 ml of H 2 In O, N 2 15 ml of initiator 2-2' -azoacetamidinylpropane dihydrochloride (concentration 1 g/L) was added under protection and the temperature was raised to 45 ℃ and held for 4 h. Then 30 ml of 0.5 g/ml aqueous hydrochloric acid solution and oneThe temperature is increased to 106 ℃ and kept for 4 h. And after the reaction is finished, adding acetone to obtain a precipitated white precipitate, and precipitating, filtering, washing and drying to obtain the target polyamidine.
By the use of R 1 、R 2 Are respectively hydrogen and X is Cl - Preparing an aqueous solution of 0.05 percent of polyamidine and 8 percent of calcium hydroxide, stirring and mixing the two according to the volume ratio of 10 percent, and introducing CO 2 The gas flow rate is 1.2L/h per gram of calcium hydroxide, and the reaction temperature is 16 ℃. Monitoring the pH value of the system in the reaction process, and continuously introducing CO after the pH value reaches 7 2 And (5) stopping the reaction after the gas is used for 10 min. After the reaction is finished, filtering, washing and drying are carried out, wherein the drying temperature is 60 ℃, irregular nano calcium carbonate is obtained, and the disc and the rod-shaped nano calcium carbonate are mixed.
Comparative example 2
Preparing aqueous solution with calcium hydroxide concentration of 10%, stirring while introducing CO 2 The gas flow rate is 1.2L/h per gram of calcium hydroxide, and the reaction temperature is 16 ℃. Monitoring the pH value of the system in the reaction process, and continuously introducing CO after the pH value reaches 7 2 And (5) stopping the reaction after the gas is used for 10 min. After the reaction is finished, filtering, washing and drying are carried out, wherein the drying temperature is 60 ℃, and the scalelike nano calcium carbonate is obtained.
As can be seen from comparative examples 1 to 2, when no directing agent is added or the structure of the selected cyclic polyamidine directing agent does not contain an aromatic ring unit, regular discotic nano calcium carbonate cannot be induced to be generated even through a similar carbonization process. This further illustrates the necessity of the cyclic polyamidine structure employed in this case.
The foregoing is illustrative of the present invention and is not to be construed as limiting thereof. All such modifications and substitutions are intended to be included within the scope of the present invention.
Claims (6)
1. A method for preparing disc-shaped nano calcium carbonate by using a polyamidine type guiding agent is characterized by comprising the following steps: the method comprises the steps of mixing an aqueous solution of polyamidine with the concentration of 0.05 to 5 percent and Ca (OH) with the concentration of 6 to 12 percent 2 After mixing the aqueous solutions, CO was introduced 2 Reacting gas at 5 to 30 ℃, monitoring the pH value of the system in the reaction process,continuously introducing CO when the temperature reaches 6.8 to 7.2 2 Stopping the reaction after the gas is used for 10 to 30 min; and after the reaction is finished, filtering and washing the system, and drying to obtain the disc-shaped nano calcium carbonate.
2. The method of claim 1, wherein the disc-shaped nano calcium carbonate is prepared by using a polyamidine-type directing agent, wherein: the polyamidine powder in the polyamidine aqueous solution contains five-membered ring amidino units, the surface of the polyamidine powder is provided with positive charges, and the structural general formula of the polyamidine powder is as follows:
in the formula: r 1 、R 2 Is one of H, C1-C8 alkane or aryl, and R 1 、R 2 At least one is an aryl group; n =40 to 110; x = Cl - 、Br - Or HSO 4 - One kind of (1).
3. The method of claim 1, wherein the disc-shaped nanocalcium carbonate is prepared using a polyamidine-type directing agent, and the method comprises the following steps: the aqueous polyamidine solution is mixed with the Ca (OH) 2 The volume ratio of the aqueous solution is 0.05 to 10 percent.
4. The method of claim 1, wherein the disc-shaped nanocalcium carbonate is prepared using a polyamidine-type directing agent, and the method comprises the following steps: said CO 2 The flow rate is controlled to be 0.8 to 2.5L/h per gram of calcium hydroxide.
5. The method of claim 1, wherein the disc-shaped nanocalcium carbonate is prepared using a polyamidine-type directing agent, and the method comprises the following steps: the CO is 2 The concentration is more than 28 percent.
6. The method of claim 1, wherein the disc-shaped nanocalcium carbonate is prepared using a polyamidine-type directing agent, and the method comprises the following steps: the drying temperature is 45-105 ℃, and the time is 8-20 h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210984466.4A CN115259197B (en) | 2022-08-17 | 2022-08-17 | Method for preparing disc-shaped nano calcium carbonate by using polyamidine type guiding agent |
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| CN1333802A (en) * | 1998-11-13 | 2002-01-30 | 三井化学株式会社 | Organic polymer/fine inorganic particle aqueous dispersion with excellent dispersion stability and use thereof |
| JP2004210631A (en) * | 2002-12-18 | 2004-07-29 | Maruo Calcium Co Ltd | Calcium carbonate having uneven surface and its manufacturing method |
| WO2005061386A1 (en) * | 2003-12-16 | 2005-07-07 | Imerys Pigments, Inc. | Method and system for growing larger precipitated calcium carbonate crystals |
| JP2007126333A (en) * | 2005-11-04 | 2007-05-24 | New Raimu Kenkyusha:Kk | Vaterite type disk-shaped calcium carbonate and its production method |
| CN102963918A (en) * | 2012-11-08 | 2013-03-13 | 广西华纳新材料科技有限公司 | Carbonation reaction method of nano calcium carbonate |
| CN102976387A (en) * | 2012-12-07 | 2013-03-20 | 陕西科技大学 | Improved preparation technology of white mud calcium carbonate for papermaking filler |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333802A (en) * | 1998-11-13 | 2002-01-30 | 三井化学株式会社 | Organic polymer/fine inorganic particle aqueous dispersion with excellent dispersion stability and use thereof |
| JP2004210631A (en) * | 2002-12-18 | 2004-07-29 | Maruo Calcium Co Ltd | Calcium carbonate having uneven surface and its manufacturing method |
| WO2005061386A1 (en) * | 2003-12-16 | 2005-07-07 | Imerys Pigments, Inc. | Method and system for growing larger precipitated calcium carbonate crystals |
| JP2007126333A (en) * | 2005-11-04 | 2007-05-24 | New Raimu Kenkyusha:Kk | Vaterite type disk-shaped calcium carbonate and its production method |
| CN102963918A (en) * | 2012-11-08 | 2013-03-13 | 广西华纳新材料科技有限公司 | Carbonation reaction method of nano calcium carbonate |
| CN102976387A (en) * | 2012-12-07 | 2013-03-20 | 陕西科技大学 | Improved preparation technology of white mud calcium carbonate for papermaking filler |
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