CN109399683B - Preparation method of nano calcium carbonate for yield enhancement of PVC (polyvinyl chloride) automobile primer - Google Patents
Preparation method of nano calcium carbonate for yield enhancement of PVC (polyvinyl chloride) automobile primer 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 102
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 51
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 39
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000839 emulsion Substances 0.000 claims abstract description 78
- 239000003607 modifier Substances 0.000 claims abstract description 40
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 23
- 239000013078 crystal Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000003292 glue Substances 0.000 claims abstract description 10
- 235000019738 Limestone Nutrition 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 230000029087 digestion Effects 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000006028 limestone Substances 0.000 claims abstract description 7
- 230000009974 thixotropic effect Effects 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000007873 sieving Methods 0.000 claims abstract description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000292 calcium oxide Substances 0.000 claims description 27
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 27
- 239000012066 reaction slurry Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 12
- 239000000920 calcium hydroxide Substances 0.000 claims description 12
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 239000004006 olive oil Substances 0.000 claims description 5
- 235000008390 olive oil Nutrition 0.000 claims description 5
- 235000019483 Peanut oil Nutrition 0.000 claims description 4
- 239000003240 coconut oil Substances 0.000 claims description 4
- 235000019864 coconut oil Nutrition 0.000 claims description 4
- 239000000312 peanut oil Substances 0.000 claims description 4
- 229940077386 sodium benzenesulfonate Drugs 0.000 claims description 4
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 4
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 4
- ZTEPAMQURYRDPM-UHFFFAOYSA-M sodium;n,n-diethylcarbamothioate Chemical compound [Na+].CCN(CC)C([O-])=S ZTEPAMQURYRDPM-UHFFFAOYSA-M 0.000 claims description 4
- 239000011362 coarse particle Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- KFZUDNZQQCWGKF-UHFFFAOYSA-M sodium;4-methylbenzenesulfinate Chemical group [Na+].CC1=CC=C(S([O-])=O)C=C1 KFZUDNZQQCWGKF-UHFFFAOYSA-M 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 8
- 238000010790 dilution Methods 0.000 abstract description 2
- 239000012895 dilution Substances 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract description 2
- 239000010419 fine particle Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 14
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 12
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 12
- 239000002987 primer (paints) Substances 0.000 description 10
- 235000011837 pasties Nutrition 0.000 description 8
- 239000008187 granular material Substances 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 229920001944 Plastisol Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000004999 plastisol Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 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
- C01F11/18—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
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A preparation method of nano calcium carbonate for yield enhancement of PVC (polyvinyl chloride) automobile primer glue comprises the following steps: (1) calcining and crushing limestone into fine particles; adding hot water for digestion; (2) sieving to obtain emulsion; (3) adding water for dilution, and placing the solution in a micro-bubble type superfine calcium carbonate synthesis reactor when the temperature is less than or equal to 30 ℃; (4) introducing mixed gas during stirring; when the conductivity is increased after the first time of reduction to the bottom of the grain, adding a crystal touch change modifier; standing when the conductivity rises back to the initial value; while stirring again, aerating until the pH is 7; (5) placing the mixture in a reaction kettle for heating and heat preservation. Adding the surface thixotropic modifier and stirring uniformly; (6) filtering, drying and crushing. The product obtained by the method can effectively improve the yield value of the rubber product under the condition of the same viscosity.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of nano calcium carbonate for yield enhancement of PVC (polyvinyl chloride) automobile primer.
Background
At present, most of automobile bottom glue is a PVC plastisol product, and the main components of the automobile bottom glue are base materials, fillers, plasticizers, adhesives and other auxiliary materials. The PVC automobile primer needs good stone impact resistance, relatively low construction viscosity and high yield value, so that the PVC automobile primer is easy to spray in the construction process and can keep the form of the PVC automobile primer not to flow after spraying.
The nano calcium carbonate is used as a common filler in the automobile bottom coating, so that the cost can be reduced, and the rheological property of the automobile bottom coating can be improved; evaluating the influence of the nano calcium carbonate on the viscosity and yield value of the prepared glue for PVC automobile, wherein the viscosity and yield value of the mixed paste emulsion of the nano calcium carbonate and a plasticizer (DOP) can be detected for characterization; the existing common nano calcium carbonate product has moderate viscosity, low yield value and too high viscosity with high yield value. If 50g of common nano calcium carbonate and 70g of DOP are mixed and dissolved, a Haake viscometer is used for detecting the pasty emulsion, and the Bingham viscosity is generally 700-1200 mPas and the yield value is 200-500 Pa.
Due to the needs of the industrial fields such as adhesives and the like, calcium carbonate products for reducing viscosity and improving yield value or research results are published at home and abroad; some of these efforts have been directed to treating the surface of calcium carbonate particles with low molecular weight fatty acids such as lauric acid, myristic acid, etc. to obtain a low viscosity calcium carbonate product; some calcium carbonate products are treated on the surface by adopting high molecular weight fatty acid such as palmitic acid, stearic acid and the like to obtain high thixotropy calcium carbonate products; some calcium carbonate products are prepared by mixing low molecular weight fatty acid and high molecular weight fatty acid according to a specified ratio to treat the surface of calcium carbonate so as to obtain the calcium carbonate product with viscosity and yield value between the viscosity and the yield value. However, with the development of the adhesive industry and the further improvement of the requirements on the performance of the adhesive product, the defects of the calcium carbonate products are exposed, and the existing products cannot meet the requirements of PVC primer coating; there is a need for calcium carbonate having lower viscosity, higher yield value, and higher adhesive bonding strength and film-forming mechanical strength.
Disclosure of Invention
The invention aims to provide a preparation method of nano calcium carbonate for yield enhancement of PVC (polyvinyl chloride) automobile base coat adhesive, which is characterized in that a modifier is added in the carbonization reaction process and subjected to static reaction, and then the surface treatment is carried out by the modifier in the continuous carbonization reaction, so that the nano calcium carbonate has the property of easy dispersion, and when the nano calcium carbonate is used for the PVC automobile base coat adhesive, the PVC automobile base coat adhesive is endowed with higher yield value, good mechanical property and excellent construction performance under the condition of moderate viscosity.
The method of the invention is carried out according to the following steps:
1. calcining limestone into calcium oxide at 800-1000 ℃, and then crushing until the particle size is less than or equal to 20mm to prepare calcium oxide fine granules; adding hot water with the temperature of 95-100 ℃ into the calcium oxide fine granules for digestion to prepare digested slurry; wherein the adding amount of the hot water is 3-6 times of the mass of the calcium oxide fine powder;
2. sieving the digested slurry with 400 mesh sieve to remove coarse particles and impurities to obtain calcium hydroxide emulsion;
3. a micro-bubble type superfine calcium carbonate synthesis reactor is adopted as synthesis reaction equipment; adding water into the calcium hydroxide emulsion to dilute the calcium hydroxide emulsion until the mass concentration is 6-9% to prepare diluted emulsion; when the temperature of the diluted emulsion is reduced to be less than or equal to 30 ℃, placing the diluted emulsion in synthesis reaction equipment;
4. introducing mixed gas into the diluted emulsion under the stirring condition for synthesis; detecting the conductivity and pH value of the diluted emulsion on line during synthesis; when the conductivity of the diluted emulsion is reduced to the valley bottom for the first time and then the diluted emulsion is raised, adding a crystal touch change modifier into the diluted emulsion, wherein the addition amount of the crystal touch change modifier accounts for 0.5-1% of the total mass of the calcium oxide fine powder; the crystal touch change modifier is sodium p-toluenesulfinate, sodium benzenesulfonate, sodium lignosulfonate or sodium diethylthiocarbamate; when the conductivity of the diluted emulsion is increased back to the value at the beginning of synthesis, stopping introducing the mixed gas and stopping stirring, and standing the diluted emulsion for 30-50 min; introducing mixed gas into the diluted emulsion under the stirring condition for synthesis, and stopping reaction until the pH value of the diluted emulsion is reduced to 7 to obtain reaction slurry; the volume percentage of carbon dioxide in the mixed gas is 30-80%, and the balance is air;
5. placing the reaction slurry in a reaction kettle, heating to 90-120 ℃, standing and preserving heat for 20-30 min, then adding a surface thixotropic modifier, uniformly stirring, and carrying out wet modification treatment to obtain modified slurry; wherein the surface contact change modifier accounts for 2-6% of the total mass of calcium carbonate in the reaction slurry; the surface contact change modifier is modified coconut oil, modified olive oil or modified peanut oil;
6. and filtering the modified slurry, drying to remove water, and crushing the agglomerated part to prepare the nano calcium carbonate for PVC automobile primer yield enhancement.
The particle size D50 of the nano calcium carbonate for yield enhancement of the PVC automobile primer glue is less than or equal to 100nm, and the specific surface area is 30-130 m2/g。
In the method, a crystal touch change modifier is added for primary modification treatment during synthesis, then the surface of calcium carbonate particles in reaction slurry is subjected to autonomous modification in the standing and heat preservation process, and a surface thixotropic modifier is added for secondary modification treatment to ensure that the nano calcium carbonate has the property of easy dispersion; mixing nano calcium carbonate for PVC (polyvinyl chloride) automobile prime coat adhesive yield enhancement and DOP (dioctyl phthalate) according to the mass ratio of 5:7 to prepare a pasty emulsion; the Bingham viscosity of the pasty emulsion is 700-1200 mPas, the yield value is 800-1100 Pa, namely the yield value of the adhesive product can be effectively improved under the condition of the same viscosity.
Detailed Description
The water used in the examples of the present invention is deionized water.
The micro-bubble type superfine calcium carbonate synthesis reactor adopted in the embodiment of the invention is the micro-bubble type superfine calcium carbonate synthesis reactor in the patent with the publication number of CN 204434303U.
The sodium p-toluenesulfinate, the sodium benzenesulfonate, the sodium lignosulfonate and the sodium diethylthiocarbamate adopted in the embodiment of the invention are commercially available products.
The modified coconut oil, the modified olive oil or the modified peanut oil adopted in the embodiment of the invention are commercially available products.
DOP (dioctyl phthalate) used in the examples of the present invention was a commercially available product.
In the embodiment of the invention, the dilution to the mass concentration of 6-9% means that the mass concentration of calcium hydroxide is 6-9%.
Example 1
1. Calcining limestone into calcium oxide at 950 ℃, and then crushing until the particle size is less than or equal to 20mm to prepare calcium oxide fine granules; adding hot water with the temperature of 95 ℃ into the calcium oxide fine granules for digestion to prepare digested slurry; wherein the adding amount of the hot water is 3 times of the mass of the calcium oxide fine powder;
2. sieving the digested slurry with 400 mesh sieve to remove coarse particles and impurities to obtain calcium hydroxide emulsion;
3. a micro-bubble type superfine calcium carbonate synthesis reactor is adopted as synthesis reaction equipment; adding water to dilute the calcium hydroxide emulsion to 6% of mass concentration to prepare diluted emulsion; when the temperature of the diluted emulsion is reduced to 30 ℃, placing the diluted emulsion in synthesis reaction equipment;
4. introducing mixed gas into the diluted emulsion under the stirring condition for synthesis; detecting the conductivity and pH value of the diluted emulsion on line during synthesis; when the conductivity of the diluted emulsion is reduced to the bottom of the valley for the first time and then the diluted emulsion is raised, adding a crystal touch change modifier into the diluted emulsion, wherein the addition amount of the crystal touch change modifier accounts for 0.5 percent of the total mass of the calcium oxide fine powder; the crystal touch change modifier is sodium paratoluenesulfite; when the conductivity of the diluted emulsion is increased back to the value at the beginning of synthesis, stopping introducing the mixed gas and stopping stirring, and standing the diluted emulsion for 30 min; introducing mixed gas into the diluted emulsion under the stirring condition for synthesis, and stopping reaction until the pH value of the diluted emulsion is reduced to 7 to obtain reaction slurry; the volume percentage of carbon dioxide in the mixed gas is 30 percent, and the balance is air;
wherein the conductivity of the diluted emulsion is 7.7ms/cm when the synthesis is started, the conductivity is 4.1ms/cm when the diluted emulsion is firstly reduced to the bottom of a trough, and the crystal touch change modifier is added when the diluted emulsion is started to rise to 7.7ms/cm after the conductivity reaches 4.1 ms/cm;
5. placing the reaction slurry in a reaction kettle, heating to 90 ℃, standing and preserving heat for 30min, then adding a surface thixotropic modifier, uniformly stirring, and carrying out wet modification treatment to obtain modified slurry; wherein the surface contact change modifier accounts for 2 percent of the total mass of calcium carbonate in the reaction slurry; the surface contact change modifier is modified coconut oil;
6. filtering the modified slurry, drying to remove water, crushing the agglomerated part to prepare the nano calcium carbonate for PVC automobile prime coat adhesive yield enhancement, wherein the particle size D50 is 92nm, and the specific surface area is 30m2/g；
50g of nano calcium carbonate for PVC (polyvinyl chloride) automobile primer glue yield enhancement is mixed with 70g of DOP, and the yield strength of the pasty emulsion is 867Pa when the Bingham viscosity of the pasty emulsion is 938mPa & s measured by a Haake viscometer.
Example 2
The method is the same as example 1, except that:
(1) calcining limestone into calcium oxide at 900 ℃; adding hot water with the temperature of 97 ℃ into the calcium oxide fine granules for digestion; wherein the adding amount of the hot water is 4 times of the mass of the calcium oxide fine powder;
(2) adding water to dilute the calcium hydroxide emulsion to a mass concentration of 7%; when the temperature of the diluted emulsion is reduced to 29 ℃, placing the diluted emulsion in synthesis reaction equipment;
(3) the addition amount of the crystal touch change modifier is 0.6 percent of the total mass of the calcium oxide fine powder; the crystal touch change modifier is sodium benzenesulfonate; standing the diluted emulsion for 40 min; the volume percentage of carbon dioxide in the mixed gas is 40 percent;
when the synthesis is started, the electric conductivity of the diluted emulsion is 7.7ms/cm, when the diluted emulsion is firstly reduced to the bottom of the grain, the electric conductivity is 3.9ms/cm, and when the electric conductivity reaches 3.9ms/cm, the diluted emulsion is started to be raised to 7.7ms/cm, and a crystal touch change modifier is added;
(4) heating the reaction slurry to 100 ℃, standing and preserving heat for 25min, wherein the added surface contact change modifier accounts for 3% of the total mass of calcium carbonate in the reaction slurry; the surface contact change modifier is modified olive oil;
(5) the PVC automobile prime coat adhesive yield-enhancing nano calcium carbonate has the particle size D50 of 95nm and the specific surface area of 90m2/g；
After 50g of nano calcium carbonate for yield enhancement of PVC (polyvinyl chloride) automobile prime coat glue is mixed with 70g of DOP (dioctyl phthalate), when the Bingham viscosity of the pasty emulsion is 973mPa & s measured by a Haake viscometer, the yield value is 1023 Pa.
Example 3
The method is the same as example 1, except that:
(1) calcining limestone into calcium oxide at 800 ℃; adding hot water with the temperature of 99 ℃ into the calcium oxide fine granules for digestion; wherein the adding amount of the hot water is 5 times of the mass of the calcium oxide fine powder;
(2) adding water to dilute the calcium hydroxide emulsion to 8% of mass concentration; when the temperature of the diluted emulsion is reduced to 28 ℃, placing the diluted emulsion in synthesis reaction equipment;
(3) the addition amount of the crystal touch change modifier is 0.8 percent of the total mass of the calcium oxide fine powder; the crystal touch change modifier is sodium lignosulfonate; standing the diluted emulsion for 45 min; the volume percentage of carbon dioxide in the mixed gas is 60 percent;
when the synthesis is started, the electric conductivity of the diluted emulsion is 7.7ms/cm, when the diluted emulsion is firstly reduced to the bottom of the grain, the electric conductivity is 3.5ms/cm, and when the electric conductivity reaches 3.5ms/cm, the diluted emulsion is started to be raised to 7.7ms/cm, and a crystal touch change modifier is added;
(4) heating the reaction slurry to 110 ℃, standing and preserving heat for 25min, wherein the added surface contact change modifier accounts for 4% of the total mass of calcium carbonate in the reaction slurry; the surface contact change modifier is modified olive oil;
(5) the nanometer calcium carbonate for PVC automobile prime coat adhesive yield enhancement has the particle size D50-94 nm and the specific surface area of 100m2/g；
After 50g of nano calcium carbonate for PVC (polyvinyl chloride) automobile prime coat adhesive yield enhancement is mixed with 70g of DOP, when the Bingham viscosity of the pasty emulsion is 864mPa & s measured by a Hack viscometer, the yield value is 882 Pa.
Example 4
The method is the same as example 1, except that:
(1) calcining limestone into calcium oxide at 1000 ℃; adding hot water with the temperature of 100 ℃ into the calcium oxide fine granules for digestion; wherein the adding amount of the hot water is 6 times of the mass of the calcium oxide fine powder;
(2) adding water to dilute the calcium hydroxide emulsion to a mass concentration of 9%; when the temperature of the diluted emulsion is reduced to 27 ℃, placing the diluted emulsion in synthesis reaction equipment;
(3) the addition amount of the crystal touch change modifier is 1 percent of the total mass of the calcium oxide fine powder; the crystal touch change modifier is sodium diethylthiocarbamate; standing the diluted emulsion for 50 min; the volume percentage of carbon dioxide in the mixed gas is 80 percent;
when the synthesis is started, the conductivity of the diluted emulsion is 7.7ms/cm, when the diluted emulsion is firstly reduced to the bottom of the grain, the conductivity is 2.6ms/cm, and when the conductivity reaches 2.6ms/cm, the diluted emulsion is started to be raised to 7.7ms/cm, and a crystal touch change modifier is added;
(4) heating the reaction slurry to 120 ℃, standing and preserving heat for 20min, wherein the added surface contact change modifier accounts for 6% of the total mass of calcium carbonate in the reaction slurry; the surface contact change modifier is modified peanut oil;
(5) the PVC automobile prime coat adhesive yield-enhancing nano calcium carbonate has the particle size D50 of 100nm and the specific surface area of 130m2/g；
After 50g of nano calcium carbonate for PVC (polyvinyl chloride) automobile primer yield enhancement is mixed with 70g of DOP (dioctyl phthalate), when the Bingham viscosity of the pasty emulsion is 910mPa & s measured by a Haake viscometer, the yield value is 987 Pa.
Claims (2)
1. A preparation method of nano calcium carbonate for yield enhancement of PVC (polyvinyl chloride) automobile primer glue is characterized by comprising the following steps of:
(1) calcining limestone into calcium oxide at 800-1000 ℃, and crushing until the particle size is less than or equal to 20mm to prepare calcium oxide fine powder; adding hot water with the temperature of 95-100 ℃ into the calcium oxide fine powder for digestion to prepare digested slurry; wherein the adding amount of the hot water is 3-6 times of the mass of the calcium oxide fine powder;
(2) sieving the digested slurry with 400 mesh sieve to remove coarse particles and impurities to obtain calcium hydroxide emulsion;
(3) a micro-bubble type superfine calcium carbonate synthesis reactor is adopted as synthesis reaction equipment; adding water into the calcium hydroxide emulsion to dilute the calcium hydroxide emulsion until the mass concentration is 6-9% to prepare diluted emulsion; when the temperature of the diluted emulsion is reduced to be less than or equal to 30 ℃, placing the diluted emulsion in synthesis reaction equipment;
(4) introducing mixed gas into the diluted emulsion under the stirring condition for synthesis; detecting the conductivity and pH value of the diluted emulsion on line during synthesis; when the conductivity of the diluted emulsion is reduced to the valley bottom for the first time and then the diluted emulsion is raised, adding a crystal touch change modifier into the diluted emulsion, wherein the addition amount of the crystal touch change modifier accounts for 0.5-1% of the total mass of the calcium oxide fine powder; the crystal touch change modifier is sodium p-toluenesulfinate, sodium benzenesulfonate, sodium lignosulfonate or sodium diethylthiocarbamate; when the conductivity of the diluted emulsion is increased back to the value at the beginning of synthesis, stopping introducing the mixed gas and stopping stirring, and standing the diluted emulsion for 30-50 min; introducing mixed gas into the diluted emulsion under the stirring condition for synthesis, and stopping reaction until the pH value of the diluted emulsion is reduced to 7 to obtain reaction slurry; the volume percentage of carbon dioxide in the mixed gas is 30-80%, and the balance is air;
(5) placing the reaction slurry in a reaction kettle, heating to 90-120 ℃, standing and preserving heat for 20-30 min, then adding a surface thixotropic modifier, uniformly stirring, and carrying out wet modification treatment to obtain modified slurry; wherein the surface contact change modifier accounts for 2-6% of the total mass of calcium carbonate in the reaction slurry; the surface contact change modifier is modified coconut oil, modified olive oil or modified peanut oil;
(6) and filtering the modified slurry, drying to remove water, and crushing the agglomerated part to prepare the nano calcium carbonate for PVC automobile primer yield enhancement.
2. The preparation method of the nano calcium carbonate for PVC automobile primer glue yield enhancement according to claim 1, wherein the particle size D50 of the nano calcium carbonate for PVC automobile primer glue yield enhancement is less than or equal to 100nm, and the specific surface area is 30-130 m2/g。
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| PCT/CN2019/096150 WO2020113964A1 (en) | 2018-12-06 | 2019-07-16 | Method for preparing nano calcium carbonate for enhancing yield of pvc automobile primer coating |
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| CN114212812B (en) * | 2021-11-01 | 2023-11-21 | 山东宇信纳米科技有限公司 | Preparation method of nano calcium carbonate for PVC edge banding |
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