CN103421253A - Preparation method of polystyrene hollow microballs and applications thereof - Google Patents
Preparation method of polystyrene hollow microballs and applications thereof Download PDFInfo
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Abstract
The invention provides a preparation method of polystyrene hollow microballs, microballs prepared by the method, and applications thereof. The preparation method comprises following steps: dissolving polystyrene into poly monomer styrene, adding an initiator, a cross-linking agent, and a foaming agent, evenly mixing so as to obtain an oil phase; dissolving a dispersant or a dispersant and an emulsifier into water so as to obtain a water phase; fully mixing the oil phase and the water phase, homogenously dispersing the oil phase in the water phase so as to obtain an emulsion; heating to make the foaming agent to foam and the monomer to polymerize, subjecting the obtained solid phase to a suction filtration treatment, and drying so as to obtain the polystyrene hollow microballs. The polystyrene hollow microballs have the characteristics of inner hollow structure, small particles, and controllable particle size distribution, and can be well applied to the fields of oil drilling liquid, cosmetic, and paint. The preparation method has the advantages of simple preparation process, easy control of technology, and easy industrialization.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of polystyrene tiny balloon.More particularly, the present invention relates to a kind of method and application for preparing the polystyrene tiny balloon from dissolution method.
Background technology
The hollow microsphere shaped material, because its special hollow structure has unique chemistry and physical properties, causes people's concern in recent years just more and more, becomes the study hotspot of Material Field.Up to now, inorganic materials, polymer materials, metal oxide materials and semiconductor material (gallium oxide, gan) etc. all are prepared into the hollow microsphere shaped material by researcher trial both at home and abroad, and these materials present the specific function different from corresponding solid material.These hollow microsphere shaped materials with special characteristics are expected to be applied to the aspects such as microreactor, drug conveying, control release, photochemical catalysis, enzyme coating, photonic crystal.In addition, because hollow microsphere shaped material density is low, useful area is large, it is heat insulation to have, sound-absorbing and light hide performance, therefore can be used as density light-weight additive, resin additive and space-filling agent etc., be widely used in industry and the fields such as papermaking, oil production, building coating and biological medicine.
Inorganic hollow microspheres is usingd inorganic materials usually as shell, by methods such as high-temperature digestion and spray method, template, makes, and studies at present the more tiny balloons such as carbon, silicon-dioxide, titanium dioxide, aluminum oxide, hydroxyapatite that have.Inorganic hollow microspheres, except having low density characteristics, also has that hardness is high, intensity is high, an outstanding advantages such as corrosion-resistant, Heat stability is good, has a good application prospect.Wherein hollow glass bead has been ripe industrialization product, as U.S. Potters company and Belgian Glaverbel company, Pittsburgh Corning company, Minnesota Mining and Manufacturing Company etc., can produce in a large number hollow glass micropearl.Hollow glass bead is thin-walled white hollow spheroid, and main component is soda-lime, borosilicate glass, and density range can be from 0.10g/cm
3To 0.70g/cm
3, ultimate compression strength reaches as high as 124Mpa, and, along with the development of glass microballon production technology, the intensity that hollow glass micropearl can bear can be higher.
The polymer hollow particles shell structure be take organic polymer as main, and the shell kind mainly contains resol, polystyrene, polymethylmethacrylate etc. at present, and the method for preparation mainly contains template, self-assembly method and emulsion polymerization etc.This hollow microsphere is due to due to wall material self character, it has certain deformability, with Inorganic Hollow Microspheres, compare, the characteristics that polymer hollow particles is enbrittled is little, toughness is strong, therefore the polymer hollow particles material has better wear-resisting, anti-shear performance, under dynamic condition, percentage of damage is low, and this uses significant under dynamic environment for needs, such as petroleum drilling, Cementing etc.Since 21 century, domestic and international researcher has carried out a large amount of research and report to the polymer hollow particles material, but generally speaking because polymer tiny balloon preparation still exists that preparation process is loaded down with trivial details, the spheroid particle diameter controls that difficulty is large, hollow ball shell thickness and phase composite are difficult to the problems such as effectively accurately control, most only limits to the laboratory study stage, and industrialization degree is low.
Preparation method about the polystyrene tiny balloon mainly contains following several at present:
1) form the polystyrene tiny balloon by pore-creating agent.Patent 200710132704 has been introduced a kind of preparation method of nano-level crosslinked polystyrene hollow micro-sphere, at first emulsifying agent, assistant for emulsifying agent are added to the water, separately initiator is dissolved in the oil phase of vinylbenzene, Vinylstyrene and octane-iso or n-Hexadecane formation, oil phase is added to the water, ultrasonic emulsification, the polymerization that heats up under mechanical stirring, after reacting 24 hours, centrifugation, vacuum-drying, obtain Powdey cross-linked polystyrene hollow microsphere.(the low-density polystyrene atomic laboratory preparation such as bang duckweed, Hebei North institute journal (natural science edition), the 22nd the 1st phase of volume, in February, 2006) the organic phase dispersion suspension formed by monomer styrene, linking agent Vinylstyrene, initiator B PO and the pore-creating agent gasoline stirred after going to hinder is distributed in water, then the polymerization that heats up, obtained white polystyrene parcel gasoline microballoon.Filter, hot wash, remove gasoline with acetone after drying again, obtains density and be less than 0.5g/cm
3, particle diameter is less than the polystyrene tiny balloon of 50 μ m.The principle of the method utilization is that reaction monomer, coupling agent, initiator used dissolves in pore-creating agent, and the product that polymerization generates can not be dissolved in pore-creating agent, carrying out with polyreaction, pore-creating agent will be gradually to the spheroid internal migration, a shell of final formation is the commissure polymkeric substance, the microballoon of internal package pore-creating agent, just obtain the polystyrene tiny balloon by the pore-creating agent vaporized expanding or after utilizing air to replace pore-creating agent.Tiny balloon particle diameter prepared by the method is less than normal, inapplicable when preparing the greater particle size tiny balloon, viscosity due to monomer is low in addition, is easy to break through the liquid phase resistance of oil phase in perforating agent foaming or the process that expands and, in spilling into the aqueous solution, causes the destruction of hollow structure.
2) the drop oven process prepares the polystyrene tiny balloon.Utilize droplet generator to form the small droplets of polystyrene (Ps) solution, fall in the constant temperature that then drop Chi 4-5m is high (approximately 200 ~) stove. just can obtain the polystyrene tiny balloon.The forming process of tiny balloon in stove is as follows: when the polystyrene drop has just entered in the boiler tube of high temperature, due to the evaporation of volatile organic solvent, at first drop shrinks, and along with solvent constantly evaporates, the polystyrene concentration on drop surface increases gradually.In this process, drop in the heated while because evaporative process is cooled.After the drop surface forms solid film, the evaporation of solvent is suppressed, and drop starts heating, and when the drop temperature surpasses the boiling point of solvent, drop inside starts to form bubble, and spherical shell expands rapidly.In the process that spherical shell expands, due to the attenuation of ball wall, be conducive to solvent to the transporting of surface, so the evaporation of the solvent strengthening of having got back, finally just can obtain the polystyrene tiny balloon through overcooling again.The method needs special-purpose many warm areas of equipment drop stove.
3) micropackaging method.The micropackaging method is to prepare the most frequently used method of polystyrene tiny balloon in current domestic literature.Its principle is to adopt three-phase solution: the first water (W1): pure water or pure water+tensio-active agent; Oil phase (O): the homogeneous latex emulsion that PS+ organic solvent or styrene monomer and coupling agent and initiator mix; The second water (W2): pure water+dispersion agent.Take suitable mode to prepare W1/O/W2, multiple emulsion.Under certain conditions, along with organic solvent in oil phase is diffused into W2 phase or evaporation gradually, oil phase concentration increases gradually until finally fully curing, forms the PS(polystyrene) spherical shell.So just forming shell is polystyrene, the microballoon of internal package water, vacuum filtration, washing.Packaged water is removed in vacuum-drying, can obtain the polystyrene tiny balloon.The method technique is relatively simple, and the reaction times is short, but needs organic solvent in preparation process, and the output per single reactor of the method preparing product is low in addition.
The preparation method and application of the polystyrene tiny balloon in to the effect that polymer hollow microballon of the present invention, the present invention improves first method and improves, new preparation method has been proposed, control oil phase viscosity by dissolve the part polystyrene in styrene monomer, thereby can prepare the greater particle size product, and more be conducive to formation and the maintenance of hollow structure.
Summary of the invention
The object of the present invention is to provide that simple, the hollow breakage rate of a kind of preparation process is low, particle diameter is easily controlled, easy industrialized polystyrene tiny balloon preparation method and application thereof.
The method that the present invention utilizes is from the method for dissolving, be about to polymer dissolution in monomer, improve monomer viscosity, and then control condition causes monomer, tiny balloon prepared by this method had both contained original component of polymer, also contained the product composition that monomer causes post polymerization.
The invention provides a kind of method for preparing the polystyrene tiny balloon, comprise following steps:
A) preparation of oil phase: polystyrene is dissolved in styrene monomer, then adds initiator, linking agent, emulsifying agent and whipping agent, stir rear as oil phase;
B) preparation of water: add dispersion agent and emulsifying agent in distilled water, the solution be uniformly dissolved is as water.
C) under water bath condition, control temperature at room temperature condition, oil phase is distributed in water, the mass ratio of controlling oil phase and water is not more than 1: 2, and preferably 1: 5-1: 7; After oil phase is dispersed in water, bath temperature is risen to 70-95 ℃, preferably 75-80 ℃; Start reaction, after finishing reaction, utilize the suction filtration device by the product suction filtration, will take out product caught on a filter and dry and obtain the polystyrene tiny balloon.
In whole reaction process, should keep liquid phase in the dynamic scatter state, keep exactly the emulsion can not be static, can stir, always ultrasonic or do not stop circulation etc. with little pump always, until monomer polymerization solidifies.Because if liquid phase is static before having reacted, will cause creaming of emulsion or destruction.
Above-mentioned steps a) in polystyrene used be preferably used foamed plastics and/or industrialization product polystyrene raw material.
Above-mentioned steps a) in the weight of the polystyrene 2-30% that is vinylbenzene weight, be preferably the 4-20% of vinylbenzene weight; The 0.02-3% that initiator weight is styrene monomer weight, be preferably the 0.1-0.5% of styrene monomer weight; The 0-3% that linking agent weight is styrene monomer weight, be preferably the 0.5-2.5% of styrene monomer weight; The 2-10% that emulsifying agent weight is polystyrene and vinylbenzene quality sum, be preferably the 3-5% of polystyrene and vinylbenzene quality sum; The 1-15% that whipping agent weight is polystyrene weight and styrene monomer weight sum, be preferably the 1-10% of polystyrene and vinylbenzene quality sum.
Above-mentioned steps a) middle initiator is selected from least one in azo-initiator, organic peroxy class initiator, inorganic peroxy class initiator or oxidation-reduction initiator.
Above-mentioned steps a) in linking agent be selected from a kind of in divinylbenzene, vulcabond, N,N methylene bis acrylamide (MBA) or ethylene glycol dimethacrylate.
Above-mentioned steps a) in emulsifying agent be selected from the emulsifying agent of HLB value scope at 3-8, the further preferably 80(of class of department oleic acid sorbitol ester) or the 60(of class of department sorbitan tristearate), the 40(of class of department sorbitol anhydride Palmitate) or glycerin fatty acid ester at least one.
Above-mentioned steps a) middle whipping agent is selected from least one in low-carbon alkanes, octane-iso, n-Hexadecane or cyclohexanone.The preferred Skellysolve A of low-carbon alkanes, normal hexane or sherwood oil.
Above-mentioned steps b) the dispersion agent weight 0.12-8% that is distilled water weight in, be preferably the 1-3% of distilled water weight; The 0-1.0% that the weight of emulsifying agent is distilled water weight, be preferably the 0.1-0.3% of distilled water weight.
Above-mentioned steps b) dispersion agent described in is at least one in xanthan gum, gelatin, carboxymethyl cellulose, Polyvinylpyrolidone (PVP), Natvosol or polyvinyl alcohol.
Above-mentioned steps b) emulsifying agent described in is at least one in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or OP-10.
Above-mentioned steps c) reaction times of reaction described in is at least 4 hours, preferably 6-9 hour.
Above-mentioned steps c) dispersing mode described in adopts alr mode, ultrasonic power or SPG emulsifying manner.
The invention still further relates to a kind of application that utilizes the polystyrene tiny balloon of above-mentioned preparation, described polystyrene tiny balloon is joined in drilling fluid, for reducing the sticking coefficient of drilling fluid.
Beneficial effect of the present invention is:
1) the polystyrene tiny balloon particle diameter prepared by the method is even, and the product circularity is good, and product cut size can be controlled by ratio, foaming agent consumption, dispersant, dispersant dosage, the stirring velocity of adjusting polystyrene and styrene monomer.
2) the discarded polystyrene of the method utilization, as one of raw material, can be converted into " white pollution " the polystyrene tiny balloon of high added value.
3) the recyclable recycling of water used in the reaction, reduced cost, easily industrialization.
The accompanying drawing explanation
The stereoscan photograph of the external structure of the polystyrene tiny balloon that Fig. 1 is embodiment 3 preparations.
Fig. 2 is by the internal structure stereoscan photograph of the polystyrene tiny balloon of embodiment 3 gained.
Embodiment
Embodiment 1
By computer packaging polystyrene foamed plastics clean up, dry for standby;
1) configuration oil phase: take the above-mentioned clean polystyrene foamed plastics of 0.63g, add styrene monomer 31.5g, benzoyl peroxide 0.0063g, class of department 800.65g, normal hexane 4.8g, mix and make oil phase; Polystyrene is 2% of vinylbenzene weight; Initiator is 0.02% of styrene monomer weight; Coupling agent weight is 0% of styrene monomer weight; Emulsifying agent weight is 2% of polystyrene and styrene monomer weight sum; Whipping agent weight is 15% of polystyrene and styrene monomer weight sum, and the oil phase total mass is 37.5863g.
2) configuration disperses water: 0.23g gelatin, 0.14g Sodium dodecylbenzene sulfonate and 0.05g sorbitol anhydride oleate are joined in 187ml distilled water, stir and make water; Dispersion agent weight is 0.12% of water weight; Emulsifying agent weight is 0.1% of water weight, and the water total mass is 187.42g.
3) described water is poured into to the reactor (as there-necked flask) with condensing works (as prolong), put into water-bath; The adjustment rotating speed is 300r/min, under agitation condition, described oil phase is joined to water, obtains the uniform emulsion of emulsification, and wherein oil phase and water mass ratio are 1: 5; Temperature is risen to 85 ℃, maintain and stir the 6h end;
4) with the suction filtration device, described emulsion is carried out to the suction filtration separation, isolate bead, after 70 ℃ of oven dry 24h, obtain the polystyrene tiny balloon that median size is 137 μ m.
Embodiment 2
By computer packaging polystyrene foamed plastics wash clean, dry for standby;
1) configuration oil phase: take the above-mentioned clean polystyrene foamed plastics of 7.38g, add styrene monomer 24.6g and benzoyl peroxide 0.738g, add ethylene glycol dimethacrylate 0.615, the 603.198g of class of department, make oil phase after mixing; Wherein 30% of polystyrene weight styrene monomer weight; Initiator is 3.0% of styrene monomer weight; Coupling agent weight is 2.5% of styrene monomer weight; Emulsifying agent weight is 10% of polystyrene weight and styrene monomer weight sum; Whipping agent weight is 1% of polystyrene weight and styrene monomer weight sum, and the oil phase total mass is 36.531g.
2) configuration disperses water: the 8g polyvinyl alcohol is joined in 100ml distilled water, stir; Dispersion agent weight is 8% of water weight, and emulsifying agent weight is 0% of water weight, and the water total mass is 108g.
3) described water is poured into to the reactor (as there-necked flask) with condensing works (as prolong), put into water-bath; The adjustment rotating speed is 350r/min, under agitation condition, described oil phase is joined to water, obtains the uniform emulsion of emulsification, and wherein the oil water phase mass ratio is that water oil ratio is 1: 3.0; Temperature is risen to 85 ℃, maintain and stir the 9h end;
4) with the vacuum filtration device, described emulsion is carried out to the suction filtration separation, isolate bead, after 70 ℃ of oven dry 24h, obtain the polystyrene tiny balloon that median size is 168 μ m.
Embodiment 3
By computer packaging polystyrene foamed plastics wash clean, dry for standby;
1) configuration oil phase: take the above-mentioned clean polystyrene foamed plastics of 4g, add styrene monomer 100 and benzoyl peroxide 0.5g, add ethylene glycol dimethacrylate 3g, class of department 605.2g, normal hexane 5.2g, make oil phase after mixing; Wherein polystyrene weight is 4% of styrene monomer weight, and initiator is 0.5% of styrene monomer weight; Coupling agent weight is 3% of styrene monomer weight, and emulsifying agent weight is 5% of polystyrene weight and styrene monomer weight sum; Whipping agent weight is 5% of polystyrene weight and styrene monomer weight sum, and the oil phase total mass is 117.9g;
2) configuration disperses water: the 6.6g polyvinyl alcohol is joined in 220ml distilled water, then add the 2.2g sodium lauryl sulphate, stir as water; Dispersion agent weight is 3% of water weight, and emulsifying agent weight is 1.0% of water weight, and the water total mass is 228.8g;
3) described water is poured into to the reactor (as there-necked flask) with condensing works (as prolong), put into water-bath; The adjustment rotating speed is 350r/min, under agitation condition, described oil phase is joined to water, obtains the uniform emulsion of emulsification, and wherein the oil water phase mass ratio is 1: 2.0; Temperature is risen to 85 ℃, maintain and stir the 9h end;
4) with the vacuum filtration device, described emulsion is carried out to the suction filtration separation, isolate bead, after 70 ℃ of oven dry 24h, obtain the polystyrene tiny balloon that median size is 87 μ m.
Embodiment 4
Get China Petrochemical Industry's Yanshan Petrochemical product: polystyrene, the trade mark: 666D is standby;
1) configuration oil phase: take the above-mentioned clean polystyrene foamed plastics of 20g, add styrene monomer 100 and benzoyl peroxide 0.1g, add ethylene glycol dimethacrylate 0.5g, the 603.6g of class of department, normal hexane 12g, make oil phase after mixing; Wherein 20% of polystyrene weight styrene monomer weight, initiator is 0.1% of styrene monomer weight; Coupling agent weight is 0.5% of styrene monomer weight, and emulsifying agent weight is 3% of polystyrene weight and styrene monomer weight sum; Whipping agent weight is 10% of polystyrene weight and styrene monomer weight sum; The oil phase total mass is 136.2g.
2) configuration disperses water: configuration disperses water: the 9.45g polyvinyl alcohol is joined in 945ml distilled water, then add the 2.84g sodium lauryl sulphate, stir as water; Dispersion agent weight is 1% of water weight, and emulsifying agent weight is 0.3% of water weight; Disperseing the water total mass is 957.29g.
3) utilize the SPG film that aperture is 20 μ m to carry out film emulsification preparation O/w emulsion above gained water and oil phase, obtain the uniform emulsion of emulsification, wherein the oil water phase mass ratio is 1: 7.0; Emulsion is transferred in flask, stirred under 400r/min, temperature is risen to 85 ℃, maintain and stir the 9h end;
4) with the vacuum filtration device, described emulsion is carried out to the suction filtration separation, isolate bead, after 70 ℃ of oven dry 24h, obtain the polystyrene tiny balloon that median size is 73 μ m.
Embodiment 5
Get a beaker, in the 200ml tap water, add the 0.4g xanthan gum as carrying stick, add the polystyrene tiny balloon of 20g embodiment 3 preparations after being uniformly dissolved, join to obtain low density drilling fluid after stirring.Recording this drilling fluid density is 0.94g/cm
3.So polystyrene tiny balloon of the present invention can be used as the light-weight additive of drilling fluid and uses.
Remarks: the measuring method of bead density: get in the placement of 200ml tap water and beaker, add therein the 0.4g xanthan gum as carrying stick, improve liquid phase viscosity, make tiny balloon can be suspended in liquid phase; Add the 20g tiny balloon after being uniformly dissolved, join to obtain low density drilling fluid after stirring, measuring this drilling fluid density is ρ 1, and establishing bead density is the ρ ball.According to ρ=m/v principle, ρ 1=(200+0.4+20)/200+ (20/ ρ ball) (xanthan gum can be dissolved in water, and its volume is ignored), can calculate the ρ ball.The measuring method of drilling fluid density ρ 1 is shown in GB/T 16783-1997 " water-base drilling fluid On-Site Test Procedure " " 1 drilling fluid density ".
Claims (14)
1. a method for preparing the polystyrene tiny balloon comprises following steps:
A) preparation of oil phase: polystyrene is dissolved in styrene monomer, then adds initiator, linking agent, emulsifying agent and whipping agent, stir rear as oil phase;
B) preparation of water: add dispersion agent and emulsifying agent in distilled water, the solution be uniformly dissolved is as water;
C) under water bath condition, control temperature at room temperature condition, oil phase is distributed in water, after oil phase is dispersed in water, bath temperature is risen to 70-95 ℃, preferably 75-80 ℃, start reaction; After finishing reaction, utilize the suction filtration device by the product suction filtration, will take out product caught on a filter and dry and obtain the polystyrene tiny balloon.
2. method according to claim 1, is characterized in that, the polystyrene of described step in a) is used foamed plastics and/or industrialization product polystyrene raw material.
3. method according to claim 1 and 2, is characterized in that, the 2-30% that the weight of the polystyrene of described step in a) is vinylbenzene weight is preferably the 4-20% of vinylbenzene weight; The 0.02-3% that initiator weight is styrene monomer weight, be preferably the 0.1-0.5% of styrene monomer weight; The 0-3% that linking agent weight is styrene monomer weight, be preferably the 0.5-2.5% of styrene monomer weight; The 2-10% that emulsifying agent weight is polystyrene and vinylbenzene quality sum, be preferably the 3-5% of polystyrene and vinylbenzene quality sum; The 1-15% that whipping agent weight is polystyrene weight and styrene monomer weight sum, be preferably 1-10%.
4. method according to claim 1 and 2, is characterized in that, the initiator of described step in a) is selected from least one in azo-initiator, organic peroxy class initiator, inorganic peroxy class initiator or oxidation-reduction initiator.
5. method according to claim 1 and 2, is characterized in that, the linking agent of described step in a) is selected from a kind of in divinylbenzene, vulcabond, N,N methylene bis acrylamide or ethylene glycol dimethacrylate.
6. method according to claim 1 and 2, is characterized in that, the emulsifying agent of described step in a) is selected from the emulsifying agent of HLB value scope at 3-8, further preferred at least one in class of department 80 or class of department 60, class 40 of department or glycerin fatty acid ester.
7. method according to claim 1 and 2, is characterized in that, the whipping agent of described step in a) is selected from least one in low-carbon alkanes, octane-iso, n-Hexadecane or cyclohexanone; The preferred Skellysolve A of low-carbon alkanes, normal hexane or sherwood oil.
8. method according to claim 1 and 2, is characterized in that, described step b) in the dispersion agent weight 0.12-8% that is distilled water weight, be preferably the 1-3% of distilled water weight; The 0-1.0% that the weight of emulsifying agent is distilled water weight, be preferably the 0.1-0.3% of distilled water weight.
9. method according to claim 1 and 2, is characterized in that, described step b) described in dispersion agent be selected from least one in xanthan gum, gelatin, carboxymethyl cellulose, Polyvinylpyrolidone (PVP), Natvosol or polyvinyl alcohol.
10. method according to claim 1 and 2, is characterized in that, described step b) described in emulsifying agent be selected from least one in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or OP-10.
11. method according to claim 1 and 2, is characterized in that, described step c) in oil phase and the mass ratio of water be not more than 1: 2, preferably 1: 5-1: 7.
12. method according to claim 1 and 2, is characterized in that, described step c) reaction times of described reaction is at least 4 hours, preferred 6-9 hour.
13. method according to claim 1 and 2, is characterized in that, described step c) described in dispersion adopt alr mode, ultrasonic power or SPG emulsifying manner.
14. the application of the tiny balloon prepared according to the described method of claim 1 or 2, comprise described polystyrene tiny balloon joined in drilling fluid, for reducing the density of drilling fluid.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101125903A (en) * | 2007-09-24 | 2008-02-20 | 南京大学 | Method for preparing nano-level crosslinked polystyrene hollow micro-sphere |
| CN102417552A (en) * | 2011-09-22 | 2012-04-18 | 中国科学院过程工程研究所 | Polymer nanomicrosphere product with uniform and controllable size and preparation method thereof |
-
2012
- 2012-05-17 CN CN201210154379.2A patent/CN103421253B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101125903A (en) * | 2007-09-24 | 2008-02-20 | 南京大学 | Method for preparing nano-level crosslinked polystyrene hollow micro-sphere |
| CN102417552A (en) * | 2011-09-22 | 2012-04-18 | 中国科学院过程工程研究所 | Polymer nanomicrosphere product with uniform and controllable size and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| WEI BIN,ET AL.: "Preparation of hollow microspheres from waste foamed polystyrene plastics: control of tap density and average diameter", 《材料导报》, vol. 24, no. 1, 31 January 2010 (2010-01-31), pages 94 - 99 * |
| 梁志武等: "中空结构聚合物微粒的制备方法", 《高分子通报》, no. 5, 31 October 2003 (2003-10-31), pages 36 - 40 * |
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