CN102311555B - Preparation method for coating silica by utilizing polymer hollow microspheres - Google Patents
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Abstract
The invention relates to a preparation method which is characterized by taking styrene and acrylics as monomers to synthesize a hollow polymer to coat silica by a sol-gel method. The preparation method comprises the following steps: firstly synthesizing a polymer core through emulsion polymerization, then forming a polymer intermediate on the polymer core through seeding polymerization, finally forming a polymer shell layer on the intermediate through seeding polymerization, and then forming hollow microspheres through alkali treatment; and coating inorganic mineral matters such as silica and the like by the sol-gel method on the basis of the hollow microspheres. The method has the following beneficial effects: organic solvent dissolution, strong acid and alkali etching or high-temperature calcination is not needed to remove a hollow microsphere template, so the method is safe in preparation processes and is simple and convenient to operate; the hollow microspheres formed by different chemical components can be obtained by changing the raw materials of the core and the shell; and the application of the hollow microspheres in different occasions can be improved by modification of different inorganic mineral matters.
Description
Technical field
The present invention relates to a kind of preparation method of polymer hollow particles, particularly can carry out the emulsion system of the surface coating formation stable homogeneous of all kinds of inorganic minerals by this hollow microsphere.
Background technology
At present, coating industry be unable to do without the demand of titanium dioxide, improve wet hiding power and dry film opacifying power in the coating, must add the high color stuffing of refraction coefficient, and general common mineral substance shading factor is mostly between 1.4-1.7, can't form effectively to hide.At present the most effective is exactly that refraction coefficient reaches 2.7 titanium dioxide.But the titanium dioxide industry is the industry of a highly energy-consuming and high pollution, and domestic most employing method for producing gtitanium dioxide with sulphuric acid particularly destroys the demand of ecotope and the energy especially greatly.Though common hollow microsphere can play certain dry film covering effect, hide not too big help for wet film, particularly common hollow microsphere is because the polymer core rigidity modulus is less, is easy to destroy under the effect of external force and subsides.The paint film of working it out like this is easy to occur the unexpected variation of gloss, so hollow microsphere can not add in coating and surpass 8%, and can only seldom partly replace titanium dioxide.To replace in the coating dependence to titanium dioxide completely, must aspect two, make raising, improve the rigidity modulus of polymer hollow particles itself on the one hand, on the other hand polymer hollow particles being carried out the inorganics surface coats, particularly silica sphere coats, and reaches the purpose that improves shading factor.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method at polymer hollow particles surface coated silica, it is added in the coating can thoroughly replace titanium dioxide, satisfy dry film and wet film simultaneously for the demand of opacifying power.
The present invention is achieved through the following technical solutions:
A kind of preparation method at polymer hollow particles surface coated silica, concrete steps are as follows:
(1) at first by letex polymerization synthetic polymer nuclear, on polymer core, forms intermediate polymer by seeding polymerization then, on intermediate, form the polymkeric substance shell by seeding polymerization at last, form hollow microsphere by alkaline purification afterwards.
Above-mentioned polymer hollow particles comprises synthetic polymer core/intermediate/three layers of emulsion system of shell, and wherein, main component and the weight proportion of described polymer core are as follows:
Methymethacrylate 10-12%
Methacrylic acid 6-8%
Fourth fat 10-12%
Ethylene glycol dimethacrylate 0.1-0.3%
Sodium laurylsulfonate 0.002-0.004%
Ammonium persulphate 0.2-0.5%
Water 68-72%;
Concrete component and the weight proportion of described intermediate polymer are as follows:
Methymethacrylate 8-14%
Methacrylic acid 1-3%
Vinylbenzene 2-5%
Ammonium persulphate 0.1-0.3%
Water 60-65%
Polymer core 16-24%;
Main component and the weight proportion of described polymer shell are as follows:
Vinylbenzene 16-20%
Fourth fat 0.5-1%
Vinylstyrene 0.5-1%
Ammonium persulphate 0.1-0.3%
Water 13-20%
Intermediate polymer 60-65%.
The preparation method of above-mentioned polymer hollow particles, its concrete steps are as follows:
(1) preparation of polymer core, concrete technology is: add whole water earlier, account for the ammonium persulphate of total amount 1/4 and account for methymethacrylate, methacrylic acid, fourth fat and the ethylene glycol dimethacrylate of total amount 1/20,80
oPolymerization is 40 minutes under the C, drips methymethacrylate, methacrylic acid, fourth fat, the ethylene glycol dimethacrylate of residue 19/20 and the ammonium persulphate that remains 3/4 then, and this process need is 80
oContinue 4.5 hours under the C, be warmed up to 90 afterwards
oC kept this temperature 30 minutes simultaneously, the polymer core emulsion that obtains synthesizing;
(2) preparation of intermediate polymer, its concrete technology is: earlier above-mentioned synthetic polymer core emulsion is diluted to 10% solid content, component and proportioning by above-mentioned intermediate polymer continues to drip methymethacrylate, methacrylic acid, vinylbenzene, ammonium persulphate and water then, 80
oIn the presence of ammonium persulphate, continue reaction 40-60 minute under the C, obtain the intermediate polymer emulsion;
(3) preparation of polymer shell, its concrete technology is: be added drop-wise in the intermediate polymer emulsion, 90 by the mixing with vinylbenzene, fourth fat and Vinylstyrene of the composition of above-mentioned polymer shell and proportioning
oAmmonium persulphate exists and to continue reaction down 2-3 hour under the C, afterwards the polymkeric substance cool to room temperature is formed the emulsion system of three layers in polymer core/intermediate/shell;
(4) carry out alkaline purification, the polymer core/intermediate/three layers of emulsion system of shell that synthesized are put into water bath with thermostatic control, in the alkali environment, handle under the speed conditions of maintenance 400r/min, can make the synthetic polymer hollow microsphere.
Described alkali envrionment conditions is: under the situation of using the ammoniacal liquor neutralization, the water bath with thermostatic control temperature remains on 50-100 degree centigrade, and dropping alkali acid mol ratio is that the ammoniacal liquor of 0.75-3.5 reacted 1-6 hour; Perhaps under the situation of using the sodium hydroxide neutralization, the water bath with thermostatic control temperature remains on 85-95 degree centigrade, the sodium hydroxide reaction that the sour mol ratio of dropping alkali is 1.1-1.5 2-4 hour.
(2) carry out the silicon-dioxide parcel with sol-gel method, its concrete technology is:
(1) elder generation drips polymer hollow particles 9% water dispersion that makes the polyethyleneimine: amine aqueous solution of 1mg/ml under the stirring velocity of 100r/min, wherein the weight proportion of polymer hollow particles 9% water dispersion and polyethyleneimine: amine aqueous solution is 1:2, carries out centrifugation after lasting 6 hours under 9000r/min and obtains the polymer hollow particles particle;
(2) the polymer hollow particles particle of gained is distributed to again forms 10% hollow microsphere water dispersion in the water, then with the hollow microsphere water dispersion with 10% concentration dilution in alcohol concn is 80% ethanolic soln, with ultra-sonic oscillation 15 minutes, add 36% concentrated hydrochloric acid or the ammoniacal liquor of 25% concentration afterwards and carry out pH regulator;
(3) under the stirring velocity that keeps 100r/min, drip tetraethyl-silica alkane at last, continue 24 hours; Under the centrifugal speed of 5400r/min, separate afterwards and obtained the hollow microsphere that there is the silicon-dioxide parcel on the surface in 15 minutes.
The present invention does not need to remove the hollow microsphere template by organic solvent dissolution, strong acid and strong base etching or high-temperature calcination, safe preparation process, easy and simple to handle, can improve the feature of environmental protection greatly, and can obtain the polymer hollow particles that different chemical is formed by changing raw material, through this polymer hollow particles of surperficial coated silica, with can thoroughly replacing titanium dioxide in its adding coating, satisfy dry film and wet film simultaneously for the demand of opacifying power; Modification by different inorganic minerals simultaneously can improve the application of hollow microsphere in different occasions.
[embodiment]
A kind of with vinylbenzene, methymethacrylate is the synthetic polymer hollow particles of monomer, and passes through the preparation method of sol-gel method coated silica, and concrete steps are as follows:
(1) at first by letex polymerization synthetic polymer nuclear, on polymer core, forms intermediate polymer by seeding polymerization then, on intermediate, form the polymkeric substance shell by seeding polymerization at last, form hollow microsphere by alkaline purification afterwards.
Described polymer hollow particles comprises polymer shell, intermediate, polymer core and coated with silica layer, and concrete set of dispense ratio and preparation method are as follows:
1, the making of polymer core:
Methymethacrylate 10-12%
Methacrylic acid 6-8%
Fourth fat 10-12%
Ethylene glycol dimethacrylate 0.1-0.3%
Sodium laurylsulfonate 0.002-0.004%
Ammonium persulphate 0.2-0.5%
Water 68-72%;
Raw material is described as follows:
Methymethacrylate: MMA, common commercially available;
Methacrylic acid: MAA, common commercially available;
Fourth fat: common commercially available;
Ethylene glycol dimethacrylate: EDGMA, common commercially available;
Sodium laurylsulfonate: SDS, common commercially available;
Ammonium persulphate: APS, common commercially available;
Water: distilled water.
The preparation technology of above-mentioned polymer core is as follows: add earlier whole water, account for the ammonium persulphate of total amount 1/4 and account for methymethacrylate, methacrylic acid, fourth fat and the ethylene glycol dimethacrylate of total amount 1/20,80
oPolymerization is 40 minutes under the C, drips methymethacrylate, methacrylic acid, fourth fat, the ethylene glycol dimethacrylate of residue 19/20 and the ammonium persulphate that remains 3/4 then, and this process need is 80
oContinue 4.5 hours under the C, be warmed up to 90 afterwards
oC kept this temperature 30 minutes simultaneously, the polymer core emulsion that obtains synthesizing;
Main component and the weight proportion of embodiment one are as follows:
Methymethacrylate 10%
Methacrylic acid 6%
Fourth fat 11.398%
Ethylene glycol dimethacrylate 0.1%
Sodium laurylsulfonate 0.002%
Ammonium persulphate 0.5%
Water 72%
Main component and the weight proportion of embodiment two are as follows:
Methymethacrylate 11%
Methacrylic acid 7%
Fourth fat 10%
Ethylene glycol dimethacrylate 0.2%
Sodium laurylsulfonate 0.003%
Ammonium persulphate 0.4%
Water 71.397%
Main component and the weight proportion of embodiment three are as follows:
Methymethacrylate 11%
Methacrylic acid 7%
Fourth fat 12%
Ethylene glycol dimethacrylate 0.25%
Sodium laurylsulfonate 0.003%
Ammonium persulphate 0.35%
Water 69.397%
Main component and the weight proportion of embodiment four are as follows:
Methymethacrylate 12%
Methacrylic acid 8%
Fourth fat 11.496%
Ethylene glycol dimethacrylate 0.3%
Sodium laurylsulfonate 0.004%
Ammonium persulphate 0.2%
Water 68%;
2, the making of intermediate polymer:
Its main component and weight proportion are as follows:
Methymethacrylate 8-14%
Methacrylic acid 1-3%
Vinylbenzene 2-5%
Ammonium persulphate 0.1-0.3%
Water 60-65%
Polymer core 16-24%;
Raw material is described as follows:
Methymethacrylate: MMA, common commercially available;
Methacrylic acid: MAA, common commercially available;
Vinylbenzene: ST, common commercially available;
Ammonium persulphate: APS, common commercially available;
Water: distilled water.
The preparation technology of above-mentioned intermediate polymer is as follows:
Earlier above-mentioned synthetic polymer core emulsion is diluted to 10% solid content, component and the proportioning by above-mentioned intermediate polymer continues to drip methymethacrylate, methacrylic acid, vinylbenzene, ammonium persulphate and water then, 80
oIn the presence of ammonium persulphate, continue reaction 40-60 minute under the C, obtain the intermediate polymer emulsion;
Main component and the weight proportion of embodiment one are as follows:
Methymethacrylate 8%
Methacrylic acid 3%
Vinylbenzene 2%
Ammonium persulphate 0.1%
Water 62.9%
Polymer core emulsion 24%
Main component and the weight proportion of embodiment two are as follows:
Methymethacrylate 12.8%
Methacrylic acid 2%
Vinylbenzene 4%
Ammonium persulphate 0.2%
Water 65%
Polymer core emulsion 16%
Main component and the weight proportion of embodiment three are as follows:
Methymethacrylate 14%
Methacrylic acid 1%
Vinylbenzene 5%
Ammonium persulphate 0.3%
Water 60%
Polymer core emulsion 19.7%;
3, the making of polymer shell:
Its main component and weight proportion are as follows:
Vinylbenzene 16-20%
Fourth fat 0.5-1%
Vinylstyrene 0.5-1%
Ammonium persulphate 0.1-0.3%
Water 13-20%
Intermediate polymer 60-65%.
Raw material is described as follows:
Vinylbenzene: ST, common commercially available;
Vinylstyrene; DVB, common commercially available;
Fourth fat: common commercially available;
Ammonium persulphate: APS, common commercially available;
Water: distilled water.
The preparation technology of above-mentioned polymer shell is as follows:
With vinylbenzene, the mixture of fourth fat and Vinylstyrene is added drop-wise in the synthetic emulsion system, 90
oAmmonium persulphate exists and to continue reaction down 2-3 hour under the C, afterwards the polymkeric substance cool to room temperature is formed the emulsion system of three layers in polymer core/intermediate/shell;
Main component and the weight proportion of embodiment one are as follows:
Vinylbenzene 16 %
Fourth fat 1%
Vinylstyrene 1%
Ammonium persulphate 0.1%
Water 16.9%
Intermediate polymer 65%
Main component and the weight proportion of embodiment two are as follows:
Vinylbenzene 18.7 %
Fourth fat 0.5%
Vinylstyrene 0.5%
Ammonium persulphate 0.3%
Water 20%
Intermediate polymer 60%
Main component and the weight proportion of embodiment three are as follows:
Vinylbenzene 20 %
Fourth fat 0.85%
Vinylstyrene 0.85%
Ammonium persulphate 0.8%
Water 13%
Intermediate polymer 64.5%
4, carry out alkaline purification:
Polymer core/intermediate/three layers of the emulsion system of shell that synthesized are put into water bath with thermostatic control, under the situation of using the ammoniacal liquor neutralization, the water bath with thermostatic control temperature remains on 75 degrees centigrade, and the ammoniacal liquor (alkali acid ratio) that drips 2 mol ratios under the speed conditions of maintenance 400r/min reacted 4 hours; Perhaps under the situation of use sodium hydroxide neutralization, the water bath with thermostatic control temperature remains on 90 degrees centigrade, the sodium hydroxide of dropping 1.3 mol ratios under the speed conditions of maintenance 400r/min (alkali acid ratio) reaction 3 hours.
Concrete alkaline purification condition and range such as following table:
| The alkali kind | Alkali acid mol ratio | Temperature | Time |
| Ammoniacal liquor | 0.75-3.5 | 50-100 | 1-6 hour |
| Sodium hydroxide | 1.1-1.5 | 85-95 | 2-4 hour |
(2) carry out the silicon-dioxide parcel with sol-gel method, specific as follows:
(1) elder generation drips polymer hollow particles 9% water dispersion that makes the polyethyleneimine: amine aqueous solution of 1mg/ml under the stirring velocity of 100r/min, wherein the weight proportion of polymer hollow particles 9% water dispersion and polyethyleneimine: amine aqueous solution is 1:2, carries out centrifugation after lasting 6 hours under 9000r/min and obtains the polymer hollow particles particle;
(2) the polymer hollow particles particle of gained is distributed to again forms 10% hollow microsphere water dispersion in the water, then with the hollow microsphere water dispersion with 10% concentration dilution in alcohol concn is 80% ethanolic soln, with ultra-sonic oscillation 15 minutes, add 36% concentrated hydrochloric acid or the ammoniacal liquor of 25% concentration afterwards and carry out pH regulator;
(3) under the stirring velocity that keeps 100r/min, drip tetraethyl-silica alkane at last, continue 24 hours; Under the centrifugal speed of 5400r/min, separate afterwards and obtained the hollow microsphere that there is the silicon-dioxide parcel on the surface in 15 minutes.
Wherein, the proportioning of above-mentioned polymer hollow particles preferred embodiment is as follows:
Polymer core:
The composition weight proportioning
Methymethacrylate 11.63 %
Methacrylic acid 7.09%
Fourth fat 10.30%
Ethylene glycol dimethacrylate 0.18%
Sodium laurylsulfonate 0.003%
Ammonium persulphate 0.28%
Water 70.517%;
Intermediate polymer:
The composition weight proportioning
Methymethacrylate 8.61%
Methacrylic acid 1.02%
Vinylbenzene 2.47%
Ammonium persulphate 0.12%
Water 64.06%
Polymer core emulsion 23.72%;
Polymer shell:
The composition weight proportioning
Vinylbenzene 18.22%
Fourth fat 0.69%
Vinylstyrene 0.69%
Ammonium persulphate 0.15%
Water 15.39%
Intermediate polymer 64.86%.
Claims (2)
1. preparation method at polymer hollow particles surface coated silica, it is characterized in that: its concrete technology is:
(1) preparation method of polymer hollow particles, its concrete steps are as follows:
A. the preparation of polymer core, concrete technology is: add whole water earlier, account for the ammonium persulphate of total amount 1/4 and account for methymethacrylate, methacrylic acid, fourth fat and the ethylene glycol dimethacrylate of total amount 1/20,80
oPolymerization is 40 minutes under the C, drips methymethacrylate, methacrylic acid, fourth fat, the ethylene glycol dimethacrylate of residue 19/20 and the ammonium persulphate that remains 3/4 then, and this process need is 80
oContinue 4.5 hours under the C, be warmed up to 90 afterwards
oC kept this temperature 30 minutes simultaneously, the polymer core emulsion that obtains synthesizing;
B. the preparation of intermediate polymer, its concrete technology is: earlier above-mentioned synthetic polymer core emulsion is diluted to 10% solid content, component and proportioning by above-mentioned intermediate polymer continues to drip methymethacrylate, methacrylic acid, vinylbenzene, ammonium persulphate and water then, 80
oIn the presence of ammonium persulphate, continue reaction 40-60 minute under the C, obtain the intermediate polymer emulsion;
C. the preparation of polymer shell, its concrete technology is: be added drop-wise in the intermediate polymer emulsion, 90 by the mixing with vinylbenzene, fourth fat and Vinylstyrene of the composition of above-mentioned polymer shell and proportioning
oAmmonium persulphate exists and to continue reaction down 2-3 hour under the C, afterwards the polymkeric substance cool to room temperature is formed the emulsion system of three layers in polymer core/intermediate/shell;
D. carry out alkaline purification, the polymer core/intermediate/three layers of emulsion system of shell that synthesized are put into water bath with thermostatic control, in the alkali environment, handle under the speed conditions of maintenance 400r/min, can make the synthetic polymer hollow microsphere;
(2) polymer hollow particles 9% water dispersion that makes is dripped the polyethyleneimine: amine aqueous solution of 1mg/ml under the stirring velocity of low speed, wherein the weight proportion of polymer hollow particles 9% water dispersion and polyethyleneimine: amine aqueous solution is 1:2, separates obtaining the polymer hollow particles particle after lasting 6 hours under centrifugal speed at a high speed;
(3) the polymer hollow particles particle of gained is distributed to again forms 10% hollow microsphere water dispersion in the water, then with the hollow microsphere water dispersion with 10% concentration dilution in alcohol concn is 80% ethanolic soln, with ultra-sonic oscillation 15 minutes, add 36% concentrated hydrochloric acid or the ammoniacal liquor of 25% concentration afterwards and carry out pH regulator;
(4) under the stirring velocity that keeps low speed, drip tetraethyl-silica alkane at last, continue 24 hours; Under the centrifugal speed of middling speed, separate afterwards and obtained the hollow microsphere that there is the silicon-dioxide parcel on the surface in 15 minutes;
Described polymer hollow particles comprises synthetic polymer core/intermediate/three layers of emulsion system of shell, and wherein, main component and the weight proportion of described polymer core are as follows:
Methymethacrylate 10-12%
Methacrylic acid 6-8%
Fourth fat 10-12%
Ethylene glycol dimethacrylate 0.1-0.3%
Sodium laurylsulfonate 0.002-0.004%
Ammonium persulphate 0.2-0.5%
Water 68-72%;
Concrete component and the weight proportion of described intermediate polymer are as follows:
Methymethacrylate 8-14%
Methacrylic acid 1-3%
Vinylbenzene 2-5%
Ammonium persulphate 0.1-0.3%
Water 60-65%
Polymer core 16-24%;
Main component and the weight proportion of described polymer shell are as follows:
Vinylbenzene 16-20%
Fourth fat 0.5-1%
Vinylstyrene 0.5-1%
Ammonium persulphate 0.1-0.3%
Water 13-20%
Intermediate polymer 60-65%.
2. the preparation method of polymer hollow particles according to claim 1, it is characterized in that: described alkali envrionment conditions is: under the situation of using the ammoniacal liquor neutralization, the water bath with thermostatic control temperature remains on 50-100 degree centigrade, and dropping alkali acid mol ratio is that the ammoniacal liquor of 0.75-3.5 reacted 1-6 hour; Perhaps under the situation of using the sodium hydroxide neutralization, the water bath with thermostatic control temperature remains on 85-95 degree centigrade, the sodium hydroxide reaction that the sour mol ratio of dropping alkali is 1.1-1.5 2-4 hour.
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| WO2017128300A1 (en) * | 2016-01-29 | 2017-08-03 | 深圳大学 | Hollow polymer microsphere, preparing method therefor and use thereof |
| CN105802010B (en) * | 2016-04-01 | 2018-04-24 | 星威国际家居有限公司 | PP composite material of big thick poor precise injection molding part and preparation method thereof |
| CN109694436A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of alkene-alkene alkoxide polymer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1454924A (en) * | 2003-05-15 | 2003-11-12 | 复旦大学 | Multifunctional organic-inorganic composite polymeric microball and preparing method thereof |
| CN101113183A (en) * | 2007-04-03 | 2008-01-30 | 南开大学 | Mono-dispersed nano/micron polymer hollow microsphere resin and method for synthesizing the same |
| CN101941736A (en) * | 2010-10-21 | 2011-01-12 | 北京科技大学 | Preparation method of echinoid titanium dioxide microspheres in single/double layer cavity structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1454924A (en) * | 2003-05-15 | 2003-11-12 | 复旦大学 | Multifunctional organic-inorganic composite polymeric microball and preparing method thereof |
| CN101113183A (en) * | 2007-04-03 | 2008-01-30 | 南开大学 | Mono-dispersed nano/micron polymer hollow microsphere resin and method for synthesizing the same |
| CN101941736A (en) * | 2010-10-21 | 2011-01-12 | 北京科技大学 | Preparation method of echinoid titanium dioxide microspheres in single/double layer cavity structure |
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