CN103387625B - The preparation method of polystyrene hollow microsphere and application thereof - Google Patents
The preparation method of polystyrene hollow microsphere and application thereof Download PDFInfo
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Abstract
The present invention relates to the preparation method and application of polystyrene hollow microsphere, polystyrene is dissolved in styrene monomer and configures oil phase, oil phase viscosity is controlled by controlling polystyrene concentrations, the reaction such as precipitation solidification of the initiated polymerization of styrene monomer, polystyrene is achieved in W1/O/W2 triple emulsion, thus form the polystyrene hollow microsphere with hollow structure, and this polystyrene hollow microsphere application in drilling fluid and cementing fluid.
Description
Technical field
The present invention relates to a kind of polystyrene hollow microsphere and its preparation method and application.More particularly, the present invention relates to employing package method and prepare polystyrene hollow microsphere and the application in well drilling industry thereof.
Background technology
Hollow microsphere shaped material has unique chemistry and physical properties due to its special hollow structure, cause the concern of people in recent years just more and more, become the study hotspot of Material Field.Up to now, inorganic materials, polymer materials, metal oxide materials and semiconductor material (gallium oxide, gan) etc. are attempted being prepared into hollow microsphere shaped material by domestic and international researcher all, 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, Co ntrolled release, photochemical catalysis, enzyme are coated, 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 as density light-weight additive, resin additive and space weighting agent etc., industry and the fields such as papermaking, oil production, building coating and biological medicine can be widely used in.
Inorganic Hollow Microspheres, usually using inorganic materials as shell, is obtained by high-temperature digestion and the method such as spray method, template, and what research was more at present has the hollow microspheres such as carbon, silicon-dioxide, titanium dioxide, aluminum oxide, hydroxyapatite.Inorganic Hollow Microspheres, except having low density feature, 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 glass hollow microballon has had ripe industrialization product, as Potters company of the U.S. and Belgian Glaverbel company, Pittsburgh Corning company, Minnesota Mining and Manufacturing Company etc., can produce hollow glass microbead in a large number.Glass hollow microballon is thin-walled White hollow spheroid, main component is soda-lime, borosilicate glass, density range can from 0.10g/cm3 to 0.70g/cm3, ultimate compression strength reaches as high as 124MPa, and, along with the development of glass microballon production technology, the intensity that hollow glass microbead can bear can be higher.
Polymer hollow particles shell structure is based on organic polymer, and its temperature resistance, anti-pressure ability are main relevant with Shell Materials used, and the shell kind of current bibliographical information mainly contains resol, polystyrene, polymethylmethacrylate etc.This hollow microsphere is caused by wall material self character, there is certain deformability, compared with Inorganic Hollow Microspheres, polymer hollow particles is enbrittled little, that toughness is strong feature, therefore polymer hollow particles material has better wear-resisting, anti-shear performance, percentage of damage is low in a dynamic condition, and this uses significant for needs under dynamic environment, such as petroleum drilling, Cementing etc.Since 21 century, domestic and international researcher has carried out large quantifier elimination and report to polymer hollow particles, but generally speaking due to polymer hollow particles still also exist that preparation process is loaded down with trivial details, spheroid size controlling difficulty is large, hollow ball shell thickness and phase composite are difficult to the problems such as effectively accurately control, current great majority are only limitted to the laboratory study stage, also do not have ripe industrialization product.
The package method of improvement that to the effect that utilizes of the present invention prepares polystyrene organic hollow microballoon.Package method, also known as emulsification-solidification method, is prepare the most frequently used method of polystyrene hollow microsphere in current domestic literature.Its principle adopts three-phase solution: the first aqueous phase (W1): pure water or pure water+tensio-active agent; Oil phase (O): the homogeneous solution that polystyrene+organic solvent or styrene monomer and coupling agent and initiator mix; Second aqueous phase (W2): pure water+dispersion agent.Suitable mode is taked to prepare W1/O/W2 triple emulsion.Under certain conditions, along with organic solvent in oil phase is diffused into W2 phase or evaporation gradually, or monomer polymerization, oil phase concentration increases until finally solidify completely gradually, forms polystyrene spherical shell.So just form the microballoon that shell is polystyrene, internal package water, vacuum filtration, washing, vacuum-drying removing packaged water, can obtain polystyrene hollow microsphere.Zhang Lin etc. take into polystyrene as ball material, adopt that package method prepares that diameter is 100 ~ 300 μm, wall thickness be 2 ~ 8 μm, the polystyrene hollow microsphere (Zhang Lin of sphericity >=95%, concentricity >=90%, surfaceness≤300nm, Cui Baoshun, Zhou Lan etc. microencapsulation techniques prepares hollow plastic microsphere. light laser and particle beam, 1995,7(1): 151-156).Tsuji R and Ogushi Y adopts package method to prepare the polystyrene hollow microsphere that can be used as ICF target, diameter is approximately 520 μm of (Tsuji R, OgushiY.Fabrication of polystyrene hollow pellet with high Z microparticles oninner surface for measurement of temperature and density in ICF plasma.Fusion Engineering and Design, 1997,34-35:811-814).
From the above mentioned, package method used at present is mainly realized by three-phased emulsions, and O phase can be the oil phase of monomer and coupling agent and initiator composition, also can be that polystyrene is dissolved in organic solvent and is made into O phase.The oil phase of monomer composition does not need with an organic solvent in reaction process, but because the viscosity of monomer is low at the easy breakdown of emulsion of formation W1/O phase time, and the hollow microsphere particle diameter formed is less than normal; Be dissolved in organic solvent by polystyrene and be made into O phase and mainly there is two problems: (1) owing in use needing to use organic solvent, have injury to environmental and human health impacts; (2) the viscosity of oil phase is directly proportional to the concentration of polystyrene, and therefore when preparing oil phase, the concentration of polystyrene can not too high (being generally no more than 15%), otherwise can not effectively will disperse because O phase viscosity is too large, and therefore output per single reactor is low.
Summary of the invention
The object of the invention is to for solving the problem, providing that simple, the hollow breakage rate of a kind of preparation process is low, particle diameter easily controls, easy industrialized polystyrene hollow microsphere, and provide the preparation method and application of this polystyrene hollow microsphere.
Technical scheme of the present invention is:
A preparation method for polystyrene hollow microsphere, it comprises following steps
1) oil phase O is prepared: be dissolved in styrene monomer by polystyrene, then add initiator, linking agent and emulsifying agent, as oil phase after stirring; Wherein the weight of polystyrene is 2% ~ 30% of vinylbenzene weight, is preferably 4 ~ 20% of vinylbenzene weight; Initiator weight is 0.02 ~ 3% of styrene monomer weight, is preferably 0.1 ~ 0.5% of styrene monomer weight; Linking agent weight is the 0-3% of styrene monomer weight, is preferably the 0.5-2.5% of styrene monomer weight; Emulsifying agent dosage is the 2-10% of polystyrene and vinylbenzene weight sum, is preferably the 3-5% of polystyrene and vinylbenzene weight sum;
2) prepare W1 phase: add in distilled water emulsifiers dissolve evenly after as W1 phase, the weight of emulsifying agent is the 0.5-8% of distilled water weight, is preferably the 2-5% of distilled water weight;
3) W2 phase is prepared: in distilled water, add dispersion agent and emulsifying agent, as W2 phase after being uniformly dissolved; The weight of the dispersion agent added is the 0.12-8% of distilled water weight, is preferably the 1-3% of distilled water weight; The weight of the emulsifying agent added is the 0-1.0% of distilled water weight, is preferably the 0.1-0.3% of distilled water weight;
4) W1 is added in O phase, fully emulsified, obtained W1/O emulsion, W1 phase is 1:5.2-1:1.7 with the mass ratio of O phase, is preferably 1:2.5-1:3;
5) under water bath condition, control temperature is at room temperature condition, and W1/O emulsion evenly spread in W2 phase, W1/O emulsion is not more than 1: 2.5 with the mass ratio of W2 phase, and preferably 1: 5 ~ 1: 7; Namely start after being uniformly dispersed to heat up, bath temperature is risen to 70-95 DEG C, preferred 75-80 DEG C, at least react 4 hours, preferred 6-9 hour; Rear end reaction, keeps liquid phase to be in dynamic scatter in whole reaction process, utilizes Suction filtration device by product suction filtration; Product caught on a filter will be taken out dry and obtain product.
The state of above-mentioned dynamic scatter keeps emulsion can not be static exactly, can adopt stirring, ultrasonic or do not stop circulation etc. with little pump, until monomer polymerization solidification.If because liquid phase is static before reaction does not complete, creaming of emulsion or destruction will be caused.
Above-mentioned steps 1) in use polystyrene be polystyrene waste plastic and/or industrialization product polystyrene raw material;
Above-mentioned steps 1) in the initiator that uses be selected from least one in azo-initiator, organic peroxy class initiator, inorganic peroxy class initiator or oxidation-reduction initiator.
Above-mentioned steps 1) in the linking agent that uses be selected from divinylbenzene, vulcabond, the one in N,N methylene bis acrylamide (MBA) or ethylene glycol dimethacrylate.
Above-mentioned steps 1) in the emulsifying agent that uses be selected from the emulsifying agent of HLB scope between 3-8, at least one preferably in class 80 of department, class 60 of department or glycerin fatty acid ester.
Above-mentioned steps 2) in the emulsifying agent that uses comprise at least one in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or OP-10.
Above-mentioned steps 3) in the dispersion agent that uses comprise at least one in xanthan gum, gelatin, carboxymethyl cellulose, Polyvinylpyrolidone (PVP), Natvosol or polyvinyl alcohol.
Above-mentioned steps 3) in use emulsifying agent comprise sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, class of department 80, department class 60 or OP-10 at least one.
Above-mentioned steps 4) in emulsification can adopt mode (rotating speed >=1000r/min, the preferred 9000r/min of stirring; Stir 2-20min, preferred 5-10min) or utilize SPG film carry out emulsification or carry out ultrasonic emulsification.
Above-mentioned steps 5) dispersion can adopt ultrasonic disperse mode, SPG film emulsifying manner or alr mode.
According to a polystyrene hollow microsphere prepared by above-mentioned preparation method, this microballoon had both comprised the polystyrene of the non-commissure that early stage adds, and also comprised the later stage is polymerized generation polystyrene by styrene monomer.
The application of polystyrene hollow microsphere prepared by aforesaid method:
Polystyrene hollow microsphere is as the application of fluid light-weight additive in low density drilling fluid, wherein, in drilling fluid, directly add polystyrene hollow microsphere and be uniformly dispersed, the add-on of polystyrene hollow microsphere is preferably every 100ml drilling fluid and adds polystyrene hollow microsphere 1-30g.
Polystyrene hollow microsphere is as the application of fluid light-weight additive in low-density well cementing liquid, wherein, in cementing fluid, directly add polystyrene hollow microsphere and be uniformly dispersed, the add-on of polystyrene hollow microsphere is preferably every 100ml drilling fluid and adds polystyrene hollow microsphere 1-30g.
Beneficial effect of the present invention is:
1) dissolve appropriate polystyrene in vinylbenzene and can improve monomer viscosity, avoid the simple emulsion instability problem using monomer to cause because viscosity is too low, greater particle size product can be prepared, and be more conducive to formation and the maintenance of hollow structure.
2) do not need with an organic solvent, there is not recovery and the Utilizing question of solvent, Safety and Environmental Protection is good.
3) polystyrene is generated because styrene monomer is polymerized too under the effect of initiator, therefore good with original polystyrene consistency, oil phase all can be converted into product, output per single reactor is high, and the polystyrene hollow microsphere of generation is actually dimerous by the polystyrene content of original polystyrene content and later stage polymerization generation.
4) with the polystyrene hollow microsphere uniform particle sizes that package method is prepared, product circularity is good, and product cut size can be controlled by emulsifying agent dosage, W1/O ratio, dispersant, dispersant dosage, stirring velocity in adjustment W1 phase;
5) the method can utilize discarded polystyrene as one of raw material, reaction can be made easily to carry out on the one hand, again reduce monomer usage quantity, cost-saving, also can be used as the novel method of a kind of recycling of " white pollution ";
6) used in the preparation process recyclable recycling of aqueous phase, reduces cost, also for Realization of Product industrialization provides possibility.
Accompanying drawing explanation
Fig. 1 is polystyrene plastic pellet stereoscan photograph prepared by embodiment 5
Fig. 2 is the stereoscan photograph of the internal structure of polystyrene plastic pellet prepared by embodiment 5.
Embodiment
Embodiment 1
By computer packaging polystyrene foamed plastics wash clean, dry for standby;
1) configure 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, department class 603.198g, mixes rear obtained oil phase; Wherein polystyrene weight styrene monomer weight 30%, initiator is 3.0% of styrene monomer weight; Linking agent weight is 2.5% of styrene monomer weight, and emulsifying agent weight is 10%, O phase total mass of polystyrene weight and styrene monomer weight sum is 36.531g;
2) W1 phase is configured: get 7.0g distilled water, add 0.035g Sodium dodecylbenzene sulfonate, be uniformly dissolved rear as W1 phase, emulsifying agent weight is 0.5%, W1 phase total mass of distilled water weight is 7.035g;
3) W2 phase is configured: joined in 200ml distilled water by 16g polyvinyl alcohol, stir; Dispersant weight is 8% of distilled water weight, and emulsifying agent weight is 0%, W2 phase total mass of distilled water weight is 108g;
4) be added to by W1 in O phase under whipped state and be mixed with even W1/O emulsion, emulsion, stirring velocity is 6000r/min, and stirring 5min, W1 phase quality is 1:5.2 with O phase mass ratio;
5) W2 phase is poured in the reactor with condensing works (prolong) (as there-necked flask), put into water-bath, under agitation condition by (4) the W1/O emulsion dispersion prepared of portion in W2 phase, after stablizing 15min, temperature is risen to 85 DEG C, maintain after stirring 4h and be warming up to 95 DEG C, maintain after 2 hours and terminate, W1+O phase quality is 1:5.0 with W2 phase mass ratio;
6) will take out product caught on a filter dry and obtain product, products obtained therefrom particle size average is 179 μm.
Embodiment 2
By computer packaging polystyrene foamed plastics wash clean, dry for standby;
1) configure oil phase: take the above-mentioned clean polystyrene foamed plastics of 0.63g, add styrene monomer 31.5g, benzoyl peroxide 0.0063g, department class 800.65g, mix obtained oil phase.Polystyrene is 2% of vinylbenzene weight, and initiator is 0.02% of styrene monomer weight, and coupling agent weight is 0% of styrene monomer weight, and class 80 of department weight is 2% of polystyrene and styrene monomer weight sum, and oil phase total mass is 32.78g;
2) W1 phase is configured: get 18.0g distilled water, add 1.44g sodium laurylsulfonate, be uniformly dissolved rear as W1 phase, emulsifying agent weight is 8%, W1 phase total mass of distilled water weight is 19.44g;
3) W2 phase is configured: 0.156g gelatin, 0.11g Sodium dodecylbenzene sulfonate and 0.02g sorbitol anhydride oleate are joined in 130ml distilled water, stir obtained aqueous phase; Dispersant weight is 0.12% of water weight, and emulsifying agent weight is 0.1%, W2 phase total mass of water weight is 130.286g;
4) be added to by W1 in O phase under whipped state and be mixed with even W1/O emulsion, stirring velocity is 9000r/min, and stirring 2min, W1 phase quality is 1:1.7 with O phase mass ratio;
5) W2 phase is poured in the reactor with condensing works (prolong) (as there-necked flask), put into water-bath, adjustment rotating speed is 300r/min, under agitation condition by (4) the W1/O emulsion dispersion prepared of portion in W2 phase, after stablizing 15min, temperature is risen to 85 DEG C, maintain after stirring 6h and be warming up to 90 DEG C, maintain end and terminate after 3 hours; W1+O phase quality is 1:2.5 with W2 phase mass ratio;
6) by Vacuum filtration device, described emulsion is carried out suction filtration separation, isolate bead, after drying 24h at 70 DEG C, namely obtain the polystyrene hollow microsphere that median size is 93 μm.
Embodiment 3
By computer packaging polystyrene foamed plastics wash clean, dry for standby;
1) configure 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, department class 605.2g, mixes rear obtained oil phase; Wherein polystyrene weight styrene monomer weight 4%, initiator is 0.5% of styrene monomer weight; Coupling agent weight is 3% of styrene monomer weight, and emulsifying agent weight is 5%, O phase quality sum of polystyrene weight and styrene monomer weight sum is 112.7g;
2) W1 phase is configured: get 43g distilled water, add 1.15g sodium lauryl sulphate, 1.0gOP-10, be uniformly dissolved rear as W1 phase, emulsifying agent weight is 5%, W1 phase total mass of distilled water weight is 45.15g;
3) W2 phase is configured: joined in 1070ml distilled water by 32.1g polyvinyl alcohol, then add 10.7g sodium lauryl sulphate, stir as aqueous phase; Dispersant weight is 3% of water weight, and emulsifying agent weight is 1.0%, W2 phase quality of water weight is 1112.8g;
4) be added to by W1 in O phase under whipped state and be mixed with even W1/O emulsion, stirring velocity is 1000r/min, and stirring 20min, W1 phase quality is 1:2.5 with O phase mass ratio;
5) W2 phase is poured in the reactor (as there-necked flask) with condensing works (as prolong), put into water-bath, adjustment rotating speed is 300r/min, under agitation condition by (4) the W1/O emulsion dispersion prepared of portion in W2 phase, after stablizing 15min, temperature is risen to 75 DEG C, maintain stirring, after 7 hours, temperature is risen to 90 DEG C, maintain after 3 hours and terminate; W1+O phase quality is 1:7.0 with W2 phase mass ratio;
6) by Vacuum filtration device, described emulsion is carried out suction filtration separation, isolate bead, after drying 24h at 70 DEG C, namely obtain the polystyrene hollow microsphere that median size is 107 μm.
Embodiment 4
By computer packaging polystyrene foamed plastics wash clean, dry for standby;
1) configure oil phase: take the above-mentioned clean polystyrene foamed plastics of 8g, add styrene monomer 40g, Diisopropyl azodicarboxylate 0.04g, department class 801.44g, EGDMA 1.2g mixes obtained oil phase; Polystyrene is 20% of vinylbenzene weight, and initiator is 0.1% of styrene monomer weight, and coupling agent weight is 3% of styrene monomer weight, and emulsifying agent weight is 2%, O phase quality of polystyrene and styrene monomer weight sum is 50.68g;
2) W1 phase is configured: get 17g distilled water, add 0.34g OP-10, be uniformly dissolved rear as W1 phase, emulsifying agent weight is 2%, W1 phase total mass of distilled water weight is 17.34g;
3) W2 phase is configured: by 3g gelatin, 1.05g polyvinyl alcohol, 0.7g sodium lauryl sulphate and 0.515g sorbitol anhydride oleate join in 405ml distilled water, and stir obtained aqueous phase; Dispersant weight is 1.0% of water weight, and emulsifying agent weight is 0.3%, W2 phase quality of water weight is 410.265;
4) be added to by W1 in O phase under whipped state and be mixed with even W1/O emulsion, stirring velocity is 5000r/min, and stirring 10min, W1 phase quality is 1:3.0 with O phase mass ratio;
5) W2 phase is poured in the reactor with condensing works (prolong) (as there-necked flask), put into water-bath, adjustment rotating speed is 300r/min, under agitation condition by (4) the W1/O emulsion dispersion prepared of portion in W2 phase, after stablizing 15min, temperature is risen to 70 DEG C, maintain after stirring 4h and temperature is risen to 90 DEG C, maintain after 3 hours and terminate; W1+O phase quality is 1:6.0 with W2 phase mass ratio;
6) by Vacuum filtration device, described emulsion is carried out suction filtration separation, isolate bead, after drying 24h at 70 DEG C, namely obtain the polystyrene hollow microsphere that median size is 92 μm.
Embodiment 5
Get China Petrochemical Industry's Yanshan Petrochemical product: polystyrene, the trade mark: 666D is for subsequent use;
1) configure oil phase: take the above-mentioned clean polystyrene foamed plastics of 8g, add styrene monomer 40g, Diisopropyl azodicarboxylate 0.02g, department class 600.60g, glycerin fatty acid ester 0.60g, EGDMA 0.2g mix obtained oil phase; Polystyrene is 20% of vinylbenzene weight, and initiator is 0.05% of styrene monomer weight, and coupling agent weight is 0.5% of styrene monomer weight, and oil-soluble emulsifier weight is 3%, O phase quality of polystyrene and styrene monomer weight sum is 49.42g;
2) W1 phase is configured: get 17g distilled water, add 0.34g sodium lauryl sulphate, be uniformly dissolved rear as W1 phase, emulsifying agent weight is 2%, W1 phase total mass of distilled water weight is 17.34g;
3) configuration dispersion aqueous phase: by 3g gelatin, 1g polyvinyl alcohol, 1.2g Potassium Persulphate, 0.7g sodium lauryl sulphate and 0.5g sorbitol anhydride oleate, join in 400ml distilled water, and stir obtained aqueous phase; Dispersant weight is 1.0% of water weight, and emulsifying agent weight is 0.3% of water weight, and water soluble starter is 3% of monomer mass; The quality of W2 phase is 406.4g;
4) be added in O phase by W1 under whipped state and be mixed with homogeneous latex emulsion, stirring velocity is 5000r/min, and stirring 10min, W1 phase quality is 1:2.9 with O phase mass ratio;
5) transfer in the SPG membrane emulsifier of 20 μm by above gained emulsion, external solution is W2 phase, obtains uniform three-phased emulsions by film emulsification; Three-phased emulsions is transferred in flask, stir under the rotating speed of 350r/min and be warming up to 60 DEG C, maintain and stir 5h; Temperature is risen to 85 DEG C, maintain after stirring 3h and terminate; W1+O phase quality is 1:6.1 with W2 phase mass ratio;
Described emulsion is carried out suction filtration separation by Vacuum filtration device by 6, isolates bead, namely obtains polystyrene hollow microsphere that median size be 87 μm after drying 24h at 70 DEG C.
Obtained little ball warp scanning electronic microscope characterizes, as shown in Figure 1 (this picture magnification 300 times), from plastic pellet uniform particle sizes prepared by the visible the method for figure, product circularity is good, and product cut size can carry out controlling also to control particle diameter by senior emulsification means SPG membrane emulsifier in oil phase mass ratio, W2 phase dispersant dosage, stirring velocity etc. by adjustment W1 phase.Internal structure is (this picture magnification 1047 times) as shown in Figure 2, and the hollow microsphere hollow structure prepared from the visible the method for figure is obvious, uniform wall thickness.
Embodiment 6
Getting a beaker, in 200ml tap water, adding 0.4g xanthan gum as carrying stick, add polystyrene hollow plastic bead prepared by 20g embodiment 5 after being uniformly dissolved, after stirring, namely join to obtain low density drilling fluid.This drilling fluid density is 0.91g/cm
3.The measuring method of drilling fluid density is shown in GB/T 16783-1997 " water-base drilling fluid On-Site Test Procedure " " 1 drilling fluid density.So the light-weight additive that hollow polystyrene plastic pellet of the present invention can be used as drilling fluid uses.
Claims (18)
1. a preparation method for polystyrene hollow microsphere, it comprises following steps:
1) oil phase O is prepared: be dissolved in styrene monomer by polystyrene, then add initiator, linking agent, emulsifying agent, as oil phase after stirring; Wherein the weight of polystyrene is 2% ~ 30% of vinylbenzene weight; Initiator weight is 0.02 ~ 3% of styrene monomer weight; Linking agent weight is the 0-3% of styrene monomer weight; Emulsifying agent dosage is the 2-10% of polystyrene and vinylbenzene weight sum;
2) prepare W1 phase: add in distilled water emulsifiers dissolve evenly after as W1 phase, the weight of emulsifying agent is the 0.5-8% of distilled water weight;
3) W2 phase is prepared: in distilled water, add dispersion agent and emulsifying agent, as W2 phase after being uniformly dissolved; The weight of the dispersion agent added is the 0.12-8% of distilled water weight; The weight of the emulsifying agent added is the 0-1.0% of distilled water weight;
4) W1 is added in O phase, fully emulsified, obtained W1/O emulsion, W1 phase is 1:5.2-1:1.7 with the mass ratio of O phase;
5) under water bath condition, control temperature is at room temperature condition, and W1/O emulsion evenly spread in W2 phase, W1/O emulsion is not more than 1:2.5 with the mass ratio of W2 phase; Namely start after being uniformly dispersed to heat up, bath temperature is risen to 70-95 DEG C, at least react 4 hours, keep liquid phase to be in dynamic scatter in whole reaction process, utilize Suction filtration device by product suction filtration; Product caught on a filter will be taken out dry and obtain product.
2. preparation method according to claim 1, is characterized in that, described step 1) in, the weight of described polystyrene is 4 ~ 20% of vinylbenzene weight; Described initiator weight is 0.1 ~ 0.5% of styrene monomer weight; Described linking agent weight is the 0.5-2.5% of styrene monomer weight; Described emulsifying agent dosage is the 3-5% of polystyrene and vinylbenzene weight sum.
3. preparation method according to claim 1, is characterized in that, described step 2) in, the weight of described emulsifying agent is the 2-5% of distilled water weight.
4. preparation method according to claim 1, is characterized in that, described step 3) in, the weight of described dispersion agent is the 1-3% of distilled water weight; The weight of described emulsifying agent is the 0.1-0.3% of distilled water weight.
5. preparation method according to claim 1, is characterized in that, described step 4) in, in described W1/O emulsion, W1 phase is 1:2.5-1:3 with the mass ratio of O phase.
6. preparation method according to claim 1, is characterized in that, described step 5) in, described W1/O emulsion is 1:5 ~ 1:7 with the mass ratio of W2 phase; Described bath temperature is warming up to 75-80 DEG C; The described reaction times is 6-9 hour.
7. preparation method according to claim 1, is characterized in that, described step 1) in use polystyrene be polystyrene waste plastic and/or industrialization product polystyrene raw material.
8. preparation method as claimed in any of claims 1 to 7, it is characterized in that, described step 1) in the initiator that uses be selected from least one in azo-initiator, organic peroxy class initiator, inorganic peroxy class initiator or oxidation-reduction initiator.
9. preparation method as claimed in any of claims 1 to 7, it is characterized in that, described step 1) in the linking agent that uses be selected from one in divinylbenzene, vulcabond, N,N methylene bis acrylamide or ethylene glycol dimethacrylate.
10. preparation method as claimed in any of claims 1 to 7, is characterized in that, described step 1) in use oil-soluble emulsifier be selected from the emulsifying agent of HLB scope between 3-8.
11. preparation methods according to claim 10, is characterized in that, described step 1) the middle oil-soluble emulsifier used is selected from class 80 of department, at least one of taking charge of in class 60 or glycerin fatty acid ester.
12. preparation methods as claimed in any of claims 1 to 7, is characterized in that, described step 2) in the emulsifying agent that uses comprise at least one in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or OP-10.
13. preparation methods as claimed in any of claims 1 to 7, it is characterized in that, described step 3) in the dispersion agent that uses comprise at least one in xanthan gum, gelatin, carboxymethyl cellulose, Polyvinylpyrolidone (PVP), Natvosol or polyvinyl alcohol.
14. preparation methods as claimed in any of claims 1 to 7, it is characterized in that, described step 3) in use emulsifying agent comprise sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, class of department 80, department class 60 or OP-10 at least one.
15. preparation methods as claimed in any of claims 1 to 7, is characterized in that, described step 4) in emulsification adopt high-speed stirring mode or utilize SPG film carry out emulsification or carry out ultrasonic emulsification.
16. preparation methods as claimed in any of claims 1 to 7, is characterized in that, described step 5) dispersion adopt ultrasonic disperse mode, SPG film emulsifying manner or alr mode.
Polystyrene hollow microsphere prepared by 17. preparation methods as claimed in any of claims 1 to 7 is as the application of fluid light-weight additive in low density drilling fluid, wherein, in drilling fluid, directly add polystyrene hollow microsphere and be uniformly dispersed, the add-on of polystyrene hollow microsphere is that every 100ml drilling fluid adds polystyrene hollow microsphere 1-30g.
Polystyrene hollow microsphere prepared by 18. preparation methods as claimed in any of claims 1 to 7 is as the application of fluid light-weight additive in low-density well cementing liquid, wherein, in cementing fluid, directly add polystyrene hollow microsphere and be uniformly dispersed, the add-on of polystyrene hollow microsphere is that every 100ml drilling fluid adds polystyrene hollow microsphere 1-30g.
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| CN103387691B (en) * | 2012-05-08 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of hollow polystyrene plastic pellet and its preparation method and application |
| CN103666407B (en) * | 2012-09-12 | 2016-08-24 | 中国石油化工股份有限公司 | Drilling fluid and preparation method thereof |
| CN105504566B (en) * | 2016-01-26 | 2018-01-16 | 西南科技大学 | A kind of preparation method of column styrene divinylbenzene copolymer hydrophobic catalyst carrier |
| CN108129602B (en) * | 2016-12-01 | 2020-11-20 | 广州蓝月亮实业有限公司 | Hollow polymer elastic microsphere with micro-channels on surface and preparation method and application thereof |
| CN108129599B (en) * | 2016-12-01 | 2020-11-20 | 广州蓝月亮实业有限公司 | Hollow polymer plastic microsphere with micro-channels on surface and preparation method and application thereof |
| CN107522477A (en) * | 2017-08-24 | 2017-12-29 | 浙江科屹耐火材料有限公司 | A kind of complex intensifying core shell structure refractory brick and its preparation technology |
| CN107686339A (en) * | 2017-08-29 | 2018-02-13 | 浙江攀盛冶金材料有限公司 | A kind of high magnesia refractories for tundish |
| CN108164631B (en) * | 2018-01-12 | 2019-07-19 | 东华大学 | Styrene-bifunctionality monomer copolymer hollow porous micro sphere and preparation method |
| CN110872505B (en) * | 2019-12-03 | 2020-09-15 | 成都理工大学 | Organic porous nano-particle/surfactant composite oil displacement system and preparation method thereof |
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