CN103509143B - The preparation method of organic/inorganic composite pellets - Google Patents
The preparation method of organic/inorganic composite pellets Download PDFInfo
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- CN103509143B CN103509143B CN201210217692.6A CN201210217692A CN103509143B CN 103509143 B CN103509143 B CN 103509143B CN 201210217692 A CN201210217692 A CN 201210217692A CN 103509143 B CN103509143 B CN 103509143B
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Abstract
The invention provides a kind of preparation method of organic/inorganic composite pellets, polystyrene is dissolved in its polymerization single polymerization monomer vinylbenzene, dispersed enter dewatering nano inorganic particles, add initiator and linking agent simultaneously, disperse in aqueous after being uniformly dissolved, intensification makes monomer polymerization, and the solid phase of gained is carried out suction filtration, namely obtains organo-mineral complexing bead after drying.Composite pellets prepared by the method, temperature resistance is higher than pure plastic pellet, and uniform particle sizes, any surface finish, can be used for the solid lubricant of drilling fluid.
Description
Technical field
The present invention relates to a kind of preparation method of organic/inorganic composite pellets, be specifically related to a kind of method preparing drilling fluid organic/inorganic composite solid lubricating agent bead from dissolution method.
Background technology
Along with the development of petroleum prospecting work, drilling depth constantly increases, the drilling hole number of cluster wells, high-inclination directional well and horizontal well also increases rapidly, avoid bit freezing, reduction drilling tool moment of torsion, minimizing drill string wear to become urgent problem, in drilling fluid, add lubricant effectively can avoid the accidents such as bit freezing.Solid lubricant, relative to liquid lubricant, is join in solid form in drilling fluid to play the lubrication borehole wall, prevent from adhering to the effect such as bit freezing.It has the advantages such as transport facility, unstressed configuration, lubricity are good.Solid lubricant for well drilling liquid used at present mainly contains following two kinds according to lubrication mechanism.
1) graphite-like, lubrication mechanism is mainly by the slip of interlayer.Graphite is a kind of crystal habit of carbon, has hexagonal lattice, and atom is layered arrangement, and the distance on same layer crystal face between carbon atom is 0.142nm, is covalent bonds each other; Distance is between layers 0.34nm, and combine in molecular linkage between atom, reactive force is between layers very little therefore be easy in interlayer generation relatively sliding, thus plays good anti-attrition effect.Graphite Powder 99 has high temperature resistance, unstressed configuration as lubricant, falls frictional resistance successful, dosage is little, to features such as property of drilling fluid have no adverse effects.(comprising physics and chemistry absorption) can be adsorbed after joining drilling fluid securely on drilling tool and rock of borehole surface, thus improve the Frotteurism between frictional contact surface, play the effect reducing frictional resistance.
2) rounded bulbous body, is similar to tiny ball, and lubrication mechanism is present between drill string and the borehole wall, and sliding friction is converted into rolling resistance, thus significantly reduces moment of torsion and resistance, prevents from adhering to bit freezing, mainly comprises glass pellet and plastic pellet.Glass pellet composition is vitreum, and property is crisp, very easily broken in the process of drilling, and uses, and can not be used in conventional drilling when being generally used for running casing.Plastic pellet is mainly the multipolymer of vinylbenzene and divinylbenzene, and toughness is strong, has the features such as nontoxic, unstressed configuration, recoverable.Its acidproof, alkaline-resisting, water insoluble and oils, in inertia in drilling fluid, can mate with water base and all kinds drilling fluid that is oil base, be a kind of highly-efficient lubricant, development in recent years is very fast.
Because graphite is natural minerals, glass pellet is due to fragility great Yi fragmentation, and cannot apply in the process of drilling, and plastic pellet is subject to the restriction of the second-order transition temperature of polymkeric substance own, uses certain limitation, the stratum higher in temperature cannot use.In order to improve the temperature resistance of plastic pellet, in polymeric matrix, introducing inorganic component, forming organic/inorganic composite microsphere.Current polystyrene composite plastic bead preparation method mainly contains following several:
1) organo-mineral complexing, with vinylbenzene and inorganic lamellar material for raw material, the method of in-situ monomer intercalation suspension polymerization is utilized to prepare polystyrene composite particles, polystyrene/inorganic compounding bead, can control the particle diameter of product by adjustment stirring intensity, dispersant dosage, polymerization time and temperature etc.
2) take polystyrene sphere as template, functionalization is done on polystyrene sphere surface, then inorganic powdered material is carried out coated on polystyrene sphere surface, form the complex microsphere of organic/inorganic nucleocapsid mechanism.
3) inorganic materials is done surface hydrophobicity modification, evenly spread in styrene monomer and form oil phase, add oily molten class initiator, be dispersed in aqueous phase and carry out letex polymerization, form the organo-mineral complexing microballoon of island structure.
The present invention proposes a kind of polystyrene organic/inorganic composite pellets and preparation method thereof, dissolved polystyrene in styrene monomer, add the nanometer grade powder inorganic materials after hydrophobically modified, be mixed with uniform oil phase, they are distributed in the aqueous solution containing dispersion agent and emulsifying agent, utilize the method for suspension polymerization that styrene monomer is polymerized and generate polystyrene, therefore the composition of plastic pellet is actually and is made up of the polystyrene in earlier stage added and deuterogenic polystyrene.The method mainly contains following advantage: 1) the method introduces a part of inorganic materials, can improve the thermostability of pure polystyrene microsphere; 2) waste plastic foam of a raw materials used part to be main component be polystyrene, reduces cost; 3) control particle diameter by the ratio between adjustment monomer and polymkeric substance, solve the problem that the simple bead particle diameter using monomer polymerization to prepare is too little.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of organic/inorganic composite pellets, the second-order transition temperature of bead and the particle diameter of bead can control, and reduce cost, and wherein, the second-order transition temperature of composite pellets can control at 80-90 DEG C.
The present invention uses the method from dissolving, by polymer dissolution in monomer, improve monomer viscosity, improve the stability of inorganic particulate in oil phase, and then control condition makes monomer cause, composite pellets prepared by this method, namely containing original polymkeric substance cost, also causes the product composition of post polymerization containing monomer.
The invention provides a kind of preparation method of organic/inorganic composite pellets, comprise the following steps:
1) oil phase is configured: be dissolved into by polystyrene in styrene monomer, add hydrophobic inorganic nano particle, ultrasonic disperse 15-240min, preferred 30-60min; Initiator, linking agent and emulsifying agent is added again as oil phase after being uniformly dispersed; The weight of polystyrene is the 0-30% of vinylbenzene weight, is preferably 4-15%; The weight of hydrophobic inorganic nano particle is the 0.01-10% of vinylbenzene and polystyrene weight sum, is preferably 0.1-5%; Initiator weight is the 0.02-3% of styrene monomer weight, is preferably 0.1-0.5%; Linking agent weight is the 0-4% of styrene monomer weight, is preferably 0.5-2.5%; Emulsifying agent dosage is the 2-10% of polystyrene and vinylbenzene weight sum, preferred 3-5%;
2) aqueous phase is configured: in distilled water, add dispersion agent and emulsifying agent, as aqueous phase after being uniformly dissolved; The weight of dispersion agent is the 0.12-8% of distilled water weight, and be preferably 1-3%, emulsifying agent weight is the 0-1.0% of distilled water weight, is preferably 0.1-0.3%;
3) under room temperature environment, be distributed in aqueous phase under water bath condition by oil phase, the mass ratio of oil phase and aqueous phase is not more than 1:2, preferred 1:3-1:5; After being uniformly dispersed, 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 experiment, finally utilizes Suction filtration device by product suction filtration; Product caught on a filter will be taken out dry and obtain product.
Polystyrene in step 1) is the waste or used plastics of polystyrene and/or industrial polystyrene raw material.
In step 1), hydrophobic inorganic nano particle is selected from dewatering nano silicon-dioxide, hydrophobic nano-titanium dioxide, dewatering nano calcium carbonate, dewatering nano zirconium white, dewatering nano zinc oxide, at least one in dewatering nano cupric oxide.
In step 1), initiator is selected from least one in azo-initiator, organic peroxy class initiator, inorganic peroxy class initiator, oxidation-reduction initiator.
The linking agent weight one that to be vinylbenzene be in Vinylstyrene, vulcabond, N,N methylene bis acrylamide (MBA), ethylene glycol dimethacrylate or trimethylolpropane tris first acrylate in step 1).
Emulsifying agent in step 1) is selected from the emulsifying agent of HLB scope in 3-8, the mixing of one or more preferably in class 80 of department, class 60 of department or glycerin fatty acid ester.
Step 2) in dispersion agent can comprise the mixture of one or more in xanthan gum, gelatin, carboxymethyl cellulose, Polyvinylpyrolidone (PVP), Natvosol or polyvinyl alcohol.
Step 2) in emulsifying agent can comprise the mixture of one or more in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or OP-10.
Dispersion in step 3) adopts alr mode, ultrasonic power or SPG film emulsifying manner to carry out.
Emulsion should be kept in step 3) in whole reaction process to be in dynamic process, and the state of described dynamic scatter keeps emulsion can not be static exactly, can stir or the mode such as ultrasonic always, until monomer polymerization solidification always.If because liquid phase is static before reaction does not complete, creaming of emulsion or destruction will be caused.
Described composite pellets is as the application of drilling fluid organic/inorganic composite solid lubricating agent.
Beneficial effect of the present invention
1) the composite pellets uniform particle sizes prepared of the method, product circularity is good, and product cut size can be controlled by adjustment dispersant dosage, stirring velocity, control oil phase viscosity etc.
2) the method utilizes discarded polystyrene foamed plastics as one of raw material, " white pollution " can be converted into high value-added product, can as a kind for the treatment of process of waste plastic;
3) the method introduces a part of inorganic materials, can improve the thermostability of pure polystyrene microsphere.
Accompanying drawing explanation
The organic/inorganic composite pellets stereoscan photograph of the present invention (this picture magnification 1000 times) of Fig. 1 embodiment 3 gained;
Embodiment
Embodiment 1:
By computer packaging polystyrene foamed plastics wash clean, dry for standby;
(1) oil phase is configured: take the above-mentioned clean polystyrene foamed plastics of 4.725g, add styrene monomer 31.5g, dissolve completely and add hydrophobic nano-titanium dioxide 3.623g, ultrasonic disperse 240min, then add benzoyl peroxide 0.0063g, department class 800.65g, mix obtained oil phase; Polystyrene is 15% of vinylbenzene weight, hydrophobic titanium dioxide be polystyrene and vinylbenzene weight and 10%, initiator is 0.02% of styrene monomer weight, and linking agent weight is 0% of styrene monomer weight, and emulsifying agent weight is 2% of polystyrene and styrene monomer weight sum;
(2) configuration dispersion aqueous phase: 0.48g gelatin, 0.35g Sodium dodecylbenzene sulfonate and 0.05g sorbitol anhydride oleate are joined in 400ml distilled water, stir obtained aqueous phase; Dispersant weight is 0.12% of water weight, and emulsifying agent weight is 0.1% of water weight;
(3) described aqueous phase is poured in the reactor (there-necked flask as with condensing reflux pipe) with condensate recycling device; Put into water-bath; Adjustment rotating speed is 300r/min, joins in aqueous phase under agitation by described oil phase, obtains the uniform emulsion of emulsification, and the mass ratio of oil phase and aqueous phase is 1:10; Temperature is risen to 80 DEG C, maintain stirring 6h and terminate;
(4) by Vacuum filtration device, described emulsion is carried out suction filtration separation, isolate bead, after drying 24h at 70 DEG C, namely obtain the organic/inorganic composite solid lubricating agent bead that median size is 203 μm.
Embodiment 2:
By computer packaging polystyrene foamed plastics wash clean, dry for standby;
(1) oil phase is configured: take the above-mentioned clean polystyrene foamed plastics of 7.38g, add styrene monomer 24.6g, dissolve completely and add dewatering nano silica 1 .6g, ultrasonic disperse 60min, then 0.738g benzoyl peroxide is added, add 0.615g Vinylstyrene, 3.198g Si Ban-60, mix rear obtained oil phase; Wherein polystyrene weight accounts for 30% of styrene monomer weight, and dewatering nano silica weight is 5% of polystyrene and vinylbenzene weight sum, and initiator is 3.0% of styrene monomer weight; Linking agent weight is 2.5% of styrene monomer weight, and emulsifying agent weight is 10% of polystyrene weight and styrene monomer weight sum;
(2) configuration dispersion aqueous phase: 8g polyvinyl alcohol is joined in 100ml distilled water, stirs; Dispersant weight is 8% of water weight, and emulsifying agent weight is 0% of water weight;
(3) described aqueous phase is poured into the reactor (as there-necked flask) with condensing works, put into water-bath; Adjustment rotating speed is 350r/min, joins in aqueous phase under agitation by described oil phase, obtains the uniform emulsion of emulsification, and the mass ratio of oil phase and aqueous phase is 1:3.0; Temperature is risen to 95 DEG C, maintain stirring 9h and terminate;
(4) by Vacuum filtration device, described emulsion is carried out suction filtration separation, isolate bead, after drying 24h at 70 DEG C, namely obtain the organic/inorganic composite solid lubricating agent bead that median size is 304 μm.
Embodiment 3:
By computer packaging polystyrene foamed plastics wash clean, dry for standby;
(1) oil phase is configured: take the above-mentioned clean polystyrene foamed plastics of 4g, add styrene monomer 100, dissolve completely and add dewatering nano calcium carbonate 0.104g, ultrasonic disperse 15min, add Diisopropyl azodicarboxylate 0.5g, add ethylene glycol dimethacrylate 4g, department class 605.2g, mixes rear obtained oil phase; Wherein polystyrene weight accounts for 4% of styrene monomer weight, dewatering nano weight of calcium carbonate polystyrene and vinylbenzene weight and 0.01%, initiator is 0.5% of styrene monomer weight; Linking agent weight is 4% of styrene monomer weight, and emulsifying agent weight is 5% of polystyrene weight and styrene monomer weight sum;
(2) configuration dispersion aqueous phase: 6.6g polyvinyl alcohol is joined in 220ml distilled water, then adds 2.2g sodium lauryl sulphate, stir as aqueous phase; Dispersant weight is 3% of water weight, and emulsifying agent weight is 1.0% of water weight;
(3) described aqueous phase is poured into the reactor (as there-necked flask) with condensate recycling device, put into water-bath; Adjustment rotating speed is 350r/min, joins in aqueous phase under agitation by described oil phase, obtains the uniform emulsion of emulsification, and the mass ratio of oil phase and aqueous phase is 1:2.0; Temperature is risen to 70 DEG C, maintain stirring 9h and terminate;
(4) by Vacuum filtration device, described emulsion is carried out suction filtration separation, isolate bead, after drying 24h at 70 DEG C, namely obtain the organic/inorganic composite solid lubricating agent bead that median size is 153 μm.
Gained bead scanning electronic microscope is taken, and as shown in Figure 1, from plastic pellet uniform particle sizes prepared by the visible the method for figure, product circularity is good for result, and product cut size can be controlled by adjustment dispersant dosage, stirring velocity.
Embodiment 4:
(1) configure oil phase: get styrene monomer 100, dissolve completely and add dewatering nano calcium carbonate 0.1g, ultrasonic disperse 30min, add 2,2'-Azobis(2,4-dimethylvaleronitrile) 0.1g, add trimethylolpropane tris first acrylate 0.5g, department class 603g, mixes rear obtained oil phase; Wherein polystyrene weight styrene monomer weight 0%, dewatering nano weight of calcium carbonate is 0.1% of vinylbenzene weight, and initiator is 0.1% of styrene monomer weight; Linking agent weight is 0.5% of styrene monomer weight, and emulsifying agent weight is 3% of polystyrene weight and styrene monomer weight sum;
(2) configuration dispersion aqueous phase: 2.2g xanthan gum is joined in 220ml distilled water, then adds 0.66g sodium lauryl sulphate, stir as aqueous phase; Dispersant weight is 1% of water weight, and emulsifying agent weight is 0.3% of water weight;
(3) described aqueous phase is poured into the reactor (as there-necked flask) with condensing works, put into water-bath; Adjustment rotating speed is 400r/min, joins in aqueous phase under agitation by described oil phase, obtains the uniform emulsion of emulsification, and the mass ratio of oil phase and aqueous phase is 1:2.0; Temperature is risen to 75 DEG C, maintain stirring 4h and terminate;
(4) by Vacuum filtration device, described emulsion is carried out suction filtration separation, isolate bead, after drying 24h at 70 DEG C, namely obtain the organic/inorganic composite solid lubricating agent bead that median size is 25 μm.
Embodiment 5
Get 400ml water, add 12g wilkinite (producer: Xuanhua Dongsheng Chemical Industry Co., Ltd.), at least 24h is placed after stirring, be not less than 10000r/min stir speed under add adhesive aggregation anionic cellulose (PAC in 2g, Shandong one Teng Jituan), then add 4g treated starch (CMS, the rich meticulous commercial auxiliaries company limited of Bazhou City's light), obtain drilling fluid after dissolving completely, add organic/inorganic composite solid lubricating agent bead prepared by 12g embodiment 3 afterwards.Utilize mud cake sticking coefficient determinator (NF-2 type mud cake sticking coefficient determinator, the sensible instrumentation company limited in sea, Qingdao) measure the sticking coefficient changing conditions that plastic pellet adds front and back drilling fluid, sticking coefficient measuring method is shown in standard Q/SHCG4 ~ 2011 " water-base drilling fluid is technical requirements with lubricator " 4.2.7 " mud cake sticking coefficient reduced rate ".Result shows, not adding the sticking coefficient of drilling fluid 5min before polystyrene plastic pellet of the present invention is 0.10, and after adding plastic pellet, the sticking coefficient of drilling fluid is 0.03, illustrates that polystyrene plastic pellet of the present invention has good lubricant effect.
Embodiment 6
The comparative example of obtained embodiment 2, does not add dewatering nano silicon-dioxide.
Get the sample obtained by 10g embodiment 2, put into 1# watch-glass; Get 10g comparative example, put into 2# watch-glass.Place 48 hours in 100 DEG C of baking ovens.
In 1# watch-glass, sample surfaces is smooth, and soap-free emulsion polymeization between particle and particle, shape is without change
Adhesion between sample part particle in 2# watch-glass, bead subsides, yellowish.
Claims (12)
1. a preparation method for organic/inorganic composite pellets, is characterized in that, comprises the following steps:
1) oil phase is configured: be dissolved into by polystyrene in styrene monomer, add hydrophobic inorganic nano particle, add initiator, linking agent and emulsifying agent after being uniformly dispersed again as oil phase; The weight of polystyrene is the 0-30% of vinylbenzene weight; The weight of hydrophobic inorganic nano particle is the 0.01-10% of vinylbenzene and polystyrene weight sum; Initiator weight is the 0.02-3% of styrene monomer weight; Linking agent weight is the 0-4% of styrene monomer weight; Emulsifying agent dosage is the 2-10% of polystyrene and vinylbenzene weight sum; Described dispersion adopts ultrasonic disperse 15-240min;
2) aqueous phase is configured: in distilled water, add dispersion agent and emulsifying agent, as aqueous phase after being uniformly dissolved; The weight of dispersion agent is the 0.12-8% of distilled water weight, and emulsifying agent weight is the 0-1.0% of distilled water weight;
3) under room temperature environment, be distributed in aqueous phase under water bath condition by oil phase, the mass ratio of oil phase and aqueous phase is not more than 1:2; After being uniformly dispersed, bath temperature is risen to 70-95 DEG C, at least react 4 hours, rear end experiment, finally utilizes Suction filtration device by product suction filtration; Product caught on a filter will be taken out dry and obtain product.
2. method according to claim 1, is characterized in that:
Step 1) in the weight of polystyrene be the 4-15% of vinylbenzene weight; The weight of hydrophobic inorganic nano particle is the 0.1-5% of vinylbenzene and polystyrene weight sum; Initiator weight is the 0.1-0.5% of styrene monomer weight; Linking agent weight is the 0.5-2.5% of styrene monomer weight; Emulsifying agent dosage is the 3-5% of polystyrene and vinylbenzene weight sum; Described dispersion adopts ultrasonic disperse 30-60min;
Step 2) in the weight of dispersion agent be the 1-3% of distilled water weight, emulsifying agent weight is the 0.1-0.3% of distilled water weight;
Step 3) in the mass ratio of oil phase and aqueous phase be 1:3-1:5; After being uniformly dispersed, bath temperature is risen to 75-80 DEG C, reaction 6-9 hour.
3. method according to claim 1 and 2, is characterized in that, described step 1) in polystyrene be the waste or used plastics of polystyrene and/or industrial polystyrene raw material.
4. method according to claim 1 and 2, it is characterized in that, described step 1) in hydrophobic inorganic nano particle be selected from least one in dewatering nano silicon-dioxide, hydrophobic nano-titanium dioxide, dewatering nano calcium carbonate, dewatering nano zirconium white, dewatering nano zinc oxide or dewatering nano cupric oxide.
5. method according to claim 1 and 2, is characterized in that, described step 1) in initiator be selected from least one in azo-initiator, organic peroxy class initiator, inorganic peroxy class initiator, oxidation-reduction initiator.
6. method according to claim 1 and 2, it is characterized in that, described step 1) in the linking agent one that to be vinylbenzene be in Vinylstyrene, vulcabond, N,N methylene bis acrylamide (MBA), ethylene glycol dimethacrylate or trimethylolpropane tris first acrylate.
7. method according to claim 1 and 2, is characterized in that, described step 1) in emulsifying agent be selected from the emulsifying agent of HLB scope in 3-8.
8. method according to claim 7, is characterized in that, described step 1) in emulsifying agent be selected from department class 80, department class 60 or glycerin fatty acid ester at least one.
9. method according to claim 1 and 2, is characterized in that, described step 2) 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 2) in emulsifying agent be selected from least one in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or OP-10.
11. methods according to claim 1 and 2, is characterized in that, described step 3) in dispersion adopt alr mode, ultrasonic power or SPG film emulsifying manner carry out.
12. composite pellets that method prepares according to claim 1 or 2 are as the application of drilling fluid organic/inorganic composite solid lubricating agent.
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| CN103736996B (en) * | 2014-01-24 | 2016-03-30 | 云南大学 | A kind of method being covered with the composite microsphere material of conductive submicron line/rod preparing porous |
| KR101787205B1 (en) * | 2014-12-05 | 2017-10-18 | 주식회사 엘지화학 | Heat resistance resin and method for preparing the resin |
| CN105859934A (en) * | 2016-04-07 | 2016-08-17 | 江苏建亚环保科技股份有限公司 | Preparation method of solid lubricant high-polymer spheres for drilling fluids |
| CN106334541B (en) * | 2016-10-09 | 2018-07-27 | 南开大学 | A kind of adsorbent and preparation method thereof removing inflammatory factor in systemic inflammatory response blood samples of patients |
| CN109422841B (en) * | 2017-08-30 | 2020-12-29 | 天津大学 | Polystyrene-vinylbenzyl dimethyl dodecyl ammonium chloride-barium titanate composite material and preparation method thereof |
| CN110117487B (en) * | 2019-05-22 | 2021-03-23 | 西南石油大学 | Foam discharging agent for drainage and gas recovery of high-inclination horizontal well |
| CN110257028B (en) * | 2019-06-17 | 2022-04-05 | 同济大学 | Enzymatic polymerization macromolecule composite slurry and preparation method thereof |
| CN111729625A (en) * | 2020-06-15 | 2020-10-02 | 宁波锋成先进能源材料研究院 | Nano composite micro-rubber ball and preparation method and application thereof |
| CN113416528B (en) * | 2021-06-22 | 2022-10-28 | 西南石油大学 | Organic/inorganic nano composite gel plugging agent and oil-based drilling fluid |
| US11479705B1 (en) | 2022-06-01 | 2022-10-25 | King Fahd University Of Petroleum And Minerals | Invert emulsion drilling fluid containing hydrophobic metallic zinc nanoparticles and method of drilling subterranean geological formation |
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| CN101343370A (en) * | 2008-08-19 | 2009-01-14 | 中国科学院广州化学研究所 | Water dispersible magnetic polymer microsphere and preparing method |
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| CN101343370A (en) * | 2008-08-19 | 2009-01-14 | 中国科学院广州化学研究所 | Water dispersible magnetic polymer microsphere and preparing method |
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