CN111439768B - Preparation method of high-activity nano calcium hydroxide - Google Patents
Preparation method of high-activity nano calcium hydroxide Download PDFInfo
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- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 title claims abstract description 63
- 239000000920 calcium hydroxide Substances 0.000 title claims abstract description 63
- 229910001861 calcium hydroxide Inorganic materials 0.000 title claims abstract description 63
- 230000000694 effects Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 33
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000292 calcium oxide Substances 0.000 claims abstract description 33
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 13
- ANJPRQPHZGHVQB-UHFFFAOYSA-N hexyl isocyanate Chemical compound CCCCCCN=C=O ANJPRQPHZGHVQB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 239000004202 carbamide Substances 0.000 claims description 17
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 5
- 235000013539 calcium stearate Nutrition 0.000 claims description 5
- 239000008116 calcium stearate Substances 0.000 claims description 5
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 5
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 5
- QCEOZLISXJGWSW-UHFFFAOYSA-K 1,2,3,4,5-pentamethylcyclopentane;trichlorotitanium Chemical compound [Cl-].[Cl-].[Cl-].CC1=C(C)C(C)([Ti+3])C(C)=C1C QCEOZLISXJGWSW-UHFFFAOYSA-K 0.000 claims description 3
- QOXHZZQZTIGPEV-UHFFFAOYSA-K cyclopenta-1,3-diene;titanium(4+);trichloride Chemical compound Cl[Ti+](Cl)Cl.C=1C=C[CH-]C=1 QOXHZZQZTIGPEV-UHFFFAOYSA-K 0.000 claims description 3
- ZQIDWLVPOWGCCM-UHFFFAOYSA-N CC1=C(C(=C(C(=C1CO[Ti](OCC1=CC=CC=C1)(OCC1=CC=CC=C1)C1C=CC=C1)C)C)C)C Chemical compound CC1=C(C(=C(C(=C1CO[Ti](OCC1=CC=CC=C1)(OCC1=CC=CC=C1)C1C=CC=C1)C)C)C)C ZQIDWLVPOWGCCM-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 15
- 239000000047 product Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000843 powder Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- -1 pentamethylcyclopentadienyl tribenzyloxy titanium trichloride Chemical compound 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- 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
- C01F11/02—Oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
-
- 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
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of high-activity nano calcium hydroxide, which comprises the steps of dissolving hydroxyl-terminated polybutadiene in toluene, adding an organic titanium catalyst, adding triethylamine, reacting under stirring to obtain a mixed solution, and performing centrifugal separation on the mixed solution to remove precipitates to obtain a solution A; adding n-hexyl isocyanate into the solution A for reaction, then adding methanol with the same volume, filtering to obtain a precipitate B, then adding water into the precipitate B, heating to 70 ℃ under the stirring condition, keeping the temperature constant, after the precipitate B is completely dissolved, rapidly cooling to room temperature to obtain a mixture C, and then adding high-purity calcium oxide into the mixture C for reaction to obtain a mixture D; and then slowly heating the mixture B to 60-70 ℃, filtering to obtain a precipitate E and a filtrate, and drying the precipitate E in vacuum to obtain the nano calcium hydroxide. The method is convenient to control the crystal form and the structure of the nano calcium hydroxide in the production process, and a high-activity nano calcium hydroxide product is obtained.
Description
Technical Field
The invention belongs to the technical field of calcium hydroxide production, and particularly relates to a preparation method of high-activity nano calcium hydroxide.
Background
Calcium hydroxide is a strong base, has bactericidal and preservative capabilities, and is widely applied in industry. It is a common building material and also used as a bactericide, a chemical raw material and the like. The conventional preparation method of calcium hydroxide comprises a lime slaking method, namely, after limestone is calcined into calcium oxide, the limestone is selected and is slaked with water in proportion to generate calcium hydroxide feed liquid, the calcium hydroxide feed liquid is purified, separated and deslagged, and then is centrifugally dehydrated, dried and screened to obtain a finished product of calcium hydroxide; or dissolving calcium chloride in water, heating, adding filtered sodium hydroxide solution, reacting to obtain calcium hydroxide, suction filtering the obtained slurry mixture, washing, and washing with sodium hydroxide solution to remove a large amount of chloride ions to obtain the final product of calcium hydroxide. However, the calcium hydroxide powder obtained by the above method has irregular shape and larger particle size, and sometimes further optimization is performed to obtain nano calcium hydroxide with high specific surface area, for example, a method for preparing nano calcium hydroxide powder is disclosed in chinese patent application No. CN201510931831.5, which includes the following steps: a) mixing a dispersing agent and a surfactant in a liquid medium according to a proportion to form a dissolved solution; b) reacting the dissolved solution, the high-purity calcium oxide and the defoaming agent in a ball mill to form suspension slurry; c) and drying the slurry by using a sprayer, and ball-milling and scattering to obtain the nano-scale calcium hydroxide powder. The nano calcium hydroxide powder prepared by the method has the advantages of high product yield, stable quality, narrow particle size distribution, easily controlled reaction conditions and suitability for industrial production. However, the existing preparation methods of nano calcium hydroxide focus on controlling the particle size of nano calcium hydroxide, neglect the control of the crystal form of nano calcium hydroxide, nano calcium hydroxide prepared by different methods can present different structures and crystal forms, different structures and crystal forms can influence the application of nano calcium hydroxide, and some structures can limit the application of nano calcium hydroxide.
Disclosure of Invention
Aiming at the defects, the invention discloses a preparation method of high-activity nano calcium hydroxide, which is convenient for controlling the crystal form and the structure of the nano calcium hydroxide in the production process and obtaining a high-activity nano calcium hydroxide product.
The invention is realized by adopting the following technical scheme:
a preparation method of high-activity nano calcium hydroxide comprises the following steps:
(1) dissolving hydroxyl-terminated polybutadiene in toluene, adding an organic titanium catalyst, adding triethylamine, reacting for 12-24 hours under a stirring condition to obtain a mixed solution, and performing centrifugal separation on the mixed solution to remove precipitates to obtain a solution A; the mass ratio of the hydroxyl-terminated polybutadiene to the toluene is (0.12-0.15) g:1ml, the mass ratio of the organic titanium catalyst to the hydroxyl-terminated polybutadiene is (3-4) 1, and the mass ratio of the hydroxyl-terminated polybutadiene to the triethylamine is (5-6) g:1 ml;
(2) adding n-hexyl isocyanate into the solution A to react for 24-32 h, then adding methanol with the same volume, filtering to obtain a precipitate B, then adding water into the precipitate B, heating to 70 ℃ under stirring, keeping the temperature constant, after the precipitate B is completely dissolved, rapidly cooling to room temperature to obtain a mixture C, wherein the mass ratio of water to the precipitate B in the mixture C is 1 (0.05-0.1), then adding high-purity calcium oxide into the mixture C to react, after 15-20 min, respectively adding stearate and urea, after the addition of the high-purity calcium oxide, the stearate and the urea is completed, continuing to react for 50-90 min to obtain a mixture D; the molar ratio of the n-hexyl isocyanate to the hydroxyl-terminated polybutadiene is (80-100): 1, the addition amount of the high-purity calcium oxide is 20-30% of the mass of water, and the mass ratio of the high-purity calcium oxide, the stearate and the urea is 1 (0.01-0.02): 0.01-0.02);
(3) and slowly heating the mixture D to 60-70 ℃, filtering to obtain a precipitate E and a filtrate, and drying the precipitate E in vacuum to obtain the nano calcium hydroxide.
Further, the organic titanium catalyst in the step (1) is any one of cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride and pentamethylcyclopentadienyl tribenzyloxy titanium trichloride.
Further, the stirring speed in the step (1) is 100-200 r/min.
Further, after the precipitate B is completely dissolved in the step (2), rapidly cooling to room temperature at a cooling speed of 5-10 ℃/min to obtain a mixture C. The polymer chains can move freely by controlling the cooling speed and gradually form a network structure with the lowest free energy through physical action, if the cooling speed is too low, the polymer chains can ensure the lowest energy state at the current temperature by continuously adjusting the spatial distribution and the connection length, and finally the polymer chains cannot reach the equilibrium state and cannot form a gel state.
Further, the purity of the high-purity calcium oxide in the step (2) is more than 95%.
Further, in the step (2), the stearate is any one of sodium stearate, zinc stearate and calcium stearate.
Further, in the step (3), the mixture B is slowly heated to 60-70 ℃ according to a temperature rise speed of 2-3 ℃/min. The free movement of macromolecules in the gel can be ensured to break the original structure by controlling the temperature rise, and meanwhile, the agglomeration phenomenon of nano calcium hydroxide particles can not occur due to the temperature rise of the nano calcium hydroxide crystals.
Further, the filtrate obtained in the step (3) is recovered, then cooled to room temperature, and the filtrate is mixed with water to dissolve the precipitate B in the step (2).
Compared with the prior art, the technical scheme has the following beneficial effects:
1. according to the invention, hydroxyl-terminated polybutadiene and n-hexyl isocyanate are used and made into thermoreversible gel under the action of an organic titanium catalyst to serve as a crystallization medium of calcium hydroxide, calcium hydroxide molecules are continuously transmitted to a growth surface by utilizing a network structure of the gel, so that the crystal growth of the calcium hydroxide molecules is more regular, the crystal morphology can be maintained, the interaction between the crystal and the wall of a crystallizer or between the crystal and other crystals can be reduced, the crystallization speed of nano calcium hydroxide is improved, and the calcium hydroxide can be crystallized in a mild and non-pressurized environment; meanwhile, the stearic salt and the urea are added, so that under the combined action of the stearic salt and the urea, the crystal form of the calcium hydroxide crystal is improved, the generation of a calcium hydroxide product into a vaterite crystal with a smaller crystal form is promoted, the surface property of the nano calcium hydroxide is improved, the dispersity is improved, and the particle agglomeration phenomenon is prevented.
2. The invention uses the thermal reversible gel to form the gel with a stable grid structure at normal temperature by means of chemical crosslinking among molecular chains, physical action formed by macromolecule entanglement or self-assembly of a supermolecule structure and the like, when the gel is heated to a higher temperature, macromolecules in the solution move freely to aggravate and destroy the original structure and recover to a solution state.
3. The method has the advantages of simple process, convenient operation and strong controllability, and is suitable for the automatic and industrial production of nano calcium hydroxide products.
Detailed Description
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto. The specific experimental conditions and methods not indicated in the following examples are generally conventional means well known to those skilled in the art.
Example 1:
a preparation method of high-activity nano calcium hydroxide comprises the following steps:
(1) dissolving hydroxyl-terminated polybutadiene in toluene, adding an organic titanium catalyst, adding triethylamine, reacting for 18 hours under the stirring condition at the speed of 100r/min to obtain a mixed solution, and performing centrifugal separation on the mixed solution to remove precipitates to obtain a solution A; the mass ratio of the hydroxyl-terminated polybutadiene to the toluene is 0.12g:1ml, the mass ratio of the organic titanium catalyst to the hydroxyl-terminated polybutadiene is 3:1, and the mass ratio of the hydroxyl-terminated polybutadiene to the triethylamine is 5g:1 ml; the organic titanium catalyst is cyclopentadienyl titanium trichloride;
(2) adding n-hexyl isocyanate into the solution A for reaction for 30 hours, then adding methanol with the same volume, filtering to obtain a precipitate B, then adding water into the precipitate B, heating to 70 ℃ under stirring, keeping the temperature constant, after the precipitate B is completely dissolved, rapidly cooling to room temperature according to the cooling speed of 8 ℃/min to obtain a mixture C, adding high-purity calcium oxide into the mixture C according to the mass ratio of the water to the precipitate B of 1:0.05, then adding the high-purity calcium oxide into the mixture C for reaction, respectively adding zinc stearate and urea after the high-purity calcium oxide is added for 15min, and continuing to react for 65min after the high-purity calcium oxide, the zinc stearate and the urea are added to obtain a mixture D; the molar ratio of the n-hexyl isocyanate to the hydroxyl-terminated polybutadiene is 100:1, the addition amount of the high-purity calcium oxide is 20% of the mass of water, and the mass ratio of the high-purity calcium oxide to the zinc stearate to the urea is 1:0.01: 0.01; the purity of the high-purity calcium oxide is more than 95 percent;
(3) and slowly heating the mixture D to 65 ℃ according to the heating rate of 2 ℃/min, then filtering to obtain a precipitate E and a filtrate, and drying the precipitate E in vacuum to obtain the nano calcium hydroxide.
The purity of the nano calcium hydroxide obtained by the method of the embodiment is 99.7%, the particle size is 30-40 nm, and the specific surface area of the nano calcium hydroxide is 86m2/g。
Example 2:
a preparation method of high-activity nano calcium hydroxide comprises the following steps:
(1) dissolving hydroxyl-terminated polybutadiene in toluene, adding an organic titanium catalyst, adding triethylamine, reacting for 24 hours under the stirring condition of the speed of 150r/min to obtain a mixed solution, and performing centrifugal separation on the mixed solution to remove precipitates to obtain a solution A; the mass ratio of the hydroxyl-terminated polybutadiene to the toluene is 0.15g:1ml, the mass ratio of the organic titanium catalyst to the hydroxyl-terminated polybutadiene is 4:1, and the mass ratio of the hydroxyl-terminated polybutadiene to the triethylamine is 6g:1 ml; the organic titanium catalyst is pentamethyl cyclopentadienyl titanium trichloride;
(2) adding n-hexyl isocyanate into the solution A for reaction for 32 hours, then adding methanol with the same volume, filtering to obtain a precipitate B, then adding water into the precipitate B, heating to 70 ℃ under stirring, keeping the temperature constant, after the precipitate B is completely dissolved, rapidly cooling to room temperature according to the cooling speed of 10 ℃/min to obtain a mixture C, adding high-purity calcium oxide into the mixture C according to the mass ratio of the water to the precipitate B of 1:0.075, then adding the high-purity calcium oxide into the mixture C for reaction, respectively adding calcium stearate and urea after 18min of starting adding the high-purity calcium oxide, and continuing to react for 90min after the addition of the high-purity calcium oxide, the calcium stearate and the urea is completed to obtain a mixture D; the molar ratio of the n-hexyl isocyanate to the hydroxyl-terminated polybutadiene is 90:1, the addition amount of the high-purity calcium oxide is 25% of the mass of water, and the mass ratio of the high-purity calcium oxide to the calcium stearate to the urea is 1:0.02: 0.02; the purity of the high-purity calcium oxide is more than 95 percent;
(3) and slowly heating the mixture D to 70 ℃ according to the heating rate of 3 ℃/min, then filtering to obtain a precipitate E and a filtrate, and drying the precipitate E in vacuum to obtain the nano calcium hydroxide.
The purity of the nano calcium hydroxide obtained by the method of the embodiment is 99.7%, the particle size is 10-15 nm, and the specific surface area of the nano calcium hydroxide is 95m2/g。
Example 3:
a preparation method of high-activity nano calcium hydroxide comprises the following steps:
(1) dissolving hydroxyl-terminated polybutadiene in toluene, adding an organic titanium catalyst, adding triethylamine, reacting for 12 hours under the stirring condition at the speed of 200r/min to obtain a mixed solution, and performing centrifugal separation on the mixed solution to remove precipitates to obtain a solution A; the mass ratio of the hydroxyl-terminated polybutadiene to the toluene is 0.135g:1ml, the mass ratio of the organic titanium catalyst to the hydroxyl-terminated polybutadiene is 3.6:1, and the mass ratio of the hydroxyl-terminated polybutadiene to the triethylamine is 5.5g:1 ml; the organic titanium catalyst is pentamethyl cyclopentadienyl tribenzyloxy titanium;
(2) adding n-hexyl isocyanate into the solution A for reacting for 24 hours, then adding methanol with the same volume, filtering to obtain a precipitate B, then adding water into the precipitate B, heating to 70 ℃ under stirring, keeping the temperature constant, after the precipitate B is completely dissolved, rapidly cooling to room temperature according to the cooling speed of 5 ℃/min to obtain a mixture C, adding high-purity calcium oxide into the mixture C according to the mass ratio of the water to the precipitate B of 1:0.1, reacting, adding sodium stearate and urea after the high-purity calcium oxide is added for 20min, and continuing to react for 50min after the high-purity calcium oxide, the sodium stearate and the urea are added to obtain a mixture D; the molar ratio of the n-hexyl isocyanate to the hydroxyl-terminated polybutadiene is 80:1, the addition amount of the high-purity calcium oxide is 30% of the mass of water, and the mass ratio of the high-purity calcium oxide to the sodium stearate to the urea is 1:0.0125: 0.015; the purity of the high-purity calcium oxide is more than 95 percent;
(3) and slowly heating the mixture D to 60 ℃ according to the heating rate of 3 ℃/min, then filtering to obtain a precipitate E and a filtrate, and drying the precipitate E in vacuum to obtain the nano calcium hydroxide.
The purity of the nano calcium hydroxide obtained by the method of the embodiment is 99.5%, the particle size is 45-60 nm, and the specific surface area of the nano calcium hydroxide is 82m2/g。
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (8)
1. A preparation method of high-activity nano calcium hydroxide is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving hydroxyl-terminated polybutadiene in toluene, adding an organic titanium catalyst, adding triethylamine, reacting for 12-24 hours under a stirring condition to obtain a mixed solution, and performing centrifugal separation on the mixed solution to remove precipitates to obtain a solution A; the mass ratio of the hydroxyl-terminated polybutadiene to the toluene is (0.12-0.15) g:1ml, the mass ratio of the organic titanium catalyst to the hydroxyl-terminated polybutadiene is (3-4) 1, and the mass ratio of the hydroxyl-terminated polybutadiene to the triethylamine is (5-6) g:1 ml;
(2) adding n-hexyl isocyanate into the solution A to react for 24-32 h, then adding methanol with the same volume, filtering to obtain a precipitate B, then adding water into the precipitate B, heating to 70 ℃ under stirring, keeping the temperature constant, after the precipitate B is completely dissolved, rapidly cooling to room temperature to obtain a mixture C, wherein the mass ratio of water to the precipitate B in the mixture C is 1 (0.05-0.1), then adding high-purity calcium oxide into the mixture C to react, after 15-20 min, respectively adding stearate and urea, after the addition of the high-purity calcium oxide, the stearate and the urea is completed, continuing to react for 50-90 min to obtain a mixture D; the molar ratio of the n-hexyl isocyanate to the hydroxyl-terminated polybutadiene is (80-100): 1, the addition amount of the high-purity calcium oxide is 20-30% of the mass of water, and the mass ratio of the high-purity calcium oxide, the stearate and the urea is 1 (0.01-0.02): 0.01-0.02);
(3) and slowly heating the mixture D to 60-70 ℃, filtering to obtain a precipitate E and a filtrate, and drying the precipitate E in vacuum to obtain the nano calcium hydroxide.
2. The method for preparing high-activity nano calcium hydroxide according to claim 1, which is characterized in that: the organic titanium catalyst in the step (1) is any one of cyclopentadienyl titanium trichloride, pentamethyl cyclopentadienyl titanium trichloride and pentamethyl cyclopentadienyl tribenzyloxy titanium.
3. The method for preparing high-activity nano calcium hydroxide according to claim 1, which is characterized in that: the stirring speed in the step (1) is 100-200 r/min.
4. The method for preparing high-activity nano calcium hydroxide according to claim 1, which is characterized in that: and (3) after the precipitate B is completely dissolved in the step (2), rapidly cooling to room temperature at a cooling speed of 5-10 ℃/min to obtain a mixture C.
5. The method for preparing high-activity nano calcium hydroxide according to claim 1, which is characterized in that: the purity of the high-purity calcium oxide in the step (2) is more than 95%.
6. The method for preparing high-activity nano calcium hydroxide according to claim 1, which is characterized in that: the stearate in the step (2) is any one of sodium stearate, zinc stearate and calcium stearate.
7. The method for preparing high-activity nano calcium hydroxide according to claim 1, which is characterized in that: in the step (3), the mixture B is slowly heated to 60-70 ℃ according to the heating rate of 2-3 ℃/min.
8. The method for preparing high-activity nano calcium hydroxide according to claim 1, which is characterized in that: and (3) recovering the obtained filtrate in the step (3), cooling to room temperature, and mixing the filtrate with water for dissolving the precipitate B in the step (2).
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