CN103897438B - A kind of preparation method of composite calcium carbonate - Google Patents
A kind of preparation method of composite calcium carbonate Download PDFInfo
- Publication number
- CN103897438B CN103897438B CN201410155069.1A CN201410155069A CN103897438B CN 103897438 B CN103897438 B CN 103897438B CN 201410155069 A CN201410155069 A CN 201410155069A CN 103897438 B CN103897438 B CN 103897438B
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- titanium dioxide
- preparation
- composite calcium
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 132
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 35
- 239000002002 slurry Substances 0.000 claims abstract description 22
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 20
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 20
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229950007687 macrogol ester Drugs 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000005255 carburizing Methods 0.000 claims abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- -1 polyoxyethylene Polymers 0.000 abstract description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 abstract description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 7
- 235000011089 carbon dioxide Nutrition 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 239000008187 granular material Substances 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000002070 germicidal effect Effects 0.000 abstract 1
- 235000010215 titanium dioxide Nutrition 0.000 description 31
- 238000000576 coating method Methods 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 18
- 238000001035 drying Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000011246 composite particle Substances 0.000 description 5
- BAJCNPGPHMFYJP-UHFFFAOYSA-L calcium oxygen(2-) titanium(4+) carbonate Chemical compound [O-2].[O-2].[Ca+2].[Ti+4].[O-]C([O-])=O BAJCNPGPHMFYJP-UHFFFAOYSA-L 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000036561 sun exposure Effects 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
The preparation method of composite calcium carbonate of the present invention belongs to Inorganic synthese technical field.The invention provides a kind of preparation method of composite calcium carbonate, with polyoxyethylene glycol or macrogol ester for dispersion agent, in calcium hydroxide slurry, add titanium dioxide and dispersion agent, pass into carbonic acid gas and nitrogen volume ratio be 1: 2 mixed gas carry out carburizing reagent and obtain composite calcium carbonate.The composite calcium carbonate product obtained, its structure is spindle-type calcium carbonate granule coated with uniform titania nanoparticles.Composite calcium carbonate prepared by the present invention has that uv-absorbing intensity is high, whiteness is high, strong covering power and the feature such as weathering resistance is strong, and has germicidal action; Preparation method of the present invention has that manufacture craft is simple, reaction conditions is gentle and be easy to realize the features such as suitability for industrialized production.
Description
Technical field
The present invention relates to Inorganic synthese technical field, be specifically related to a kind of preparation method of composite calcium carbonate.
Background technology
Calcium carbonate, as a kind of important Inorganic Chemicals, has the characteristics such as resource reserve is abundant, nontoxic, tasteless, excellent property, is widely used in the fields such as coating, plastics, papermaking, rubber, ink.Especially in paint field, calcium carbonate receives increasing concern, and can prevent coating sedimentation at water-borne coatings industry calcium carbonate, make coating good dispersity, glossiness is high, and the consumption of calcium carbonate in water-borne coatings accounts for 20% ~ 60%.In coating, calcium carbonate not only plays skeleton function, can also increase coating thickness, improves the wear resistance of coating, significantly enhances the sticking power of coating.Calcium carbonate is added in coating, the rheological of coating, the toughness of coating, water tolerance, weathering resistance, stability can be changed.But at present calcium carbonate also exist opacifying power strong, under long sun exposure, easily there is the defects such as powder phenomenon-tion, which has limited the range of application of calcium carbonate.In addition, the whiteness of calcium carbonate is not high, cannot be used as the pigment auxiliary agent in coating, directly and rutile titanium dioxide used in combination, although can whiteness be improved, there is particle dispersion bad, and intergranular bonding is insecure.
For head it off, domestic and international many scholars are studied, patent CN1444543A provides a kind of preparation method of titanium dioxide-calcium carbonate composite particles, it is characterized in that, by carburizing reagent, TiO 2 particles is directly coated on the surface of calcium carbonate under without any the condition of additive; Its preparation process be in calcium hydroxide slurry, under agitation pass into carbonic acid gas and air mixture until the pH of slurry is 7.This patent takes the lead in proposing the technology utilizing carborization to prepare titanium dioxide-calcium carbonate composite particles, achieves titanium dioxide coated in the part of calcium carbonate surface, improves the whiteness of product, and is used successfully to paper industry.But titanium dioxide-calcium carbonate composite particles prepared by this method exists composite particles instability, titanium dioxide easily to be peeled off and the not high phenomenon of clad ratio of calcium carbonate.Patent CN101302359A provides a kind of preparation method of composite titanium dioxide, it is characterized in that using water glass as binding agent and coating agent, at light calcium carbonate surface inserting titanium dioxide granule.This method achieves the coated of calcium carbonate and completes with the substep of coating in carbonation reaction process of titanium dioxide, but the titanium dioxide amount that this method is added is bigger than normal, improve production cost, and this technical operating procedure is complicated, realizes industrialization and is faced with certain difficulty.In addition, because titanium dioxide is different with the proportion of calcium carbonate, cause titanium dioxide in product very large in the clad ratio difference of calcium carbonate surface so add titanium white slurries in the carbonating later stage, this is unfavorable for the scale operation of titanium dioxide-calcium carbonate composite particles.Patent CN103194089 provides a kind of preparation method of composite titanium dioxide, it is characterized in that, using metatitanic acid as titanium source coating, adding water glass is binding agent and coating, and through suction filtration, washing, dry, pulverize and obtain composite titanium dioxide.This invention changes the raw material of titanium dioxide into metatitanic acid by commodity-type titanium dioxide, reduces production cost; And complete in preparation process calcium carbonate first coated with titanium dioxide after coating, but due to the proportion difference of titanium dioxide and calcium carbonate comparatively large, make the clad ratio difference of calcium carbonate in product also very large; And metatitanic acid particle diameter is tens nanometers, be easy to reunite, the combination of the metatitanic acid particle after secondary agglomeration and calcium carbonate may be made firm not, and the temperature of required drying is higher, the time is longer.In addition, sulfuric acid process of this invention is prepared metatitanic acid process and can be caused certain pollution to environment.
Summary of the invention
The technical problem to be solved in the present invention is, not high and easily peel off, cause because titanium dioxide is different with the density of calcium carbonate the defect that in product, the clad ratio of titanium dioxide differs greatly when the carburizing reagent later stage adds titanium dioxide without coated by titanium dioxide rate in calcium carbonate-TiO 2 particles during dispersion agent in carbonation reaction.For solving the problems of the technologies described above, the technical solution used in the present invention adds dispersion agent polyoxyethylene glycol or macrogol ester and titanium dioxide at the carbonization initial stage, by once reinforced mode, and directly acquisition composite calcium carbonate product.
The composite calcium carbonate product that the present invention obtains, its structure is spindle-type calcium carbonate granule coated with uniform titania nanoparticles.
The concrete technical scheme that the present invention adopts is, 40 ~ 60 DEG C, under the condition of stirring velocity 800 ~ 1000 revs/min, be in the calcium hydroxide slurry of 5% ~ 15%, add polyoxyethylene glycol or macrogol ester and titanium dioxide to massfraction, then under the condition of speed 50 ~ 120 liters/min, passing into carbonic acid gas and nitrogen volume ratio is that the mixed gas of 1:2 carries out carburizing reagent 30 ~ 60 minutes, until pH value is 7 obtain white water slurries; Described white water slurries are carried out centrifuge dehydration, dry, obtain composite calcium carbonate; Described polyoxyethylene glycol or macrogol ester, the massfraction of titanium dioxide to calcium hydroxide are respectively 0.074% ~ 0.74%, 3.7% ~ 14.8%.
Described polyoxyethylene glycol or macrogol ester preferred molecular weight are 1000 ~ 10000.
Described titanium dioxide particle diameter preferably 200 ~ 300nm.
The preferred rutile-type of described titanium dioxide.
The addition of preferred polyoxyethylene glycol or macrogol ester is account for calcium hydroxide quality 0.296%, and the addition of best rutile titanium dioxide is account for calcium hydroxide quality 11.1%.
Described drying, can in 120 DEG C of dryings 4 hours.
The composite calcium carbonate utilizing preparation method of the present invention to obtain is spindle-type, and calcium carbonate crystal formation is calcite.Gained composite calcium carbonate has the advantage that uv-absorbing intensity is high, strong covering power, whiteness are high, weathering resistance is strong, and under the irradiation of UV-light, composite calcium carbonate can produce the hydroxyl radical free radical with very Strong oxdiative ability, its cell walls that can penetrate bacterium enters thalline, stop the transport of filmogen, thus effectively kill bacterium.When the composite calcium carbonate of gained being used as the pigment in coating, not only whiteness meets the performance requriements of pigment, and safety, environmental protection, nontoxic.In addition, when gained composite calcium carbonate is used as the filler in coating, can not only opacifying power be significantly improved, and the physical strength of film and stability etc. can be improved.Production technique of the present invention is simple, can control to pass into the speed of gas and the addition of titanium dioxide, thus the size of titanium dioxide granule and the clad ratio of calcium carbonate can be adjusted, and then adjust germ resistance and the opacifying power of matrix material, production control cost, and the clad ratio of calcium carbonate is high, output is high, and reaction conditions is gentle and be easy to realize suitability for industrialized production.
Accompanying drawing explanation
The scanning electron microscope (SEM) photograph of Fig. 1 embodiment 2 composite calcium carbonate.
Fig. 2 calcium carbonate, rutile titanium dioxide and embodiment 2 uv-absorbing figure of gained composite calcium carbonate.
Embodiment
Further illustrate the present invention below by way of specific embodiment, but these embodiments do not limit to the present invention.
Embodiment 1
40 DEG C, under the condition of stirring velocity 800 revs/min, be add in the calcium hydroxide slurry of 10% to account for the rutile titanium dioxide of calcium hydroxide quality 7.4% and the polyoxyethylene glycol of 0.074% or macrogol ester (molecular weight 1000) to massfraction, mechanical stirring 30 minutes, then under 120 liters/min of speed, the mixed gas passing into carbonic acid gas and nitrogen volume ratio 1:2 carries out carburizing reagent, when the pH value of solution is 7, stopped reaction, obtains white water slurries; Described white water slurries are carried out centrifuge dehydration, in 120 DEG C of dryings 4 hours.
The whiteness value of composite calcium carbonate is 96.3, and productive rate is 97%, and the clad ratio of calcium carbonate reaches 94%.When with scanning electron microscopic observation composite calcium carbonate, rutile titanium dioxide is coated on the surface of calcium carbonate, does not have independent titanium dioxide.
Embodiment 2
50 DEG C, under the condition of stirring velocity 800 revs/min, be add in the calcium hydroxide slurry of 10% to account for the rutile titanium dioxide of calcium hydroxide quality 11.1% and the polyoxyethylene glycol of 0.296% or macrogol ester (molecular weight 2000) to massfraction, mechanical stirring 40 minutes, then under 90 liters/min of speed, the mixed gas passing into carbonic acid gas and nitrogen volume ratio 1:2 carries out carbonation reaction, when the pH value of reaction soln is 7, stopped reaction, obtains white water slurries; Described white water slurries are carried out centrifuge dehydration, then in 120 DEG C of dryings 4 hours.
The whiteness value of composite calcium carbonate is 97.2, and productive rate is 98%, and the clad ratio of calcium carbonate is 96%.When with scanning electron microscopic observation composite calcium carbonate, rutile titanium dioxide is coated on the surface of calcium carbonate, does not have independent titanium dioxide.
Embodiment 3
50 DEG C, under the condition of stirring velocity 900 revs/min, be add in the calcium hydroxide slurry of 15% to account for the rutile titanium dioxide of calcium hydroxide quality 14.8% and the polyoxyethylene glycol of 0.518% or macrogol ester (molecular weight 6000) to massfraction, mechanical stirring 50 minutes, then under 80 liters/min of speed, passing into carbonic acid gas and nitrogen volume is that the mixed gas of 1:2 carries out carbonation reaction, when the pH value of reaction soln is 7, stopped reaction, obtains white water slurries; Described white slurries are carried out centrifuge dehydration, then in 120 DEG C of dryings 4 hours.
The whiteness value of composite calcium carbonate is 96.8, and productive rate is 97%, and the clad ratio of calcium carbonate is 94%.When with scanning electron microscopic observation composite calcium carbonate, rutile titanium dioxide is coated on the surface of calcium carbonate, does not have independent titanium dioxide.
Embodiment 4
60 DEG C, under the condition of stirring velocity 1000 revs/min, be add in the calcium hydroxide slurry of 15% to account for the rutile titanium dioxide of calcium hydroxide quality 14.8% and the polyoxyethylene glycol of 0.74% or macrogol ester (molecular weight 8000) to massfraction, mechanical stirring 60 minutes, then under 50 liters/min of speed, the mixed gas passing into carbonic acid gas and nitrogen volume ratio 1:2 carries out carbonation reaction, when the pH value of solution is 7, stopped reaction, obtains white water slurries; Described white water slurries are carried out centrifuge dehydration, then in 120 DEG C of dryings 4 hours.
The whiteness value of composite calcium carbonate is 96.4, and productive rate is 97%, and the clad ratio of calcium carbonate is 92%.When with scanning electron microscopic observation composite calcium carbonate, rutile titanium dioxide is coated on the surface of calcium carbonate, does not have independent titanium dioxide.
Known by comparing above-described embodiment, best polyoxyethylene glycol or the addition of macrogol ester are account for calcium hydroxide quality 0.296%, and the addition of best rutile titanium dioxide is account for calcium hydroxide quality 11.1%.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For the person of ordinary skill of the art, can according to technical scheme of the present invention and inventive concept, make corresponding change and substitute, and performance or purposes identical, all should be considered as protection scope of the present invention.
Claims (4)
1. the preparation method of a composite calcium carbonate, it is characterized in that, 40 ~ 60 DEG C, under the condition of stirring velocity 800 ~ 1000 revs/min, be add macrogol ester and titanium dioxide in the calcium hydroxide slurry of 5% ~ 15% to massfraction, then under the condition of speed 15 ~ 120 liters/min, passing into titanium dioxide and nitrogen volume ratio is that the mixed gas of 1:2 carries out carburizing reagent 30 ~ 60 minutes, until pH value is 7 obtain white water slurries; Described white water slurries are carried out centrifuge dehydration, dry, obtain composite calcium carbonate; Described macrogol ester, the titanium dioxide massfraction to calcium hydroxide is respectively 0.074% ~ 0.74%, 3.7% ~ 14.8%.
2. the preparation method of a kind of composite calcium carbonate according to claim 1, it is characterized in that, described macrogol ester is 0.296% to the massfraction of calcium hydroxide, and described titanium dioxide is rutile titanium dioxide, and rutile titanium dioxide is 11.1% to the massfraction of calcium hydroxide.
3. the preparation method of a kind of composite calcium carbonate according to claim 1, is characterized in that, the molecular weight of described macrogol ester is 1000 ~ 10000.
4. the preparation method of a kind of composite calcium carbonate according to claim 1, is characterized in that, most titanium dioxide particle diameter is 200 ~ 300nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410155069.1A CN103897438B (en) | 2014-04-17 | 2014-04-17 | A kind of preparation method of composite calcium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410155069.1A CN103897438B (en) | 2014-04-17 | 2014-04-17 | A kind of preparation method of composite calcium carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103897438A CN103897438A (en) | 2014-07-02 |
| CN103897438B true CN103897438B (en) | 2016-01-06 |
Family
ID=50989029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410155069.1A Active CN103897438B (en) | 2014-04-17 | 2014-04-17 | A kind of preparation method of composite calcium carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103897438B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105107537B (en) * | 2015-09-07 | 2017-04-19 | 安徽中烟工业有限责任公司 | Nano calcium carbonate catalyst wrapped by Ag-loaded titanium dioxide nanoparticles, as well as preparation method and application of nano calcium carbonate catalyst |
| CN109183497B (en) * | 2018-09-18 | 2021-07-13 | 吉林大学 | Nano TiO for papermaking2Preparation method of/wollastonite compound |
| CN115197603B (en) * | 2022-07-11 | 2023-07-28 | 内蒙古普诺思新材料科技有限公司 | Preparation method of composite calcium carbonate-titanium dioxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1444543A (en) * | 2000-07-04 | 2003-09-24 | 日铁矿业株式会社 | Titanium dioxide-calcium carbonate composite particles |
| CN1597530A (en) * | 2004-09-08 | 2005-03-23 | 吉林大学 | Biomimetic mintralization in situ preparation method of functional nanometer calcium carbonate |
-
2014
- 2014-04-17 CN CN201410155069.1A patent/CN103897438B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1444543A (en) * | 2000-07-04 | 2003-09-24 | 日铁矿业株式会社 | Titanium dioxide-calcium carbonate composite particles |
| CN1597530A (en) * | 2004-09-08 | 2005-03-23 | 吉林大学 | Biomimetic mintralization in situ preparation method of functional nanometer calcium carbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103897438A (en) | 2014-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10259945B2 (en) | Pigment particle composition, its method of manufacture and its use | |
| CN106517285B (en) | A kind of preparation method of rod-like nano calcium carbonate | |
| AU2012234470B2 (en) | Self-binding pigment hybrid | |
| EP2798012B1 (en) | Use of precipitated carbonate in the manufacture of a fibre product | |
| CN104087029B (en) | A kind of preparation method of silicone sealant special active calcium carbonate | |
| CN104098932B (en) | A kind of preparation method of white mineral-titanium dioxide composite powder pigment | |
| CN103897438B (en) | A kind of preparation method of composite calcium carbonate | |
| CN110484022A (en) | A kind of production technology of the nanometer calcium carbonate of transparent membrane | |
| CN101531495B (en) | Attapulgite outer wall emulsion varnish | |
| CN109809458B (en) | Rugby-shaped calcium carbonate and preparation process thereof | |
| CN108410017A (en) | A kind of preparation method for the high-dispersion barium sulfate composite material in plastic matrix | |
| CN108821322A (en) | A kind of preparation method of layer structure microballoon winnofil | |
| CN103435082B (en) | A kind of method utilizing lignin from pulping black liquor to regulate and control calcium carbonate crystal particle growth | |
| CN113087005A (en) | Preparation method of cubic superfine calcium carbonate and preparation method of PVC (polyvinyl chloride) calendered film | |
| CN108130815B (en) | Facing base paper for outdoor high-strength board and preparation method thereof | |
| CN109321002B (en) | Preparation method of titanium dioxide silicon zirconium aluminum ternary coating film by chlorination process | |
| CN108793217B (en) | Preparation method of spherical light calcium carbonate | |
| CN114291835A (en) | Preparation method of precipitated calcium carbonate with dispersed size and cube | |
| CN114408959A (en) | Preparation method of monodisperse calcium carbonate with regular appearance and narrow particle size distribution | |
| CN110511598B (en) | Production process of titanium dioxide special for high-light-fastness papermaking | |
| Lin et al. | Preparation of calcium carbonate particles coated with titanium dioxide | |
| CN111925669A (en) | Surface treatment method of special titanium dioxide for high-covering-power papermaking | |
| CN112441605B (en) | Preparation method of vermicular precipitated calcium carbonate | |
| CN107012728B (en) | A kind of preparation method for facing paper production sun-screening agent | |
| CN112759982A (en) | PVA/CNC composite coating and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 130000 Qinhuangdao Road, Changchun Economic Development Zone, Jilin, No. 555 Patentee after: TIANCHENG HIGH-TECH NANO-COMPOSITE MATERIAL CO.,LTD. Address before: 130000 Qinhuangdao Road, Changchun Economic Development Zone, Jilin, No. 555 Patentee before: CHANGCHUN TIANCHENG HIGH-NEW NANO COMPOSITE Co.,Ltd. |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20140702 Assignee: Jilin runqi nano New Material Co.,Ltd. Assignor: TIANCHENG HIGH-TECH NANO-COMPOSITE MATERIAL Co.,Ltd. Contract record no.: X2020220000004 Denomination of invention: Preparation method of composite calcium carbonate Granted publication date: 20160106 License type: Common License Record date: 20200427 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| PP01 | Preservation of patent right | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20210709 Granted publication date: 20160106 |
|
| PD01 | Discharge of preservation of patent | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20220708 Granted publication date: 20160106 |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220812 Address after: Unit 601, Unit 3, Building 19, No. 2, Hsinchu Road, Shinan District, Qingdao City, Shandong Province, 266000 Patentee after: Cui Shaohua Address before: No. 555, Qinhuangdao Road, Economic Development Zone, Changchun City, Jilin Province, 130000 Patentee before: TIANCHENG HIGH-TECH NANO-COMPOSITE MATERIAL CO.,LTD. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220831 Address after: Room 396, 3rd Floor, Building 1, No. 50, Shun South Road, Shunyi District, Beijing 100000 Patentee after: Beijing Zhonghu Ruishi New Material Technology Co.,Ltd. Address before: Unit 601, Unit 3, Building 19, No. 2, Hsinchu Road, Shinan District, Qingdao City, Shandong Province, 266000 Patentee before: Cui Shaohua |