CN100434447C - Nanometer and micron water-soluble microgel reservoir oil material and preparation method thereof - Google Patents
Nanometer and micron water-soluble microgel reservoir oil material and preparation method thereof Download PDFInfo
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- CN100434447C CN100434447C CNB2005101024201A CN200510102420A CN100434447C CN 100434447 C CN100434447 C CN 100434447C CN B2005101024201 A CNB2005101024201 A CN B2005101024201A CN 200510102420 A CN200510102420 A CN 200510102420A CN 100434447 C CN100434447 C CN 100434447C
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Abstract
The present invention relates to nanometer and micron polymer material, and is especially one kind of nanometer and micron water soluble microgel oil-displacing material with wide size range and its reverse emulsion polymerizing preparation process. In the reverse emulsion polymerization process, water soluble monomer and cross-linking agent react to form pre-crosslinked spheroid water soluble microgel polymer with certain elasticity. As one kind of oil-displacing material, the nanometer and micron water soluble microgel material is opaque reverse emulsion, and has excellent flowability and stability, viscosity at 25 deg.c lower than 400 mPa.s, no obvious delamination. When the material and water soluble surfactant are injected simultaneously into water, the material will disperse fast and swelled to form microgel grains of 100 nm to 20 micron size.
Description
Technical field
The invention belongs to water-solubility function polymer nano and micro materials field, be particularly related to and receive the wide size range water-soluble microgel reservoir oil material of micron, and adopt the stable method of receiving the wide size range water-soluble microgel reservoir oil material of micron of reversed-phase emulsion thermopolymerization method preparation.
Background technology
Water-soluble polymer microgel type profile-controlling and plugging agent begins to use in the most of oil field of China as a kind of type material that can effectively improve the oil recovery ratio in recent years.At present, this microgranular cross linked water soluble polymer preparation methods mainly contains three kinds: (1) online crosslinking polymerization, promptly polymkeric substance/linking agent dilute solution is crosslinked in the on-the-spot generation in the stratum of injecting, and forms microgel.Partially hydrolyzed polyacrylamide (HPAM)/metal ion Al for example
3+, CR
3+, linking agents such as formaldehyde under conditions suitable, can keep flowability and injectability in the long term, thus the deep rate of permeation is hidden in adjustable fuel-economizing.But this reactive mode is subjected to the influence of stratum and impurity, and fractionation by adsorption easily takes place, and effects such as flocculation sediment were lost efficacy system.Simultaneously, again because of the diluent injection rate is big, there are many difficulties in actual applications in the energy consumption height.(2) ground surface crosslinking system promptly utilizes polymkeric substance and linking agent to carry out precrosslink on ground, and prepared gel has good reliability.But, because system viscosity is very big, can not enter earth formation deep, generally can only be used for nearly well profile control or water blockoff.And because shear on the stratum, the gel particle size can be more and more littler, loses the effect of shutoff at last.(3) precrosslink polymerization, promptly monomer/linking agent adopts suitable polymerizing condition to carry out crosslinking polymerization, forms the microgel of certain size.This method can satisfy the water plugging and profile controlling needs of reality according to the situation of the stratal configuration and the penetrating passage in actual oil field by structure, the form of polymerization control microgel.(In-Depth Colloidal Dispersion Gels Improve Oil RecoveryEfficiency uses colloid dispersion gel deep transfer drive with raising oil recovery Mark.J.C., Smith J.E., and SPE 27780.527～539, and 1994; Lower concentration partially hydrolyzed polyacrylamide and Tiorco 677 cross-linking system rheology study Sun Aijun, Wu Zhaoliang, Lin Meiqin, Li Mingyuan, University of Petroleum's journal: natural science edition 2004,28 (5) 65～69).
Summary of the invention
A purpose of the present invention provide receive the micron a wide size range water-soluble microgel reservoir oil material.
Another object of the present invention provides the method that adopts the preparation of reversed-phase emulsion thermopolymerization method to receive the wide size range water-soluble microgel reservoir oil material of micron, this method has simple to operate, a polymerization can be prepared the micro-gel particles of size distribution from tens nanometers to several microns, energy consumption of reaction is low, characteristics such as easy to control, be convenient to design and the microgel oil displacing material of synthetic different size and different structure, prepare receive the micron wide size range the water-soluble microgel reservoir oil material room temperature under can keep stable for a long time, tangible profit demixing phenomenon do not occur, can adapt to the needs of different reservoir formation structures and injection technology.
The present invention adopts reversed-phase emulsion thermopolymerization method to make water-soluble monomer and linking agent reaction formation have the spherical precrosslink water-soluble microgel of certain elastic class polymkeric substance.
Inverse emulsion polymerization is that employing external phase is that oil phase, disperse phase are water, utilizes tensio-active agent that monomer solution is cut apart the methods that are surrounded as several reaction microcells and prepares the water-soluble microgel polymkeric substance.Profit phase demixing phenomenon promptly takes place in the microgel system poor stability that general inverse emulsion polymerization is prepared in the short period of time, product can not satisfy the needs of the actual injection technology of oil field profile control and water plugging material.The microgel that reversed-phase emulsion thermopolymerization method of the present invention is prepared ties up under the room temperature condition and can keep stable for a long time, and viscosity is low, good fluidity, compare with other cross-linked polymer microgel, in oil field practice application, it is simple to have injection device, and energy consumption is low, easy to operate, little advantage influenced by ambient temperature.This preparation method, a polymerization can be prepared the micro-gel particles of size distribution from tens nanometers to several microns, adjustment by degree of hydrolysis and crosslinking degree, can control the size after particle disperses to expand effectively in water, thereby can be good at satisfying the profile control and water plugging needs of oil-bearing formation under the broad permeability range condition.
The present invention adopt reversed-phase emulsion thermopolymerization method directly preparation receive the wide size range microgel oil displacing material of micron, receive the wide size range microgel oil displacing material of micron by adopting acrylamide/anionic monomer/the 3rd monomer to synthesize terpolymer; Low temperature thermal decomposition type initiator causes in the employing; Adopt the composite use of kinds of surface promoting agent, help the stable of reversed-phase emulsion system like this, help the control of particle diameter, help product and in water, have good dispersiveness.
The micron water-soluble microgel reservoir oil material of receiving of the present invention is opaque reversed-phase emulsion state, wherein the water microgel is the class sphere, particle diameter is 50nm～2 μ m, it has good flowability and stable, 25 ℃ of following viscosity＜400mPa.s of room temperature, leaving standstill does not have obvious profit demixing phenomenon 15 days～half a year, injects water soluble surfactant active and this material in water simultaneously, can directly disperse fast, the micro-gel particles particle diameter after fully disperseing to expand is 100nm～20 μ m.
The micron water-soluble microgel reservoir oil material of receiving of the present invention, by percentage to the quality, this oil displacing material by:
Acrylamide (AM) 10～30%
Soluble anionic monomers 0.1～20%
The 3rd monomer (M
3) 0.1～10%
Tensio-active agent 1～15%
Solvent 1 (oil phase) 20～60%
Solvent 2 (oil phase) 0.1～0.5%
Deionized water 20～35%
And the thermal initiator that accounts for the linking agent of reaction monomers total mass 0.01～10% and account for reaction monomers total mass 0.1～1.0% is formed.
Employing reversed-phase emulsion thermopolymerization method of the present invention preparation is received the method for micron water-soluble microgel reservoir oil material and be may further comprise the steps, by percentage to the quality,
(1) monomer solution preparation
The acrylamide that accounts for reaction system 10～30% is dissolved in the deionized water that accounts for reaction system 20～35%, after stirring makes it dissolving, add the soluble anionic monomers that accounts for reaction system 0.1～20%, add the 3rd monomer that accounts for reaction system 0.1～10% again, after treating to dissolve fully, add the linking agent that accounts for reaction monomers total mass 0.1～10% again, be stirred well to the no solid insoluble of solution clarification, adopt the 1wt%NaOH aqueous solution that solution is adjusted to pH=7.
(2) reversed-phase emulsion system preparation
The tensio-active agent that accounts for reaction system 1～15% is dissolved in the solvent 1 that accounts for reaction system 20～60%, after treating that abundant dispersing and dissolving evenly, the monomer solution of step (1) is slowly added, fully stir, can obtain opaque inverse emulsion polymerization reaction system.
(3) heat polymerization
After the thermal initiator usefulness that accounts for reaction monomers total mass 0.1～1.0% being accounted for solvent 2 dissolvings of reaction system 0.1～0.5%, join in the reversed-phase emulsion system of step (2), after stirring, feed rare gas element more than 1 hour, with the oxygen of replacement(metathesis)reaction system, make to be reflected under the deoxygenation conditions and carry out, slowly be warming up to 45 ℃～65 ℃, and kept 5～8 hours, reaction system remains opaque emulsion state, wherein the water microgel is the class sphere, and particle diameter is 50nm～2 μ m.
Of the present inventionly receive micron water-soluble microgel reservoir oil material in use, in water, inject water soluble surfactant active and Na micron water-soluble microgel reservoir oil material simultaneously, can directly disperse fast, the water micro-gel particles particle diameter of micron water-soluble microgel reservoir oil material received after fully disperseing to expand is 100nm～20 μ m.
It is the crosslinked terpolymer of a class that the present invention adopts the microgranular water-soluble microgel of reversed-phase emulsion thermopolymerization method synthetic, and it contains non-ionic water-soluble monomer, soluble anionic monomers and the 3rd monomer (M
3), the 3rd monomer (M wherein
3) can select various monomers to give new character of product and function by different needs, the 3rd monomer accounts for 10～50% of monomer total mass in polymerization reaction system, and preferred 30～40%.The ratio that non-ionic water-soluble monomer and soluble anionic monomers are occupied is not less than 50% of monomer total mass, should be controlled at more than 70% of monomer total mass generally speaking.
Described non-ionic water-soluble monomer is acrylamide (AM).
Described soluble anionic monomers is selected from one or more the mixture etc. in vinylformic acid, sodium acrylate, methacrylic acid, sodium methacrylate, 2-acrylamido-2-methyl propane sulfonic acid sodium, sodium allyl sulfonate, the Sodium styrene sulfonate.
Described the 3rd monomer (M
3) be selected from one or more the mixture etc. in acrylamide derivative, acrylate or acrylate, methacrylic ester, N-vinyl pyridine salt, the N-vinyl pyrrolidone.
Described acrylamide derivative is selected from one or more the mixture etc. in N methacrylamide, N-ethyl acrylamide, N-butyl acrylamide, the N-hydroxyethyl acrylamide.
Described acrylate is selected from Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinylformic acid hydroxy butyl ester, beta-amido ethyl propylene acid esters, N, N dimethylamine base ethyl propylene acid esters, N, the mixture of one or more in the N dimethylamine base oxethyl acrylate etc.
Described acrylate is selected from N, N dimethylamine base ethylacrylic acid vitriol, N, N dimethylamine base ethylacrylic acid hydrochloride, N, the mixture of one or more in the N dimethylamine base oxethyl acrylic acid hydrochloride etc.
Described methacrylic ester is hydroxyethyl methylacrylate or dimethylaminoethyl methacrylate.
The linking agent of selecting among the present invention is to adopt bifunctional or polyfunctional group water-soluble cross-linker, as one or more the mixture etc. in N,N methylene bis acrylamide, diallyldimethylammonium chloride, polyoxyethylene glycol double methacrylate, the pentaerythritol triacrylate.Consumption is 0.1%～10%.
Reversed-phase emulsion thermopolymerization system of the present invention, oil-continuous phase medium (solvent 1) can be selected one or more the mixture etc. in aliphatic hydrocarbon, various model solvent oil or the aromatic hydrocarbons for use, its ratio is generally 20～60% (mass percentage concentration), is good with 30～50% especially.
Described aliphatic hydrocarbon is selected from one or more the mixture etc. in octane, decane, the hexanaphthene.
Described solvent oil is selected from one or more the mixture etc. in kerosene, white oil, diesel oil, gasoline, the petroleum naphtha.
Described aromatic hydrocarbons is selected from one or more the mixture etc. in the benzene,toluene,xylene.
The solvent of solution heat initiator among the present invention (solvent 2) can be selected aromatic hydrocarbons for use, as: the mixture of one or more in the benzene,toluene,xylene etc.
Tensio-active agent among the present invention is one or more the mixture etc. in department class (Span) series, tween (Tween) series, polyoxyethylene castor oil (EL) series, the two different monooctyl ester sulfonate (AOT) of succsinic acid, sodium laurylsulfonate (SDS), the cetyl trimethylammonium bromide (CTAB).Oleophylic-the hydrophilic balance of tensio-active agent (HLB) answers＜9, is good with 6～8 especially.But the character according to different monomers and oil phase combination can change, to obtain the inverse emulsion polymerization system of best stabilized.The consumption of tensio-active agent is generally 1～15%, is good with 5～10% especially.
Described department class (Span) series is selected from one or more the mixture etc. among Si Ban-60, Si Ban-65, span-80, the Si Ban-85.
Described tween (Tween) series is selected from one or more the mixture etc. in tween 20, Tween-40, Tween-60, tween-80, tween-61, Tween-81, Tween-65, the tween 85.
Described polyoxyethylene castor oil (EL) series is selected from one or more the mixture etc. among EL-10, EL-20, EL-30, EL-40, EL-60, EL-80, the EL-90.
The thermal initiator that the present invention adopts belongs to the molten type initiator of single component thermal cracking oil, is selected from one or more the mixture etc. in acetophenone derivs that st-yrax, benzoin ether analog derivative, hydroxyl or amido replace, organo-peroxide, the tetrazo initiator.The thermal initiator consumption is 0.1%～1.0% of a total monomer amount.
Described benzoin ether analog derivative is selected from one or more the mixture etc. in benzoin methyl ether, Benzoin ethyl ether, the benzoin dimethylether (I-651).
The acetophenone derivs that described hydroxyl or amido replace is selected from 1-hydroxy-cyclohexyl phenyl ketone (I-184), the 2-methyl isophthalic acid-[mixture of one or more in 4-(methyl thio-phenyl)-2-morpholino acetone (I-907), 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxy-2-methyl propyl group) ketone (I-2959), the 2-hydroxy-2-methyl-1-phenyl-acetone (D-1173) etc.
Described organo-peroxide is selected from benzoyl peroxide (BPO), dicumyl peroxide, the mixture of one or more in the benzoyl peroxide tert-butyl ester etc.
Described tetrazo initiator is Diisopropyl azodicarboxylate (AIBN) or azo-bis-isobutyrate hydrochloride (AIBA).
Described rare gas element is nitrogen, argon gas, helium etc.
The present invention adopts the legal direct preparation of reversed-phase emulsion hot polymerization to receive the technology of the wide size water-soluble microgel of micron, has characteristics such as reaction is easy to control, production efficiency height, energy consumption is low, reaction system is stable, the easy control of easy and simple to handle, size.In system of the present invention, product reversed-phase emulsion gel aqueous phase particle diameter is controlled at 50nm～2 μ m, it has good flowability and stable, 25 ℃ of viscosity＜400mPa.s of room temperature, leave standstill under 25 ℃ and do not have obvious profit demixing phenomenon 15 days～half a year, inject water soluble surfactant active and this material simultaneously in water, can directly disperse fast, the micro-gel particles particle diameter after fully disperseing to expand is 100nm～20 μ m.As the material of the displacement of reservoir oil, they have good flowability and injection.
Embodiment
Embodiment 1
(1) monomer solution preparation
The acrylamide that accounts for reaction system 27% is dissolved in the deionized water that accounts for reaction system 28%, after stirring makes it dissolving, add the sodium acrylate that accounts for reaction system 0.5%, add the N-vinyl pyrrolidone that accounts for reaction system 0.1% again, after treating to dissolve fully, add the N,N methylene bis acrylamide that accounts for reaction monomers total mass 0.01% again, be stirred well to the no solid insoluble of solution clarification, adopt the 1%NaOH aqueous solution that solution is adjusted to pH==7.
(2) reversed-phase emulsion system preparation
Tensio-active agent (the span-80: 6% of reaction system 9% will be accounted for, Tween-60: 3%) dissolve in the diesel oil that accounts for reaction system 35%, after treating that abundant dispersing and dissolving evenly, the monomer solution of step (1) is slowly added, fully stir, can obtain opaque inverse emulsion polymerization reaction system.
(3) heat polymerization
After Diisopropyl azodicarboxylate (AIBN) usefulness that accounts for reaction monomers total mass 0.1% being accounted for the toluene dissolving of reaction system 0.4%, join in the reversed-phase emulsion system of step (2), after stirring, feed nitrogen more than 1 hour, oxygen with the replacement(metathesis)reaction system, make to be reflected under the deoxygenation conditions and carry out, slowly be warming up to 50 ℃, and kept 7 hours, reaction system remains opaque emulsion state, wherein the water microgel is the class sphere, particle size range 50nm～2 μ m, 25 ℃ of viscosity 350mPa.s of room temperature, leave standstill under 25 ℃ and do not have obvious profit demixing phenomenon in 3 months, inject water soluble surfactant active and this material simultaneously in water, can directly disperse fast, the micro-gel particles particle size range after fully disperseing to expand is 100nm～20 μ m.
Embodiment 2
(1) monomer solution preparation
The acrylamide that accounts for reaction system 20% is dissolved in the deionized water that accounts for reaction system 30%, after stirring makes it dissolving, add the 2-acrylamido-2-methyl propane sulfonic acid sodium that accounts for reaction system 1%, add the N-hydroxyethyl acrylamide that accounts for reaction system 0.5% again, after treating to dissolve fully, add the diallyldimethylammonium chloride that accounts for reaction monomers total mass 0.1% again, be stirred well to the no solid insoluble of solution clarification, adopt the 1%NaOH aqueous solution that solution is adjusted to pH=7.
(2) reversed-phase emulsion system preparation
Tensio-active agent (Si Ban-the 85:6% of reaction system 11% will be accounted for, EL-40:5%) dissolve in the white oil mixed solvent of the diesel oil that accounts for reaction system 20% and 17%, after treating that abundant dispersing and dissolving evenly, the monomer solution of step (1) is slowly added, fully stir, can obtain opaque inverse emulsion polymerization reaction system.
(3) heat polymerization
After Diisopropyl azodicarboxylate (AIBN) usefulness that accounts for reaction monomers total mass 0.5% being accounted for the benzene dissolving of reaction system 0.5%, join in the reversed-phase emulsion system of step (2), after stirring, feed nitrogen more than 1 hour, oxygen with the replacement(metathesis)reaction system, make to be reflected under the deoxygenation conditions and carry out, slowly be warming up to 55 ℃, and kept 6 hours, reaction system remains opaque emulsion state, wherein the water microgel is the class sphere, and particle diameter is 50nm～1 μ m, 25 ℃ of viscosity 300mPa.s of room temperature, leave standstill under 25 ℃ and do not have obvious profit demixing phenomenon in 5 months, inject water soluble surfactant active and this material simultaneously in water, can directly disperse fast, the micro-gel particles particle diameter after fully disperseing to expand is 100nm～5 μ m.
Embodiment 3
(1) monomer solution preparation
The acrylamide that accounts for reaction system 25% is dissolved in the deionized water that accounts for reaction system 26%, after stirring makes it dissolving, add the sodium allyl sulfonate that accounts for reaction system 5%, add the beta-amido ethyl propylene acid esters that accounts for reaction system 3% again, after treating to dissolve fully, add the polyoxyethylene glycol double methacrylate that accounts for reaction monomers total mass 1% again, be stirred well to the no solid insoluble of solution clarification, adopt the 1%NaOH aqueous solution that solution is adjusted to pH=7.
(2) reversed-phase emulsion system preparation
Tensio-active agent (Si Ban-the 60:7% of reaction system 10.7% will be accounted for, cetyl trimethylammonium bromide (CTAB): 3.7%) dissolve in the kerosene that accounts for reaction system 30%, after treating that abundant dispersing and dissolving evenly, the monomer solution of step (1) is slowly added, fully stir, can obtain opaque inverse emulsion polymerization reaction system.
(3) heat polymerization
To account for the azo-bis-isobutyrate hydrochloride (AIBA) of reaction monomers total mass 1% with after accounting for the xylene soluble of reaction system 0.3%, join in the reversed-phase emulsion system of step (2), after stirring, feed nitrogen more than 1 hour, oxygen with the replacement(metathesis)reaction system, make to be reflected under the deoxygenation conditions and carry out, slowly be warming up to 50 ℃, and kept 7 hours, reaction system remains opaque emulsion state, wherein the water microgel is the class sphere, and particle diameter is 80nm～800nm, 25 ℃ of viscosity 270mPa.s of room temperature, leave standstill under 25 ℃ and do not have obvious profit demixing phenomenon in 4 months, inject water soluble surfactant active and this material simultaneously in water, can directly disperse fast, the micro-gel particles particle diameter after fully disperseing to expand is 120nm～2 μ m.
Embodiment 4
(1) monomer solution preparation
The acrylamide that accounts for reaction system 15% is dissolved in the deionized water that accounts for reaction system 20%, after stirring makes it dissolving, add the Sodium styrene sulfonate that accounts for reaction system 10%, add the hydroxyethyl methylacrylate that accounts for reaction system 5% again, after treating to dissolve fully, add the pentaerythritol triacrylate that accounts for reaction monomers total mass 5% again, be stirred well to the no solid insoluble of solution clarification, adopt the 1%NaOH aqueous solution that solution is adjusted to pH=7.
(2) reversed-phase emulsion system preparation
Tensio-active agent (Si Ban-the 65:7% of reaction system 9% will be accounted for, the two different monooctyl ester sulfonate (AOT) of succsinic acid: 2%) dissolve in the hexanaphthene that accounts for reaction system 40.5%, after treating that abundant dispersing and dissolving evenly, the monomer solution of step (1) is slowly added, fully stir, can obtain opaque inverse emulsion polymerization reaction system.
(3) heat polymerization
After benzoyl peroxide (BPO) usefulness that accounts for reaction monomers total mass 2% being accounted for the toluene dissolving of reaction system 0.5%, join in the reversed-phase emulsion system of step (2), after stirring, feed helium more than 1 hour, oxygen with the replacement(metathesis)reaction system, make to be reflected under the deoxygenation conditions and carry out, slowly be warming up to 60 ℃, and kept 7 hours, reaction system remains opaque emulsion state, wherein the water microgel is the class sphere, and particle diameter is 50nm～500nm, 25 ℃ of viscosity 240mPa.s of room temperature, leave standstill under 25 ℃ and do not have obvious profit demixing phenomenon half a year, inject water soluble surfactant active and this material simultaneously in water, can directly disperse fast, the micro-gel particles particle diameter after fully disperseing to expand is 100nm～1 μ m.
Embodiment 5
(1) monomer solution preparation
The acrylamide that accounts for reaction system 20% is dissolved in the deionized water that accounts for reaction system 25%, after stirring makes it dissolving, add the sodium methacrylate that accounts for reaction system 20%, add the N that accounts for reaction system 7% again, N dimethylamine base oxethyl acrylic acid hydrochloride is after treating to dissolve fully, add the N that accounts for reaction monomers total mass 10% again, the N-methylene-bisacrylamide is stirred well to the no solid insoluble of solution clarification, adopts the 1%NaOH aqueous solution that solution is adjusted to pH=7.
(2) reversed-phase emulsion system preparation
Tensio-active agent (the span-80: 4.5% of reaction system 5% will be accounted for, sodium laurylsulfonate (SDS): 0.5%) dissolve in the petroleum naphtha that accounts for reaction system 22.7%, after treating that abundant dispersing and dissolving evenly, the monomer solution of step (1) is slowly added, fully stir, can obtain opaque inverse emulsion polymerization reaction system.
(3) heat polymerization
After benzoin dimethylether (I-651) usefulness that accounts for reaction monomers total mass 3% being accounted for the toluene dissolving of reaction system 0.3%, join in the reversed-phase emulsion system of step (2), after stirring, feed argon gas more than 1 hour, oxygen with the replacement(metathesis)reaction system, make to be reflected under the deoxygenation conditions and carry out, slowly be warming up to 65 ℃, and keep little at 8 o'clock, reaction system remains opaque emulsion state, wherein the water microgel is the class sphere, and particle diameter is 50nm～200nm, 25 ℃ of viscosity 210mPa.s of room temperature, leave standstill under 25 ℃ and do not have obvious profit demixing phenomenon half a year, inject water soluble surfactant active and this material simultaneously in water, can directly disperse fast, the micro-gel particles particle diameter after fully disperseing to expand is 100nm～800nm.
Claims (6)
1. receive micron water-soluble microgel reservoir oil material for one kind, it is characterized in that, by percentage to the quality, this oil displacing material by:
Acrylamide 10～30%
Soluble anionic monomers 0.1～20%
The 3rd monomer 0.1～10%
Tensio-active agent 1～15%
Solvent 1 20～60%
Solvent 2 0.1～0.5%
Deionized water 20～35%
And the thermal initiator that accounts for the linking agent of reaction monomers total mass 0.01～10% and account for reaction monomers total mass 0.1～1.0% is formed;
Described soluble anionic monomers is selected from one or more the mixture in vinylformic acid, sodium acrylate, methacrylic acid, sodium methacrylate, 2-acrylamido-2-methyl propane sulfonic acid sodium, sodium allyl sulfonate, the Sodium styrene sulfonate;
Described the 3rd monomer is selected from one or more the mixture in acrylamide derivative, acrylate or acrylate, methacrylic ester, N-vinyl pyridine salt, the N-vinyl pyrrolidone;
Oleophylic-the hydrophilic balance of described tensio-active agent＜9;
Described solvent 1 is selected from one or more the mixture in aliphatic hydrocarbon, solvent oil or the aromatic hydrocarbons;
Described solvent 2 is an aromatic hydrocarbons;
Described acrylamide derivative is selected from one or more the mixture in N methacrylamide, N-ethyl acrylamide, N-butyl acrylamide, the N-hydroxyethyl acrylamide;
Described acrylate is selected from Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinylformic acid hydroxy butyl ester, beta-amido ethyl propylene acid esters, N, N dimethylamine base ethyl propylene acid esters, N, the mixture of one or more in the N dimethylamine base oxethyl acrylate;
Described acrylate is selected from N, N dimethylamine base ethylacrylic acid vitriol, N, N dimethylamine base ethylacrylic acid hydrochloride, N, the mixture of one or more in the N dimethylamine base oxethyl acrylic acid hydrochloride;
Described methacrylic ester is hydroxyethyl methylacrylate or dimethylaminoethyl methacrylate;
Described linking agent is selected from one or more the mixture in N,N methylene bis acrylamide, diallyldimethylammonium chloride, polyoxyethylene glycol double methacrylate, the pentaerythritol triacrylate;
Described thermal initiator is selected from one or more the mixture in acetophenone derivs that st-yrax, benzoin ether analog derivative, hydroxyl or amido replace, organo-peroxide, the tetrazo initiator;
The particle diameter of the water micro-gel particles of described microgel oil displacing material is 50nm～2 μ m; Viscosity＜400mPa.s under the room temperature.
2. material according to claim 1 is characterized in that: described aliphatic hydrocarbon is selected from one or more the mixture in octane, decane, the hexanaphthene;
Described solvent oil is selected from one or more the mixture in kerosene, white oil, diesel oil, gasoline, the petroleum naphtha;
Described aromatic hydrocarbons is selected from one or more the mixture in the benzene,toluene,xylene.
3. material according to claim 1 is characterized in that: described tensio-active agent is selected from one or more the mixture in department class, tween, polyoxyethylene castor oil, succsinic acid pair different monooctyl ester sulfonate, sodium laurylsulfonate, the cetyl trimethylammonium bromide.
4. material according to claim 3 is characterized in that: described department class is selected from one or more the mixture among Si Ban-60, Si Ban-65, span-80, the Si Ban-85;
Described tween is selected from one or more the mixture in tween 20, Tween-40, Tween-60, tween-80, tween-61, Tween-81, Tween-65, the tween 85;
Described polyoxyethylene castor oil is selected from one or more the mixture in polyoxyethylene castor oil-10, polyoxyethylene castor oil-20, polyoxyethylene castor oil-30, polyoxyethylene castor oil-40, polyoxyethylene castor oil-60, polyoxyethylene castor oil-80, the polyoxyethylene castor oil-90.
5. material according to claim 1 is characterized in that: described benzoin ether analog derivative is selected from one or more the mixture in benzoin methyl ether, Benzoin ethyl ether, the benzoin dimethylether;
The acetophenone derivs that described hydroxyl or amido replace is selected from 1-hydroxy-cyclohexyl phenyl ketone, the 2-methyl isophthalic acid-[mixture of one or more in 4-(methyl thio-phenyl)-2-morpholino acetone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxy-2-methyl propyl group) ketone, the 2-hydroxy-2-methyl-1-phenyl-acetone;
Described organo-peroxide is selected from one or more the mixture in benzoyl peroxide, dicumyl peroxide, the benzoyl peroxide tert-butyl ester;
Described tetrazo initiator is Diisopropyl azodicarboxylate or azo-bis-isobutyrate hydrochloride.
6. one kind according to each described preparation methods of claim 1～5, and this method is to adopt the reversed-phase emulsion hot polymerization legal, may further comprise the steps, by percentage to the quality,
(1) monomer solution preparation
The acrylamide that accounts for reaction system 10～30% is dissolved in the deionized water that accounts for reaction system 20～35%, after stirring makes it dissolving, add the soluble anionic monomers that accounts for reaction system 0.1～20%, add the 3rd monomer that accounts for reaction system 0.1～10% again, after treating to dissolve fully, add the linking agent that accounts for reaction monomers total mass 0.1～10% again, be stirred well to the no solid insoluble of solution clarification, adopt the NaOH aqueous solution that solution is adjusted to pH=7;
(2) reversed-phase emulsion system preparation
The tensio-active agent that accounts for reaction system 1～15% is dissolved in the solvent 1 that accounts for reaction system 20～60%, treat that abundant dispersing and dissolving evenly after, the monomer solution of step (1) is slowly added, fully stir, obtain opaque inverse emulsion polymerization reaction system;
(3) heat polymerization
After the thermal initiator usefulness that accounts for reaction monomers total mass 0.1～1.0% being accounted for solvent 2 dissolvings of reaction system 0.1～0.5%, join in the reversed-phase emulsion system of step (2), after stirring, feed the oxygen of rare gas element, make to be reflected under the deoxygenation conditions and carry out, slowly be warming up to 45 ℃～65 ℃ with the replacement(metathesis)reaction system, and keep promptly obtaining in 5～8 hours described material, reaction system remains opaque emulsion state, and wherein the water microgel is the class sphere, and particle diameter is 50nm～2 μ m.
Priority Applications (1)
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