CN103387681B - The preparation method of polystyrene plastic pellet and application thereof - Google Patents
The preparation method of polystyrene plastic pellet and application thereof Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method and application thereof of polystyrene plastic pellet, the method from dissolving is adopted to be dissolved in styrene monomer by polystyrene, then add in the aqueous solution being dissolved with dispersion agent and emulsifying agent, control certain temperature under dynamic scatter condition and make styrene monomer initiated polymerization, can polystyrene plastic pellet be prepared.Prepared polystyrene sphere joins in drilling fluid, can reduce the sticking coefficient of drilling fluid.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of polystyrene plastic pellet.More particularly, the present invention relates to a kind of preparation method of solid lubricant for well drilling liquid plastic pellet and the application as solid lubricant thereof.
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.No matter be plastic pellet or glass pellet, due to the restriction by solids size, be easy to be removed by solid control equipment in drilling process, and in the extruding of drilling rod or under patting, have the possibility of destruction, distortion, therefore in use, receive certain restriction.
Because graphite is natural minerals, glass pellet is large due to fragility, cannot apply in the process of drilling, and solid lubricant for well drilling liquid research mainly concentrates on plastic pellet aspect, and current plastic pellet preparation method mainly contains following two kinds:
(1), based on vinylbenzene or acrylate, join diolefins copolymerization and form.Adopt the method for suspension polymerization, being monomer with vinylbenzene, take Vinylstyrene as linking agent, and dibenzoyl peroxide is initiator, and polyvinyl alcohol and gelatin are that dispersion agent synthesizes plastic pellet, and plastic pellet major part used is at present the preparation of this method.Shortcoming is that the plastic pellet particle diameter of preparation is less, is not easy preparation and is greater than more than 2 μm products.
(2) 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 plastic pellet, can control the particle diameter of product by adjustment stirring intensity, dispersant dosage, polymerization time and temperature etc.
The present invention proposes a kind of method preparing polystyrene plastic pellet, in styrene monomer, dissolve part polystyrene 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.
Summary of the invention
The object of the invention is to solve the polystyrene plastic pellet particle diameter prepared of ordinary method problem less than normal, the particle diameter of plastic pellet can control, and reduces cost, can be used as solid lubricant for well drilling liquid and uses.
The method that the present invention utilizes is the method from dissolving, by polymer dissolution in monomer, improve monomer viscosity, and then control condition makes monomer cause, plastic pellet prepared by this method, both containing original component of polymer, also causes the product composition of post polymerization containing monomer.
Technical scheme of the present invention is as follows:
Prepare a method for polystyrene plastic pellet, comprise following steps:
The preparation of (a) oil phase: polystyrene is dissolved in styrene monomer, then add initiator, linking agent and emulsifying agent as oil phase.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 0-4% 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 quality sum, is preferably the 3-5% of polystyrene and vinylbenzene quality sum.
B the preparation of () aqueous phase: add dispersion agent and emulsifying agent in distilled water, the solution be uniformly dissolved is as aqueous phase.Wherein, dispersant weight is the 0.12-8% of distilled water weight, is preferably the 1-3% of distilled water weight; The weight of emulsifying agent is the 0-1.0% of distilled water weight, is preferably the 0.1-0.3% of distilled water weight.
C (), under water bath condition, oil phase, at room temperature condition, is distributed in aqueous phase by control temperature, the mass ratio controlling oil phase and aqueous phase is not more than 1:2, preferred 1:3-1:5; Oil phase disperses and after aqueous phase, bath temperature is risen to 60-95 DEG C, preferred 75-80 DEG C; At least react 4 hours, preferred reaction 6-9 hour, utilize Vacuum filtration device by product suction filtration after reaction terminates, product caught on a filter will be taken out and dry and obtain polystyrene plastic pellet.
Polystyrene used in above-mentioned steps (a) is used foamed plastics and/or industrialization product polystyrene raw material.
In above-mentioned steps (a), initiator is selected from least one in azo-initiator, organic peroxy class initiator, inorganic peroxy class initiator, oxidation-reduction initiator.
Described azo-initiator comprises at least one in Diisopropyl azodicarboxylate and 2,2'-Azobis(2,4-dimethylvaleronitrile);
Described organic peroxy class initiator comprises at least one in Cumene Hydroperoxide 80, hydroperoxidation tertiary butyl, dibenzoyl peroxide, dilauroyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, di-isopropyl peroxydicarbonate;
Described inorganic peroxy class initiator comprises at least one in Potassium Persulphate and ammonium persulphate;
Described oxidation-reduction initiator comprises water soluble oxidized-reduction initiator and/or oil insoluble oxidation-reduction initiator; In wherein water soluble oxidized-reduction initiator, oxygenant is selected from least one in inorganic peroxy class initiator and hydrogen peroxide initiator, and reductive agent is selected from least one in divalent iron salt, sodium bisulfite, Sulfothiorine, alcohol and polyamine;
In wherein oil insoluble oxidation-reduction initiator, at least one in organic peroxy class initiator selected by oxygenant, and at least one in tertiary amine, ferrous naphthenate salt and mercaptan selected by reductive agent.
In above-mentioned steps (a), linking agent is selected from as divinylbenzene, vulcabond, the one in N,N methylene bis acrylamide (MBA), ethylene glycol dimethacrylate.
The preferred HLB value scope of emulsifying agent is at the emulsifying agent of 3-8 in above-mentioned steps (a), further preferred department class 80(oleic acid sorbitol ester), department class 60(sorbitan tristearate), department class 40(sorbitol anhydride Palmitate), at least one in glycerin fatty acid ester.
Dispersion agent described in above-mentioned steps (b) is at least one in xanthan gum, gelatin, carboxymethyl cellulose, Polyvinylpyrolidone (PVP), Natvosol, polyvinyl alcohol.
Emulsifying agent described in above-mentioned steps (b) is at least one in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, OP-10.
Dispersing mode described in above-mentioned steps (c) can adopt the ordinary methods such as alr mode, ultrasonic power or SPG emulsifying manner to carry out.
The invention still further relates to a kind of application utilizing the plastic pellet of above-mentioned preparation, described polystyrene plastic pellet is joined in drilling fluid, for reducing the sticking coefficient of drilling fluid.
Beneficial effect of the present invention is:
(1) the plastic pellet uniform particle sizes prepared of the present invention, 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) present method does not affect the chemical property of styrene monomer, and the generable reaction of styrene monomer can be carried out equally.
Accompanying drawing explanation
Fig. 1 is polystyrene plastic pellet stereoscan photograph prepared by embodiment 3.
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 0.63g, add styrene monomer 31.5g, dibenzoyl 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;
(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; Water oil ratio is 1:12.2, and dispersant weight is 0.12% of water weight, and emulsifying agent weight is 0.1% of water weight;
(3) pour described aqueous phase into there-necked flask with condensation recovery tube, 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; Temperature is risen to 85 DEG C, maintain after stirring 6h and be warming up to 90 DEG C, maintain after 3 hours 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 polystyrene plastic pellet that median size is 73 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 7.38g, add styrene monomer 24.6g and dibenzoyl peroxide 0.738g, add ethylene glycol dimethacrylate 0.615, department class 603.198g, mixes rear obtained oil phase; Wherein polystyrene weight is 30% of styrene monomer weight, and initiator is 3.0% of styrene monomer weight; Coupling 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; Water oil ratio is 1:3.0, and dispersant weight is 8% of water weight, and emulsifying agent weight is 0% of water weight;
(3) pour described aqueous phase into there-necked flask with condensation recovery tube, 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; 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;
(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 polystyrene plastic pellet that median size is 134 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 dibenzoyl 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% 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; Water oil ratio is 1:2.0, and dispersant weight is 3% of water weight, and emulsifying agent weight is 1.0% of water weight;
(3) pour described aqueous phase into there-necked flask with condensation recovery tube, 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; 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;
(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 polystyrene plastic pellet that median size is 71 μm.
Obtained little ball warp scanning electronic microscope characterizes, bead prepared by embodiment 3 as shown in Figure 1, from plastic pellet uniform particle sizes prepared by the visible the method for figure, product circularity is good, and product cut size can be undertaken controlling (this picture magnification 1000 times) by adjustment dispersant dosage, stirring velocity.
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, ethylene glycol dimethacrylate 1.6g mixes obtained oil phase; Polystyrene is 20% of vinylbenzene weight, and initiator is 0.1% of styrene monomer weight, and coupling agent weight is 4% of styrene monomer weight, and class 80 of department weight is 3% of polystyrene and styrene monomer weight sum;
(2) configuration dispersion aqueous phase: by 3g gelatin, 1g polyvinyl alcohol, 0.7g sodium laurylsulfonate and 0.5g sorbitol anhydride oleate join in 400ml distilled water, and stir obtained aqueous phase; Water oil ratio is 1:7.9, and dispersant weight is 1.0% of water weight, and emulsifying agent weight is 0.3% of water weight;
(3) pour described aqueous phase into there-necked flask with condensation recovery tube, 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; 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;
(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 polystyrene plastic pellet 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 above-mentioned 8g polystyrene plastic, add styrene monomer 40g, Diisopropyl azodicarboxylate 0.02g, department class 600.72g, glycerin fatty acid ester 0.72g, ethylene glycol dimethacrylate 1.6g mixes obtained oil phase; Polystyrene is 20% of vinylbenzene weight, and initiator is 0.05% of styrene monomer weight, and coupling agent weight is 4% of styrene monomer weight, and oil-soluble emulsifier weight is 3% of polystyrene and styrene monomer weight sum;
(2) configuration dispersion aqueous phase: by 3g gelatin, 1g polyvinyl alcohol, 1.2g Potassium Persulphate, 0.7g OP-10 and 0.5g sorbitol anhydride oleate, join in 400ml distilled water, and stir obtained aqueous phase; Water oil ratio is 1:8.0, and 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;
(3) above gained aqueous phase and oil phase are utilized aperture to be that the SPG film of 20 μm carries out emulsification preparation O/w emulsion, obtain the uniform emulsion of emulsification; Emulsion 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;
(4) by Suction filtration device, described emulsion is carried out suction filtration separation, isolate bead, after drying 24h at 70 DEG C, namely obtain the polystyrene plastic pellet that median size is 63 μm.
Embodiment 6
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 polystyrene plastic pellet 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/SHCG 4 ~ 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.
Claims (12)
1. a preparation method for polystyrene plastic pellet, comprises following steps:
The preparation of (a) oil phase: polystyrene is dissolved in styrene monomer, then add initiator, linking agent and emulsifying agent as oil phase; Wherein, the weight of polystyrene is 2 ~ 30% of vinylbenzene weight; Initiator weight is 0.1 ~ 0.5% of styrene monomer weight; Linking agent weight is the 0-4% of styrene monomer weight; Emulsifying agent weight is the 2-10% of polystyrene and vinylbenzene quality sum;
The preparation of (b) aqueous phase: add dispersion agent and emulsifying agent in distilled water, the solution be uniformly dissolved is as aqueous phase; Wherein, dispersant weight is the 0.12-8% of distilled water weight; The weight of emulsifying agent is the 0-1.0% of distilled water weight;
C (), under water bath condition, oil phase, at room temperature condition, is distributed in aqueous phase by control temperature, the mass ratio controlling oil phase and aqueous phase is 1:3-1:5; After oil phase is scattered in aqueous phase, bath temperature is risen to 60-95 DEG C, reaction 6-9 hour, utilizes Suction filtration device by product suction filtration after reaction terminates, will take out product caught on a filter and dry and obtain polystyrene plastic pellet.
2. method according to claim 1, is characterized in that, in step (a), the weight of polystyrene is 4 ~ 20% of vinylbenzene weight; Linking agent weight is the 0.5-2.5% of styrene monomer weight; Emulsifying agent weight is the 3-5% of polystyrene and vinylbenzene quality sum.
3. method according to claim 1, is characterized in that, in step (b), dispersant weight is the 1-3% of distilled water weight; The weight of emulsifying agent is the 0.1-0.3% of distilled water weight.
4. method according to claim 1, is characterized in that, polystyrene used in described step (a) is used foamed plastics and/or industrialization product polystyrene raw material.
5. the method according to any one of claim 1-4, is characterized in that, in described step (a), initiator is selected from least one in azo-initiator, organic peroxy class initiator, inorganic peroxy class initiator or oxidation-reduction initiator;
Wherein, described azo-initiator is selected from least one in Diisopropyl azodicarboxylate and 2,2'-Azobis(2,4-dimethylvaleronitrile);
Described organic peroxy class initiator is selected from least one in Cumene Hydroperoxide 80, hydroperoxidation tertiary butyl, dibenzoyl peroxide, dilauroyl peroxide, di-tert-butyl peroxide, dicumyl peroxide or di-isopropyl peroxydicarbonate;
Described inorganic peroxy class initiator is selected from least one in Potassium Persulphate and ammonium persulphate;
Described oxidation-reduction initiator is selected from water soluble oxidized-reduction initiator and/or oil insoluble oxidation-reduction initiator; Oxygenant in wherein water soluble oxidized-reduction initiator is selected from least one in inorganic peroxy class initiator and hydrogen peroxide initiator, and reductive agent is selected from least one in divalent iron salt, sodium bisulfite, Sulfothiorine, alcohol and polyamine; In wherein oil insoluble oxidation-reduction initiator, oxygenant is selected from least one in organic peroxy class initiator, and at least one in tertiary amine, ferrous naphthenate salt and mercaptan selected by reductive agent.
6. the method according to any one of claim 1-4, is characterized in that, in described step (a), linking agent is selected from divinylbenzene, vulcabond, N,N methylene bis acrylamide (MBA) or ethylene glycol dimethacrylate.
7. the method according to any one of claim 1-4, is characterized in that, in described step (a), emulsifying agent is selected from the emulsifying agent of HLB value scope at 3-8.
8. method according to claim 7, it is characterized in that, described emulsifying agent is selected from least one in class 80 of department (oleic acid sorbitol ester), class 60 of department (sorbitan tristearate), class 40 of department (sorbitol anhydride Palmitate) or glycerin fatty acid ester.
9. the method according to any one of claim 1-4, it is characterized in that, dispersion agent described in described step (b) is at least one in xanthan gum, gelatin, carboxymethyl cellulose, Polyvinylpyrolidone (PVP), Natvosol or polyvinyl alcohol.
10. the method according to any one of claim 1-4, is characterized in that, emulsifying agent described in described step (b) is at least one in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate or OP-10.
11. methods according to any one of claim 1-4, is characterized in that, the dispersion in described step (c) adopts ultrasonic disperse mode, SPG film emulsifying manner or alr mode to carry out.
The application of 12. 1 kinds of plastic pellet prepared any one of claim 1-4, joins in drilling fluid by described polystyrene plastic pellet, for reducing the sticking coefficient of drilling fluid.
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| CN103965390B (en) * | 2014-04-30 | 2015-07-01 | 辽宁德成科技集团有限公司 | Polystyrene propping agent and preparation and application thereof |
| CN104558316A (en) * | 2014-12-23 | 2015-04-29 | 安徽助成信息科技有限公司 | Method for synthesizing polystyrene microspheres based on emulsion method |
| 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 |
| CN107999037B (en) * | 2017-12-18 | 2020-07-31 | 南京大学 | Magnetic polymer adsorption material, preparation method and application |
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| CN1064280A (en) * | 1991-02-21 | 1992-09-09 | 埃勒夫阿托化学有限公司 | Preparation dissolves in the method for its composition (copolymerization) monomeric (being total to) polymkeric substance |
| CN1400242A (en) * | 2002-08-28 | 2003-03-05 | 王洪艳 | Environment-protecting type water emulsion and its preparation method |
| CN101691425A (en) * | 2009-09-27 | 2010-04-07 | 上海大学 | Method for preparing adsorptive resin materials by utilizing waste polystyrene |
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| CN1064280A (en) * | 1991-02-21 | 1992-09-09 | 埃勒夫阿托化学有限公司 | Preparation dissolves in the method for its composition (copolymerization) monomeric (being total to) polymkeric substance |
| CN1400242A (en) * | 2002-08-28 | 2003-03-05 | 王洪艳 | Environment-protecting type water emulsion and its preparation method |
| CN101691425A (en) * | 2009-09-27 | 2010-04-07 | 上海大学 | Method for preparing adsorptive resin materials by utilizing waste polystyrene |
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