CN102311555A - Preparation method for coating silica by utilizing polymer hollow microspheres - Google Patents
Preparation method for coating silica by utilizing polymer hollow microspheres Download PDFInfo
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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 through this hollow microsphere.
Background technology
At present; Coating industry be unable to do without the demand of white titanium pigment, 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.The most effectively be exactly that refraction coefficient reaches 2.7 white titanium pigment at present.But the white titanium pigment industry is the industry of a highly energy-consuming and high pollution, and particularly domestic most employing method for producing gtitanium dioxide with sulphuric acid destroys ecotope and demands for 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 destruction under the effect of external force and subsides.The paint film of working it out like this is easy to occur glossy to be changed suddenly, so hollow microsphere can not add in coating and surpass 8%, and can only seldom partly replace white titanium pigment.To replace in the coating dependence completely to white titanium pigment; 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 is carried out the inorganics surface and coat, particularly silica sphere coats, and reaches the purpose that improves shading factor.
Summary of the invention
The objective of the invention is a kind of preparation method who utilizes the polymer hollow particles coated silica, it is added in the coating can thoroughly replace white titanium pigment, satisfy dry film and wet film demand simultaneously for opacifying power.
The present invention realizes through following technical proposals:
A kind of preparation method who utilizes the polymer hollow particles coated silica, concrete steps are following:
(1) at first through letex polymerization synthetic polymer nuclear, on polymer core, forms intermediate polymer then, on midbody, form the polymkeric substance shell at last, form hollow microsphere through alkaline purification afterwards through seeding polymerization through seeding polymerization.
Above-mentioned polymer hollow particles comprises synthetic polymer core/midbody/three layers of emulsion system of shell, and wherein, the staple and the weight proportion of said polymer core are following:
Methymethacrylate 10-12%
Methylacrylic 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%;
The concrete component and the weight proportion of said intermediate polymer are following:
Methymethacrylate 8-14%
Methylacrylic acid 1-3%
Vinylbenzene 2-5%
Ammonium persulphate 0.1-0.3%
Water 60-65%
Polymer core 16-24%;
The staple and the weight proportion of said polymer shell are following:
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 following:
(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, methylacrylic acid, fourth fat and the ethylene glycol dimethacrylate of total amount 1/20,80
oPolymerization is 40 minutes under the C, drips methymethacrylate, methylacrylic 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
oC continues 4.5 hours down, is warmed up to 90 afterwards
oC kept this temperature 30 minutes simultaneously, obtained synthetic polymer core emulsion;
(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, methylacrylic 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
oThere is continuation reaction down 2-3 hour in ammonium persulphate under the C, afterwards the polymkeric substance cool to room temperature is formed the trilaminar emulsion system of polymer core/midbody/shell;
(4) carry out alkaline purification, institute's synthetic polymer core/midbody/three layers of emulsion system of shell 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.
Said alkali envrionment conditions is: when using under the ammoniacal liquor neutral situation, 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 when using under the sodium hydroxide neutral situation, the water bath with thermostatic control temperature remains on 85-95 degree centigrade, and dropping alkali acid mol ratio is that the sodium hydroxide of 1.1-1.5 reacted 2-4 hour.
(2) carry out the silicon-dioxide parcel with sol-gel method, its concrete technology is:
(1) elder generation drips the polymer hollow particles that makes 9% water dispersion 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, under 9000r/min, carries out spinning after lasting 6 hours 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, the ammoniacal liquor that adds 36% concentrated hydrochloric acid or 25% concentration afterwards carries out PH to be regulated;
(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 need not pass through organic solvent dissolution, strong acid and strong base etching or high-temperature calcination and remove the hollow microsphere template; 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 through changing raw material; Through this polymer hollow particles of surperficial coated silica,, satisfy dry film and wet film demand simultaneously for opacifying power with can thoroughly replacing white titanium pigment in its adding coating; Modification through different inorganic minerals simultaneously can improve the application of hollow microsphere in different occasions.
[embodiment]
A kind of with vinylbenzene, methymethacrylate is a monomer synthetic polymer hollow particles, and passes through the preparation method of sol-gel method coated silica, and concrete steps are following:
(1) at first through letex polymerization synthetic polymer nuclear, on polymer core, forms intermediate polymer then, on midbody, form the polymkeric substance shell at last, form hollow microsphere through alkaline purification afterwards through seeding polymerization through seeding polymerization.
Said polymer hollow particles comprises polymer shell, midbody, polymer core and coated with silica layer, and concrete set of dispense ratio and preparation method are following:
1, the making of polymer core:
Methymethacrylate 10-12%
Methylacrylic 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 explained as follows:
Methymethacrylate: MMA, common commercially available;
Methylacrylic acid: MAA, common commercially available;
Fourth fat: BA, common commercially available;
Ethylene glycol dimethacrylate: EDGMA, common commercially available;
Sodium laurylsulfonate: SDS, common commercially available;
Ammonium persulphate: APS, common commercially available;
Water: zero(ppm) water.
The preparation technology of above-mentioned polymer core is following: add earlier whole water, account for the ammonium persulphate of total amount 1/4 and account for methymethacrylate, methylacrylic acid, fourth fat and the ethylene glycol dimethacrylate of total amount 1/20,80
oPolymerization is 40 minutes under the C, drips methymethacrylate, methylacrylic 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
oC continues 4.5 hours down, is warmed up to 90 afterwards
oC kept this temperature 30 minutes simultaneously, obtained synthetic polymer core emulsion;
The staple and the weight proportion of embodiment one are following:
Methymethacrylate 10%
Methylacrylic acid 6%
Fourth fat 11.398%
Ethylene glycol dimethacrylate 0.1%
Sodium laurylsulfonate 0.002%
Ammonium persulphate 0.5%
Water 72%
Staple and the weight proportion of embodiment two are following:
Methymethacrylate 11%
Methylacrylic acid 7%
Fourth fat 10%
Ethylene glycol dimethacrylate 0.2%
Sodium laurylsulfonate 0.003%
Ammonium persulphate 0.4%
Water 71.397%
Staple and the weight proportion of embodiment three are following:
Methymethacrylate 11%
Methylacrylic acid 7%
Fourth fat 12%
Ethylene glycol dimethacrylate 0.25%
Sodium laurylsulfonate 0.003%
Ammonium persulphate 0.35%
Water 69.397%
Staple and the weight proportion of embodiment four are following:
Methymethacrylate 12%
Methylacrylic 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 staple and weight proportion are following:
Methymethacrylate 8-14%
Methylacrylic acid 1-3%
Vinylbenzene 2-5%
Ammonium persulphate 0.1-0.3%
Water 60-65%
Polymer core 16-24%;
Raw material is explained as follows:
Methymethacrylate: MMA, common commercially available;
Methylacrylic acid: MAA, common commercially available;
Vinylbenzene: ST, common commercially available;
Ammonium persulphate: APS, common commercially available;
Water: zero(ppm) water.
The preparation technology of above-mentioned intermediate polymer is following:
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, methylacrylic 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;
The staple and the weight proportion of embodiment one are following:
Methymethacrylate 8%
Methylacrylic acid 3%
Vinylbenzene 2%
Ammonium persulphate 0.1%
Water 62.9%
Polymer core emulsion 24%
Staple and the weight proportion of embodiment two are following:
Methymethacrylate 12.8%
Methylacrylic acid 2%
Vinylbenzene 4%
Ammonium persulphate 0.2%
Water 65%
Polymer core emulsion 16%
Staple and the weight proportion of embodiment three are following:
Methymethacrylate 14%
Methylacrylic acid 1%
Vinylbenzene 5%
Ammonium persulphate 0.3%
Water 60%
Polymer core emulsion 19.7%;
3, the making of polymer shell:
Its staple and weight proportion are following:
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 explained as follows:
Vinylbenzene: ST, common commercially available;
Vinylstyrene; DVB, common commercially available;
Fourth fat: BA, common commercially available;
Ammonium persulphate: APS, common commercially available;
Water: zero(ppm) water.
The preparation technology of above-mentioned polymer shell is following:
With vinylbenzene, the mixture of fourth fat and Vinylstyrene is added drop-wise in the synthetic emulsion system, 90
oThere is continuation reaction down 2-3 hour in ammonium persulphate under the C, afterwards the polymkeric substance cool to room temperature is formed the trilaminar emulsion system of polymer core/midbody/shell;
The staple and the weight proportion of embodiment one are following:
Vinylbenzene 16 %
Fourth fat 1%
Vinylstyrene 1%
Ammonium persulphate 0.1%
Water 16.9%
Intermediate polymer 65%
Staple and the weight proportion of embodiment two are following:
Vinylbenzene 18.7 %
Fourth fat 0.5%
Vinylstyrene 0.5%
Ammonium persulphate 0.3%
Water 20%
Intermediate polymer 60%
Staple and the weight proportion of embodiment three are following:
Vinylbenzene 20 %
Fourth fat 0.85%
Vinylstyrene 0.85%
Ammonium persulphate 0.8%
Water 13%
Intermediate polymer 64.5%
4, carry out alkaline purification:
Institute's synthetic polymer core/midbody/three layers of emulsion system of shell are put into water bath with thermostatic control; When using under the ammoniacal liquor neutral situation; 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 work as and use under the sodium hydroxide neutral situation, 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 the polymer hollow particles that makes 9% water dispersion 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, under 9000r/min, carries out spinning after lasting 6 hours 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, the ammoniacal liquor that adds 36% concentrated hydrochloric acid or 25% concentration afterwards carries out PH to be regulated;
(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 following:
Polymer core:
The composition weight proportioning
Methymethacrylate 11.63 %
Methylacrylic 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%
Methylacrylic 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 (4)
1. preparation method who utilizes the polymer hollow particles coated silica, it is characterized in that: its concrete technology is:
(1) elder generation drips the polymer hollow particles that makes 9% water dispersion 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, under the high speed centrifugal speed, separates obtaining the polymer hollow particles particle after lasting 6 hours;
(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, the ammoniacal liquor that adds 36% concentrated hydrochloric acid or 25% concentration afterwards carries out PH to be regulated;
(3) 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.
2. according to claims 1 described preparation method who utilizes the polymer hollow particles coated silica; It is characterized in that: said polymer hollow particles; Comprise synthetic polymer core/midbody/three layers of emulsion system of shell, wherein, the staple and the weight proportion of said polymer core are following:
Methymethacrylate 10-12%
Methylacrylic 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%;
The concrete component and the weight proportion of said intermediate polymer are following:
Methymethacrylate 8-14%
Methylacrylic acid 1-3%
Vinylbenzene 2-5%
Ammonium persulphate 0.1-0.3%
Water 60-65%
Polymer core 16-24%;
The staple and the weight proportion of said polymer shell are following:
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%.
3. according to the preparation method of claims 2 described polymer hollow particles, it is characterized in that: its concrete steps are following:
(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, methylacrylic acid, fourth fat and the ethylene glycol dimethacrylate of total amount 1/20,80
oPolymerization is 40 minutes under the C, drips methymethacrylate, methylacrylic 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
oC continues 4.5 hours down, is warmed up to 90 afterwards
oC kept this temperature 30 minutes simultaneously, obtained synthetic polymer core emulsion;
(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, methylacrylic 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
oThere is continuation reaction down 2-3 hour in ammonium persulphate under the C, afterwards the polymkeric substance cool to room temperature is formed the trilaminar emulsion system of polymer core/midbody/shell;
(4) carry out alkaline purification, institute's synthetic polymer core/midbody/three layers of emulsion system of shell 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.
4. the preparation method of polymer hollow particles according to claim 3; It is characterized in that: said alkali envrionment conditions is: when using under the ammoniacal liquor neutral situation; 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 when using under the sodium hydroxide neutral situation, the water bath with thermostatic control temperature remains on 85-95 degree centigrade, and dropping alkali acid mol ratio is that the sodium hydroxide of 1.1-1.5 reacted 2-4 hour.
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| CN105802010A (en) * | 2016-04-01 | 2016-07-27 | 星威国际家居有限公司 | Polypropylene composite material of precision injection molding part with large thickness difference and preparation method of polypropylene composite material |
| WO2017128300A1 (en) * | 2016-01-29 | 2017-08-03 | 深圳大学 | Hollow polymer microsphere, preparing method therefor and use thereof |
| WO2019080876A1 (en) * | 2017-10-24 | 2019-05-02 | 中国石油化工股份有限公司 | Olefin-olefinic alcohol copolymer, and preparation method therefor |
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| 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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| 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 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN105802010A (en) * | 2016-04-01 | 2016-07-27 | 星威国际家居有限公司 | Polypropylene composite material of precision injection molding part with large thickness difference and preparation method of polypropylene composite material |
| 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 |
| WO2019080876A1 (en) * | 2017-10-24 | 2019-05-02 | 中国石油化工股份有限公司 | Olefin-olefinic alcohol copolymer, and preparation method therefor |
| US11584843B2 (en) | 2017-10-24 | 2023-02-21 | China Petroleum & Chemical Corporation Beijing Research Institute Of Chemical Industry | Olefin-olefinic alcohol copolymer, and preparation method therefor |
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