CN114478904B - Semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent and preparation method and application thereof - Google Patents
Semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent and preparation method and application thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
The invention relates to a semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control agent in the field of oilfield auxiliaries, and a preparation method and application thereof. The semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control agent comprises a core-shell type polymer microsphere, wherein one of the core or the shell of the core-shell type polymer microsphere contains a hydrophobic structural unit, and the hydrophobic structural unit is derived from an amphiphilic hydrophobic monomer; the amphiphilic hydrophobic monomer is selected from anionic hydrophobic monomers and/or cationic hydrophobic monomers. The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent prepared by the preparation process provided by the invention still has good expansion performance and plugging performance after long-term aging under high temperature and high mineralization, and can be directly or after being compounded with other oilfield chemicals, used for field application of deep profile control, oil displacement and the like for tertiary oil recovery of high-temperature high-salt and medium-high permeability reservoirs.
Description
Technical Field
The invention relates to the field of oilfield aids, in particular to a semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent, a preparation method and application thereof.
Background
The polymer microsphere has the following advantages as a recognized deep profile control agent: the microspheres can meet the requirement of 'getting in and out and getting blocked at the pore throat of a water flow channel', can expand when meeting water and do not change when meeting oil, and are selective blocking agents; the microsphere expansion layer is diluted and peeled continuously after being washed by water for a long time, and finally oil and water are extracted from an oil well, so that pollution and damage to the stratum are avoided, and a special treatment liquid is not needed for treating a profile control well in the later period. However, the general microsphere system adopts inverse microemulsion or inverse emulsion polymerization, so that the generated particles have smaller size and are generally of a homogeneous structure, and the microsphere system has poor adaptability to high-temperature high-salt and medium-high permeability reservoir polymer microspheres and cannot play an effective role in deep profile control and displacement.
Compared with the homogeneous microsphere, the core-shell type polymer microsphere has more complex preparation process, but can introduce different monomers into the core and the shell of the polymer respectively to form different crosslinking densities, and can form certain interaction force between the core and the shell through molecular design, so that the structure is more flexible and adjustable, and the core-shell type microsphere is far superior to the homogeneous microsphere in the aspects of temperature resistance, salt resistance, hydrolysis resistance, stability and the like; the multi-step feeding polymerization mode reduces the content of the emulsifier in the system and increases the content of the water phase, and the effective content of the solid matters of the product is actually increased.
The core-shell polymer microsphere can be divided into three types, namely a core-shell distinct type, a transition layer type and a gradient type. The core-shell distinct microsphere has a clear and distinct interface between the core and the shell, and the core and the shell are two different substances; the transition layer microsphere tightly combines the core layer and the shell layer in a chemical bond mode through a (grafting, interpenetrating network or ionic bonding) transition layer between the core and the shell, so that the mechanical defect generated by the existence of a distinct phase interface can be eliminated, and the performance of the core-shell polymer microsphere can be remarkably improved; the gradient polymer microsphere is prepared by adopting a gradient feeding method (also called a power-level feeding method) when inverse emulsion polymerization is carried out, and the copolymerization composition (or blending composition) of the polymer gradually changes from the center of the microsphere to the surface of the shell of the microsphere according to a certain functional relation by multiplying the gradient, so that the prepared core-shell microsphere can be endowed with excellent performance.
In recent years, more researches are developed in the aspect of research on polyacrylamide microsphere flooding agents in China, a plurality of universities and research institutions have better progress and achievements in the aspects of polyacrylamide microsphere preparation and tertiary oil recovery and oil displacement application, and polymer microsphere emulsion with various sizes from nano-scale, submicron-scale and micron-scale is prepared, but the polymer microsphere structure obtained in field application is mostly homogeneous, and the solid content is low; the preparation process of the microsphere with the core-shell structure reported in few documents is complex, most researches on reaction mechanism, dynamics, characterization and the like are focused on basic physical properties such as molecular weight, particle size and the like of the polymer, and the stability of the polymer microsphere under the oil reservoir condition, the expansion performance of the microsphere and other factors directly influencing the application are not considered or the research result is not ideal.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control agent. In particular to a semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control agent, a preparation method and application thereof.
The invention aims to provide a semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control agent, wherein one of a core or a shell of the core-shell type polymer microsphere contains a hydrophobic structural unit, and the hydrophobic structural unit is derived from an amphiphilic hydrophobic monomer;
the amphiphilic hydrophobic monomer is selected from anionic hydrophobic monomers and/or cationic hydrophobic monomers;
preferably, the anionic hydrophobic monomer is selected from at least one of sodium alkyl sulfonate with 8-16 long chain vinyl carbon chains or sodium p-acrylamidoalkylbenzene sulfonate; the cationic hydrophobic monomer is at least one of allyl alkyl ammonium chloride with a vinyl carbon chain number of 12-20.
The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent is prepared by the reaction of the following components in the presence of a composite initiator; wherein, based on the total mass of the semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent being 100%, the total mass of the semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent is as follows:
a) 20-50% of an oil-soluble solvent; preferably 20 to 40 percent;
b) 1-10% of a composite emulsifier system; preferably 1 to 5%;
c) 40-75% of water phase; preferably 55 to 75%; the water phase contains nonionic water-soluble monomers, amphiphilic hydrophobic monomers and ionic monomers; the weight content of all monomers in the water phase is 50-70%;
d) 0.02-2% of cross-linking agent; preferably 0.02 to 1.5%;
wherein, the composite initiator comprises the following components in percentage by weight based on the total monomer weight:
(a) 0.02-1.0% of oxidant;
(b) 0.02-2.0% of reducing agent;
(c) 0.03 to 2.0 percent of azo compound.
Preferably, the method comprises the steps of,
the weight of the amphiphilic hydrophobic monomer accounts for 0.1-5% of the total mass of the nonionic water-soluble monomer, the amphiphilic hydrophobic monomer and the ionic monomer (namely the total mass of all monomers in the water phase), preferably 0.2-3%, and more preferably 0.3-1.5%.
Wherein, the liquid crystal display device comprises a liquid crystal display device,
the oil-soluble solvent may be at least one selected from aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, etc., and preferably may be a mixture of one or more of toluene, o-xylene, isoparaffins, naphthenes, paraffins, petroleum ether, toluene, xylene, white oil, and coal oil, etc.
The composite emulsifier system can be partially selected from at least one of nonionic lipophilic surfactant and hydrophilic surfactant, and can be specifically selected from at least one of fatty acid polyoxyethylene ester, alkyl acid polyoxyethylene ether, fatty alcohol polyoxyethylene ether and the like; the mass ratio of the two classes of surfactants is adjusted so that the hydrophilic-lipophilic balance (HLB) of the composite emulsifier system is between 4 and 9.
And/or, to increase the stability of the system, co-emulsifiers may also be added, which may be selected from at least one of some alcohols, salts and/or small molecule polymers. The total amount of co-emulsifier may be from 10 to 90wt%, preferably from 10 to 60wt%, of the total amount of the composite emulsifier system. Wherein the salt can be at least one selected from chloride or acetate of sodium or potassium;
the small molecule polymer may comprise oligomers, preferably at least one of polyacrylamide, polyacrylic acid, polyethylene glycol, etc., having a molecular weight of thousands (e.g., molecular weight 1000-10000).
The nonionic water soluble monomer may include, but is not limited to, at least one of acrylamide, methacrylamide, t-butyl acrylamide, N-isopropyl acrylamide, N-dimethylacrylamide, N-diethylacrylamide and N-methylolacrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyridine and N-vinylpyrrolidone, nitrogen vinylpyrrolidone, and the like; and/or the number of the groups of groups,
the ionic monomers may include, but are not limited to, anionic monomers and/or cationic monomers; the anionic monomer may include, but is not limited to, at least one of 2-acrylamido-2-methylpropanesulfonic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, and/or water soluble alkali metal salts, alkaline earth metal salts, and ammonium salts thereof; and/or the number of the groups of groups,
the cationic monomer may include, but is not limited to, at least one of dimethyldiallylammonium chloride, acryloxyethyltrimethylammonium chloride, methacryloxyethyltrimethylammonium chloride, methacryloxypropyltrimethylammonium chloride, and 2-acrylamido-2-methylpropyltrimethylammonium chloride.
The amphiphilic hydrophobic monomer may include, but is not limited to, anionic hydrophobic monomers and/or cationic hydrophobic monomers; preferably, the anionic hydrophobic monomer may include, but is not limited to, at least one of sodium long-chain alkyl sulfonate or sodium p-acrylamidoalkylbenzene sulfonate having a vinyl carbon chain number of 8 to 16, and the cationic hydrophobic monomer may be selected from allyl alkyl ammonium chloride having a vinyl carbon chain number of 12 to 20, etc., and specifically may be selected from octadecyl dimethyl trimethoxy silyl propyl ammonium chloride, dimethyl tetradecyl (2-acrylamidoethyl) ammonium chloride, etc.
The crosslinking agent may include, but is not limited to, at least one of N, N-methylenebisacrylamide, divinylbenzene, polyethylene glycol diacrylate, aldehydes containing two or more aldehyde groups, trimethylol propane trimethacrylate, pentaerythritol triacrylate, and the like. Wherein the aldehyde is specifically selected from at least one of glyoxal, glutaraldehyde, etc.
The oxidant can be at least one selected from potassium persulfate, sodium persulfate, ammonium persulfate or benzoyl peroxide; the reducing agent can be at least one selected from sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium thiosulfate, ferrous chloride and the like;
the azo compound may be at least one selected from 2,2' -azo [2- (2-imidazolin-2-yl) propane ] dihydrochloride (V044), azobisisobutylamino hydrochloride (V50), azobisisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN), and the like.
The second purpose of the invention is to provide a preparation method of the semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent, which comprises the following steps:
(a) Adding the oil-soluble solvent and the lipophilic surfactant in the composite emulsifier system into a container with a certain size, and uniformly mixing to form a continuous oil phase;
(b) Dissolving and uniformly stirring the polymerization monomer (containing or not containing amphiphilic hydrophobic monomer) needed by the preparation of microsphere core part, hydrophilic surfactant, auxiliary emulsifier, cross-linking agent and other assistants in a composite emulsifier system in water in a container with a certain size to form a water phase I; in another container, the components of the polymeric monomer (with or without amphiphilic hydrophobic monomer), auxiliary emulsifier, cross-linking agent and the like required for preparing the microsphere shell part are dissolved in water and uniformly stirred to form a water phase II. The oxidant and the reducing agent can be respectively dissolved in water to form an initiator aqueous solution, and the oil-soluble initiator can be dissolved in a small amount of solvent for standby.
Wherein, preferably, the aqueous phase I and the aqueous phase II do not simultaneously contain amphiphilic hydrophobic monomers; preferably, one of the aqueous phase I or the aqueous phase II contains an amphiphilic hydrophobic monomer, i.e. the present invention introduces an amphiphilic hydrophobic monomer into only one aqueous phase.
Preferably, the weight of the amphiphilic hydrophobic monomer is 0.3% to 6%, preferably 0.3% to 4%, more preferably 0.5% to 3% of the total mass of all monomers in the aqueous phase in which it is located (i.e. the alternative of aqueous phase I or aqueous phase II). And/or the ratio of the total weight of the monomers contained in the water phase I to the total weight of the monomers contained in the water phase II is 6:1-0.5:1, preferably 4:1 to 1:1, more preferably 3:1 to 1.5:1.
(c) Slowly adding the water phase I into the continuous oil phase, and simultaneously, shearing at high speed to form milky emulsion, and putting the milky emulsion into a reaction kettle (a homogenizing emulsifying machine can be used, and shearing at high speed for 3-30 minutes at 10000-20000 rpm); controlling the temperature in a reaction kettle at 5-30 ℃, stirring at 400-600 rpm, introducing nitrogen to deoxidize for 0.5-1 h, then dropwise adding a certain amount of oxidant to stir for 5-10 min uniformly, then continuously dropwise adding a reducing agent at a certain speed (the specific speed can be determined according to the concentration and total amount of the reducing agent, such as 0.01-10 ml/min) to initiate polymerization, controlling the polymerization reaction to release heat by the dropwise adding speed of the reducing agent, controlling the heating speed to be less than or equal to 2 ℃/min, keeping the final reaction temperature at 30-60 ℃, keeping the temperature at the highest peak, and keeping the temperature for continuous reaction for 0.5-1 h to obtain the core part of the semitransparent semi-interpenetrating network yin-yang core-shell type polymer microsphere flooding agent;
(d) Adding a water-soluble azo initiator or an oil-soluble azo initiator dissolved by a small amount of solvent into the water phase II, uniformly stirring, dripping the water-soluble azo initiator into the nuclear emulsion of the polymer microsphere obtained in the step (c) at a certain speed, stably performing polymerization through water bath temperature control, wherein the water bath temperature can be controlled between 40 and 70 ℃, finishing the reaction after 4 to 8 hours, cooling to room temperature, dripping a certain amount of phase inversion agent, and uniformly stirring to obtain the polymer microsphere. The second step reaction adopts a dripping process, and the dripping speed of the water phase can be controlled, so that the diffusion speed of the water phase in the second step into the core is ensured to be smaller than the reaction speed of the monomer, thus the second step reaction is basically carried out on the outer layer of the core, and the product structure obtained by the two steps of reaction is basically a core-shell structure. The water phase II is added dropwise within 1.5-3 hours, preferably 2-2.5 hours. The dropping speed may be 3 to 10g/min, preferably 4 to 6g/min.
The dosage of the phase inversion agent is 5-95% of the weight of the composite emulsifier, preferably 20-80%; the phase inversion agent can be a surfactant with a structure similar to that of a hydrophilic surfactant in the composite emulsifier system. The phase inversion agent may be at least one selected from hydrophilic surfactants such as fatty acid polyoxyethylene esters, alkyl acid polyoxyethylene ethers, fatty alcohol polyoxyethylene ethers, etc., except that the number of ethoxy groups therein is equal to or slightly smaller than that of the emulsifier, that is, the HLB value is close to or slightly smaller than that of the emulsifier, and the HLB value of the phase inversion agent is 10 to 20, preferably 10 to 15.
The invention further aims to provide application of the semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control agent in deep profile control and oil displacement for tertiary oil recovery of medium-high permeability oil reservoirs under high temperature and high mineralization. Specifically, the semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent can be directly or after being compounded with other oilfield chemicals, used for on-site application of deep profile control, oil displacement and the like for tertiary oil recovery of high-temperature high-salt and medium-high permeability reservoirs.
The polymer microsphere profile control agent can be compounded with other oilfield chemical additives as required, such as an oil displacement type polymer or surfactant, and the weight ratio of the oilfield chemical additives to the microspheres can be 1:10-10: 1.
according to the invention, on the basis of extensive and intensive researches on the aspects of synthesis, structural characterization and properties of polyacrylamide inverse emulsion and core-shell structure microspheres, an inverse emulsion or inverse microemulsion polymerization method is adopted, amphiphilic hydrophobic monomers are introduced into monomers of microsphere cores or shells, in the step-by-step nucleation or cladding reaction process, reactive groups of the hydrophobic monomers are copolymerized with acrylamide and other monomers in the microsphere cores or shell monomers, and hydrophobic long-chain tail groups point to an oil phase, so that the hydrophobic monomers are generally easy to be distributed on an oil-water interface, and further generate copolymerization with cladding or nucleated monomers or adsorption of anions and cations; in this way, the core and the shell of the polymer microsphere are connected through the amphiphilic hydrophobic monomer to form intermolecular association crosslinking, which is equivalent to a semi-interpenetrating network. Compared with the common core-shell microsphere, the cathode-anode core-shell microsphere has a more definite and stable structure, and improves the profile control plugging performance.
The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent can solve the problems that the bonding force between the core and the shell is poor, the forward core-shell structure is difficult to ensure and finally the blending product of the two microspheres is easy to form when the core-shell polymer microsphere is prepared in the prior art. The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent prepared by the preparation process provided by the invention has the initial particle size of hundreds of nanometers (particularly 200-900 nanometers), has good expansion performance and plugging performance after long-term aging under high temperature and high mineralization, and can be directly or after being compounded with other oilfield chemicals, used for in-situ application of deep profile control, oil displacement and the like for tertiary oil recovery of high-temperature high-salt and medium-high permeability reservoirs.
Drawings
FIG. 1 is a schematic illustration of interpenetrating network associated microspheres;
FIG. 2 is a schematic diagram of a semi-interpenetrating network core-shell microsphere described herein.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The raw materials used in the examples are all commercially available.
[ example 1 ]
650g of No. 5 white oil, 72g of SPAN80 (HLB=4.3) is firstly added into a beaker, and the mixture is stirred until the mixture is completely and uniformly mixed to be used as a mixed oil phase, and 1/4 of the mixed oil phase is reserved for supplementing; adding 500g of water, 6g of dimethylallyl octadecyl ammonium chloride, 630g of acrylamide, 260g of dimethyldiallyl ammonium chloride (60% content), 10g of potassium acetate, 0.8g of diethylenetriamine pentaacetic acid sodium salt, 8g of methylenebisacrylamide, 8g of TWEEN80 (HLB=15), and an emulsifier system consisting of SPAN80 in an oil phase, wherein the HLB=5.37 and 0.4g of V044 are uniformly stirred and dissolved to obtain a water phase I; 280g of water, 330g of acrylamide, 100g of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 5g of potassium acetate, 0.4g of diethylenetriamine pentaacetic acid sodium salt and 1.0g of methylene bisacrylamide are added into a different container, after the solvent is stirred uniformly, 5g of isopropanol solution dissolved with 0.4g of azodiisobutyronitrile is added, and the mixture is stirred uniformly to be used as a water phase II; ammonium persulfate and sodium bisulphite are respectively prepared into 1.0% and 0.05% aqueous solutions for standby. Slowly adding the water phase I into the mixed oil phase in the beaker, simultaneously starting a homogenizing emulsifying machine, shearing at a high speed for 3 minutes at 20000 revolutions per minute to form milky emulsion, and putting the milky emulsion into a reaction kettle; controlling the temperature in a reaction kettle at 20 ℃, stirring at 400rpm, introducing nitrogen to remove oxygen for 0.5h, then dripping 4g of oxidant aqueous solution, stirring for 10min to be uniform, continuously dripping reducing agent aqueous solution at a certain speed to initiate polymerization, controlling the exothermic of polymerization reaction by the dripping speed of the reducing agent aqueous solution, controlling the heating speed to be less than or equal to 2 ℃/min, raising the temperature to 43 ℃ after about 3 hours, and keeping the temperature for continuous reaction for 1.5 hours to obtain the core part of the semitransparent semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control agent; adding the reserved oil phase into a reaction kettle, uniformly stirring, continuously dripping a water phase II into the formed nuclear emulsion of the microsphere profile control agent at a certain speed, controlling the polymerization at about 56 ℃ through the water bath temperature, stably carrying out the water phase II, dripping the water phase II for about 2 hours, then preserving the heat for 2 hours, ending the reaction, cooling to room temperature, dripping 36g of OP10 (HLB=13.5), continuously stirring for 20 minutes to obtain a semitransparent product, and stably storing for more than 6 months.
The sampling analysis is referenced Q/SH1020 Chinese petrochemical group winning Petroleum administration enterprise standard polymer microsphere deep profile control agent technical condition test method test that the content of the precipitable solid is 42.5%, the initial average particle size is 530nm, the total mineralization degree is 250000mg/L at 95 ℃, ca 2+ +Mg 2+ : the polymer microspheres with the concentration of 0.2 percent are 0.5PV after being injected into a sand filling pipe with the concentration of 2000mD for 45 days, and the plugging rate is 89 percent.
[ example 2 ]
650g of No. 5 white oil and 72g of SPAN80 (HLB=4.3) are firstly added into a reaction kettle, and stirred until the mixture is completely and uniformly mixed, and 1/4 of the mixture is reserved for supplementing; 520g of water, 630g of acrylamide, 180g of methacryloyl propyl trimethyl ammonium chloride, 6g of dimethylallyl hexadecyl ammonium chloride, 8g of sodium acetate, 5g of TWEEN60 (HLB=14.9), an emulsifier system HLB=4.99 formed by SPAN80 in an oil phase, 0.5g of disodium ethylenediamine tetraacetate, 10g of isopropanol and 11g of methylenebisacrylamide are added into a container with a certain size, and uniformly stirred and dissolved to form a water phase I; 320g of water, 300g of acrylamide, 65g of 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 18g of sodium acetate, 0.5g of ethylene diamine tetraacetic acid disodium salt and 1.0g of methylene bisacrylamide are added into a different container, after a solvent is stirred uniformly, 10g of isopropanol solution dissolved with 1g of azodiisoheptanenitrile is added, and the mixture is stirred uniformly to be used as a water phase II; ammonium persulfate and sodium bisulphite are respectively prepared into 1.0% and 0.1% aqueous solutions for standby. Slowly adding the water phase I into the mixed oil phase, simultaneously starting a homogenizing emulsifying machine, shearing at a high speed of 10000 revolutions per minute for 15 minutes to form milky emulsion, and putting the milky emulsion into a reaction kettle; controlling the temperature in a reaction kettle at 18 ℃, stirring at 500rpm, introducing nitrogen to remove oxygen for 0.5h, then dripping 2g of oxidant aqueous solution, stirring for 10min to be uniform, continuously dripping reducing agent aqueous solution at a certain speed to initiate polymerization, controlling the exothermic of polymerization reaction by the dripping speed of the reducing agent aqueous solution, controlling the heating speed to be less than or equal to 1.5 ℃/min, raising the temperature to 42 ℃ after about 4 hours, preserving heat, and continuing to react for 1 hour to obtain the core part of the semitransparent semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control agent; adding the reserved oil phase into a reaction kettle, uniformly stirring, continuously dripping a water phase II into the formed nuclear emulsion of the microsphere profile control agent at a certain speed, controlling the polymerization at about 56 ℃ through the water bath temperature, stably carrying out the water phase II dripping for about 2 hours, then preserving the heat for 2 hours to finish the reaction, cooling to room temperature, dripping 30g of OP10 (HLB=13.5) and continuously stirring for 20 minutes to obtain a semitransparent product, and stably storing for more than 6 months.
The sampling analysis is referenced Q/SH1020 Chinese petrochemical group winning Petroleum administration enterprise standard polymer microsphere deep profile control agent technical condition test method test that the content of the precipitable solid is 40.7%, the initial average particle size is 620nm, the total mineralization degree is 250000mg/L at 95 ℃, ca 2+ +Mg 2+ : aging for 5 days, 15 days and 45 days under 10000mg/L saline, respectively with particle size expansion times of 4.6, 7.2 and 10.9 times, injecting 0.2% concentration polymer 0.5PV after aging for 45 days by using a sand filling pipe of 2000mD, and measuring that the plugging rate reaches 89%.
[ example 3 ]
Firstly adding 680g of 120# solvent oil, 78g of SPAN60 (HLB=4.7) into a reaction kettle, stirring until the mixture is completely and uniformly mixed, and reserving 1/4 as a mixed oil phase for supplementing; 530g of water, 15g of tetradecyldimethylallyl ammonium chloride, 630g of acrylamide, 270g of acryloyloxyethyl trimethyl ammonium chloride, 10g of sodium acetate, 10g of TWEEN60 (HLB=14.9), an emulsifier system composed of HLB=5.86 and SPAN60 in an oil phase, 1.0g of disodium ethylenediamine tetraacetate, 15g of isopropanol and 2.1g of pentaerythritol triacrylate are added into a container with a certain size, and stirred and dissolved uniformly to obtain a water phase I; in another vessel, 300g of water, 380g of acrylamide, 50g of N, N-dimethylacrylamide, 20g of sodium acetate, 0.5g of ethylenediamine tetraacetic acid disodium salt, 1.0g of methylenebisacrylamide, and after stirring and dissolving uniformly, 0.4g of 2,2' -azo [2- (2-imidazolin-2-yl) propane ] dihydrochloride (V044) was added, and stirring and dissolving uniformly to obtain a water phase II; ammonium persulfate and sodium bisulphite are respectively prepared into 1.0% and 0.1% aqueous solutions for standby. Slowly adding the water phase I into the mixed oil phase, simultaneously starting a homogenizing emulsifying machine, shearing at a high speed of 10000 revolutions per minute for 15 minutes to form milky emulsion, and putting the milky emulsion into a reaction kettle; controlling the temperature in a reaction kettle at 25 ℃, stirring at 520rpm, introducing nitrogen to remove oxygen for 0.5h, then dripping 3g of oxidant aqueous solution, stirring for 10min to be uniform, continuously dripping reducing agent aqueous solution at a certain speed to initiate polymerization, controlling the exothermic of polymerization reaction by the dripping speed of the reducing agent aqueous solution, controlling the heating speed to be less than or equal to 1.8 ℃/min, raising the temperature to 41 ℃ after about 3.5 h, keeping the temperature, and continuing to react for 1h to obtain the core part of the semitransparent semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control agent; adding the reserved oil phase into a reaction kettle, uniformly stirring, continuously dripping a water phase II into the formed nuclear emulsion of the microsphere profile control agent at a certain speed, controlling the polymerization at about 52 ℃ through the water bath temperature, finishing dripping the water phase II for about 2.5 hours, preserving heat for 2 hours after finishing dripping, finishing reaction, cooling to room temperature, dripping 30g of AEO9 (HLB=13.5), continuously stirring for 20 minutes to obtain a semitransparent product, and stably storing for more than 6 months.
Sampling analysis reference Q/SH1020 China petrochemical group winning Petroleum administration enterprise Standard aggregationThe content of the precipitated solid is 40.2% by testing the method of the deep profile control agent technical condition of the microspheres, the initial average particle size is 570nm, the total mineralization degree is 250000mg/L at 95 ℃, ca 2+ +Mg 2+ : aging for 5 days, 15 days and 45 days under 10000mg/L saline, respectively with the expansion times of particle size of 4.3, 7.2 and 10.3 times, injecting 0.2% concentration polymer 0.5PV after aging for 45 days by using a sand filling pipe of 2000mD, and measuring the plugging rate to be 91%.
[ example 4 ]
650g of 3# white oil, 72g of span80 (HLB=4.3) are firstly added into a reaction kettle, and stirred until the mixture is completely and uniformly mixed, and 1/4 of the mixture is reserved for supplementing; 550g of water, 685g of acrylamide, 200g of sodium 2-acrylamido-2-methylpropanesulfonate, 5g of OP10 (HLB=13.5), and an emulsifier system consisting of SPAN80 in an oil phase, namely HLB=4.90, 12g of sodium acetate, 0.8g of disodium ethylenediamine tetraacetate, 10g of isopropanol and 2.0g of methylene bisacrylamide are added into a container with a certain size, and uniformly stirred and dissolved to form a water phase I; adding 310g of water, 10g of octadecyl dimethyl trimethoxy silane propyl ammonium chloride, 380g of acrylamide, 40g of dimethyl diallyl ammonium chloride, 12g of sodium acetate, 0.5g of ethylene diamine tetraacetic acid disodium salt and 0.8g of polyethylene glycol diacrylate into a different container, uniformly stirring the solvent, adding 0.5g of azo diisobutyl amidine hydrochloride (V50), and uniformly stirring and dissolving to obtain a water phase II; ammonium persulfate and sodium bisulphite are respectively prepared into 1.0% and 0.1% aqueous solutions for standby. Slowly adding the water phase I into the mixed oil phase, simultaneously starting a homogenizing emulsifying machine, shearing at a high speed of 10000 revolutions per minute for 20 minutes to form milky emulsion, and putting the milky emulsion into a reaction kettle; controlling the temperature in a reaction kettle at 26 ℃, stirring at 550rpm, introducing nitrogen to remove oxygen for 0.5h, then dripping 3g of oxidant aqueous solution, stirring for 10min to be uniform, continuously dripping reducing agent aqueous solution at a certain speed to initiate polymerization, controlling the exothermic of polymerization reaction by the dripping speed of the reducing agent aqueous solution, controlling the heating speed to be less than or equal to 1.5 ℃/min, raising the temperature to 48 ℃ after about 3.8 h, and keeping the temperature for continuous reaction for 0.5h to obtain the nuclear part of the semitransparent semi-interpenetrating network yin-yang core-shell type polymer microsphere flooding agent; adding the reserved oil phase into a reaction kettle, uniformly stirring, continuously dripping a water phase II into the formed nuclear emulsion of the microsphere profile control agent at a certain speed, controlling the polymerization at about 56 ℃ through the water bath temperature, stably performing the polymerization for about 2.5 hours, keeping the temperature for 2 hours after the dripping is finished, finishing the reaction, cooling to the room temperature, dripping 28g of AEO9 (HLB=13.5), continuously stirring for 20 minutes to obtain a semitransparent product, and stably storing for more than 6 months.
The sampling analysis is referenced Q/SH1020 Chinese petrochemical group winning Petroleum administration enterprise standard polymer microsphere deep profile control agent technical condition test method test that the content of the precipitable solid is 42.5%, the initial average particle size is 720nm, the total mineralization degree is 250000mg/L at 95 ℃, ca 2+ +Mg 2+ : aging for 5 days, 15 days and 45 days under 10000mg/L saline, respectively with the expansion times of particle size of 4.9, 7.8 and 9.6 times, injecting 0.2% concentration polymer 0.5PV after aging for 45 days by using a sand filling pipe of 2000mD, and measuring that the plugging rate reaches 88%.
[ example 5 ]
640g of 90# solvent oil, 75g of span80 (hlb=4.3) are added into a reaction kettle, and stirred until the mixture is completely and uniformly mixed, and 1/4 of the mixture is reserved for supplementing; 570g of water, 12g of dimethyl tetradecyl (2-acrylamidoethyl) ammonium chloride, 720g of acrylamide, 130g of dimethyl diallyl ammonium chloride, 15g of potassium acetate, 0.7g of sodium diethylenetriamine pentaacetate, 10g of isopropanol, 7g of OP15 (HLB=15) and 8g of pentaerythritol triacrylate are added into a container with a certain size, and the mixture is uniformly stirred and dissolved to form an emulsifier system HLB=5.94 consisting of SPAN80 in an oil phase to serve as a water phase I; in another vessel, 300g of water, 350g of acrylamide, 65g of nitrogen vinyl pyrrolidone, 5g of sodium acetate, 0.8g of divinylbenzene, 8g of isopropanol, 0.8g of pentaerythritol triacrylate and 0.5g of azo diisobutyl amidine hydrochloride (V50) are added, stirred and dissolved uniformly to obtain a water phase II; ammonium persulfate and sodium bisulphite are respectively prepared into 2.0% and 0.2% aqueous solutions for standby. Slowly adding the water phase I into the mixed oil phase, simultaneously starting a homogenizing emulsifying machine, shearing at a high speed of 10000 revolutions per minute for 20 minutes to form milky emulsion, and putting the milky emulsion into a reaction kettle; controlling the temperature in a reaction kettle at 18 ℃, stirring at 500rpm, introducing nitrogen to remove oxygen for 0.5h, then dripping 1.5g of oxidant aqueous solution to stir for 10min to uniformity, continuously dripping reducing agent aqueous solution at a certain speed to initiate polymerization, controlling the exothermic of polymerization reaction by the dripping acceleration of the reducing agent aqueous solution, controlling the heating speed to be less than or equal to 1.8 ℃/min, raising the temperature to 46 ℃ after about 4.2 h, and keeping the temperature for continuous reaction for 0.5h to obtain the core part of the semitransparent semi-interpenetrating network yin-yang core-shell polymer microsphere flooding agent; adding the reserved oil phase into a reaction kettle, uniformly stirring, continuously dripping the water phase II into the formed nuclear emulsion of the microsphere profile control agent at a certain speed, controlling the polymerization at about 56 ℃ through the water bath temperature, finishing dripping the water phase II for about 2.5 hours, preserving the heat for 2 hours after finishing dripping, finishing the reaction, cooling to the room temperature, dripping 35g of OP10 (HLB=13.5), continuously stirring for 20 minutes to obtain a semitransparent product, and stably storing for more than 6 months.
The sampling analysis is referenced Q/SH1020 Chinese petrochemical group winning Petroleum administration enterprise standard polymer microsphere deep profile control agent technical condition test method test that the content of the precipitable solid is 42.1%, the initial average particle size is 530nm, the total mineralization degree is 250000mg/L at 95 ℃, ca 2+ +Mg 2+ : aging for 5 days, 15 days and 45 days under 10000mg/L saline, respectively with the expansion times of particle size of 4.6, 7.9 and 10.8 times, injecting 0.2% concentration polymer 0.5PV after aging for 45 days by using a sand filling pipe of 2000mD, and measuring the plugging rate to be 91%.
From the above examples, the semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent obtained by the invention has a submicron level with an initial particle diameter of hundreds of nanometers, a solid content of more than 40%, can effectively block a 2000mD hypertonic sand filling pipe after aging for a period of time under the condition of high-temperature and high-salt oil reservoir, and has a blocking rate of about 90% after being injected with 0.5PV with a concentration of 0.2% after aging for 45 days.
Comparative example 1
Except that dimethylallyl octadecyl ammonium chloride was removed in example 1, the remainder being the same.
Sampling analysis reference Q/SH1020 China petrochemical group winning Petroleum administration enterprise standard Polymer microsphere deep profile control agent technical ConditionThe determination method tests that the content of the precipitable solid is 42.1%, the initial average particle diameter is 430nm, the total mineralization degree is 250000mg/L at 95 ℃, ca 2+ +Mg 2+ : the polymer microspheres with the concentration of 0.2 percent are 0.5PV after being injected into a sand filling pipe with the concentration of 2000mD for 45 days, and the plugging rate is measured to be 27 percent.
Comparative example 2
The dimethylallyl octadecyl ammonium chloride of example 1 was replaced with styrene, the remainder being the same.
The sampling analysis is referenced Q/SH1020 Chinese petrochemical group winning Petroleum administration enterprise standard polymer microsphere deep profile control agent technical condition test method test that the content of the precipitable solid is 42.3%, the initial average particle size is 470nm, the total mineralization degree is 250000mg/L at 95 ℃, ca 2+ +Mg 2+ : the polymer microspheres with the concentration of 0.2 percent and 0.5PV after aging for 45 days are injected into a sand filling pipe with the concentration of 2000mD by using a sand filling pipe with the particle size expansion times of 2.9, 3.6 and 4.9 times respectively after aging for 5 days, 15 days and 45 days under 10000mg/L of saline, and the plugging rate is measured to be 34 percent.
[ comparative example 3 ]
The interpenetrating network-associated polymer microspheres obtained in example 1 of CN109666096A were evaluated under the conditions of the present invention, and the total degree of mineralization was 250000mg/L at 95℃and Ca 2+ +Mg 2+ : the polymer microspheres with the concentration of 0.2 percent are 0.5PV after being injected into a sand filling pipe with the concentration of 2000mD for 45 days, and the plugging rate is measured to be 52 percent.
Therefore, the plugging performance of the obtained microsphere is much poorer without adding amphiphilic hydrophobic monomers or adding lipophilic hydrophobic monomers. Without amphiphilic hydrophobic monomer, semi-interpenetrating network between core-shell can not be formed, and the expansion performance and plugging performance of the microsphere can be deteriorated after long-term aging under high temperature and high mineralization. The interpenetrating network microsphere obtained by adopting the CN109666096A embodiment method is of a homogeneous structure, and the aggregation adsorption effect of the microsphere after long-term aging is weaker than that of the microsphere with a semi-interpenetrating core-shell structure, so that the plugging capability is also relatively weaker.
Claims (18)
1. A semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent, wherein one of the core or shell of the core-shell polymer microsphere contains a hydrophobic structural unit, and the hydrophobic structural unit is derived from an amphiphilic hydrophobic monomer;
the amphiphilic hydrophobic monomer is selected from anionic hydrophobic monomers and/or cationic hydrophobic monomers;
the anionic hydrophobic monomer is selected from at least one of sodium long-chain alkyl sulfonate or sodium p-acrylamidoalkylbenzene sulfonate with vinyl carbon chain number of 8-16; the cationic hydrophobic monomer is at least one of allyl alkyl ammonium chloride with a vinyl carbon chain number of 12-20;
the semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent is prepared by the following components in the presence of a composite initiator; wherein, each component comprises the following components in percentage by weight:
a) 20-50% of an oil-soluble solvent;
b) 1-10% of a composite emulsifier system;
c) 40-75% of a water phase;
d) 0.02-2% of a cross-linking agent;
the semi-interpenetrating network yin-yang core-shell type polymer microsphere profile control agent is prepared by a method comprising the following steps:
(a) Uniformly mixing the oil-soluble solvent and the lipophilic surfactant in the composite emulsifier system to form a continuous oil phase;
(b) The components of a polymeric monomer required for preparing microsphere core parts, a hydrophilic surfactant, a coemulsifier and a cross-linking agent in a composite emulsifier system are dissolved in water and stirred uniformly to form a water phase I; in addition, the components including the polymerization monomer, the auxiliary emulsifier and the cross-linking agent required by the microsphere shell part preparation are dissolved in water and stirred uniformly to form a water phase II; the water phase I and the water phase II do not simultaneously contain amphiphilic hydrophobic monomers; one of the water phase I or the water phase II comprises an amphiphilic hydrophobic monomer;
(c) Slowly adding the water phase I into the continuous oil phase, shearing to form emulsion, and putting the emulsion into a reaction kettle; the temperature in the reaction kettle is controlled to be 5-30 ℃, oxygen is removed, then an oxidant is added, stirring is carried out uniformly, then a reducing agent is added to initiate polymerization, the polymerization reaction is controlled to release heat according to the adding speed of the reducing agent, the heating speed is controlled to be less than or equal to 2 ℃/min, the final reaction temperature is kept to be 30-60 ℃, and after the temperature reaches the highest peak, heat preservation is carried out for continuous reaction for 0.5-1 hour, so that the nuclear emulsion of the semi-interpenetrating network yin-yang core-shell polymer microsphere flooding agent is obtained;
(d) Adding azo initiator into water phase II, stirring, dropping into the nuclear emulsion of polymer microsphere, polymerizing, cooling, dropping phase inversion agent and stirring.
2. The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent according to claim 1, wherein the agent is characterized by:
is prepared by the reaction of the following components in the presence of a composite initiator; wherein, each component comprises the following components in percentage by weight:
a) 20-40% of an oil-soluble solvent;
b) 1-5% of a composite emulsifier system;
c) 55-75% of water phase; the water phase contains nonionic water-soluble monomers, amphiphilic hydrophobic monomers and ionic monomers; the weight content of all monomers in the water phase is 50-70%;
d) 0.02-1.5% of a cross-linking agent.
3. The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent according to claim 2, wherein the agent is characterized by:
the weight of the amphiphilic hydrophobic monomer accounts for 0.1% -5% of the total mass of the nonionic water-soluble monomer, the amphiphilic hydrophobic monomer and the ionic monomer.
4. The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent according to claim 3, wherein the profile control agent is characterized by:
the weight of the amphiphilic hydrophobic monomer accounts for 0.2% -3% of the total mass of the nonionic water-soluble monomer, the amphiphilic hydrophobic monomer and the ionic monomer.
5. The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent according to claim 4, wherein the agent is characterized by:
the weight of the amphiphilic hydrophobic monomer accounts for 0.3% -1.5% of the total mass of the nonionic water-soluble monomer, the amphiphilic hydrophobic monomer and the ionic monomer.
6. The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent according to claim 1, wherein the agent is characterized by:
the composite initiator comprises the following components in percentage by weight of all monomers:
(a) 0.02-1.0% of oxidant;
(b) 0.02-2.0% of reducing agent;
(c) 0.03 to 2.0 percent of azo compound.
7. The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent according to claim 1, wherein the agent is characterized by:
the hydrophilic-lipophilic balance value of the composite emulsifier system is between 4 and 9;
the composite emulsifier system is at least one selected from nonionic lipophilic surfactant and hydrophilic surfactant.
8. The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent according to claim 7, wherein the agent is characterized by:
the compound emulsifier system is at least one selected from fatty acid polyoxyethylene ester, alkyl acid polyoxyethylene ether and fatty alcohol polyoxyethylene ether.
9. The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent according to claim 1, which is characterized by comprising an auxiliary emulsifier;
the auxiliary emulsifier is selected from at least one of alcohols, salts and/or small molecule polymers;
the total amount of the auxiliary emulsifier is 10-90wt% of the total amount of the composite emulsifier system.
10. The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent according to claim 9, wherein the agent is characterized by:
the total amount of the auxiliary emulsifier is 10-60wt% of the total amount of the composite emulsifier system.
11. The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent according to claim 2, wherein the agent is characterized by:
the nonionic water-soluble monomer is at least one selected from acrylamide, methacrylamide, N-isopropyl acrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-methylolacrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyridine and N-vinylpyrrolidone; and/or the number of the groups of groups,
the ionic monomer is selected from anionic monomers and/or cationic monomers;
the anionic monomer is selected from at least one of 2-acrylamide-2-methylpropanesulfonic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, vinylbenzenesulfonic acid, vinylsulfonic acid and/or water-soluble alkali metal salt, alkaline earth metal salt and ammonium salt thereof; and/or the number of the groups of groups,
the cationic monomer is at least one selected from dimethyl diallyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, methacryloylpropyl trimethyl ammonium chloride and 2-acrylamido-2-methylpropyl trimethyl ammonium chloride.
12. The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent according to claim 1, wherein the agent is characterized by:
the oil-soluble solvent is at least one of aliphatic hydrocarbon, aromatic hydrocarbon and halogenated hydrocarbon;
and/or the number of the groups of groups,
the cross-linking agent is at least one selected from N, N-methylene bisacrylamide, divinylbenzene, polyethylene glycol diacrylate, aldehydes containing two or more aldehyde groups, trimethylolpropane trimethacrylate and pentaerythritol triacrylate.
13. The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent according to claim 12, wherein:
the oil-soluble solvent is selected from one or more of toluene, o-xylene, isoparaffin, cycloparaffin, paraffin, petroleum ether, toluene, xylene, white oil and kerosene.
14. The semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent according to claim 6, wherein the agent is characterized by:
the oxidant is at least one selected from potassium persulfate, sodium persulfate, ammonium persulfate or benzoyl peroxide; and/or the number of the groups of groups,
the reducing agent is at least one selected from sodium sulfite, potassium sulfite, sodium bisulfite, potassium hydrogen sulfite, sodium thiosulfate and ferrous chloride; and/or the number of the groups of groups,
the azo compound is at least one selected from 2,2' -azo [2- (2-imidazoline-2-yl) propane ] dihydrochloride, azo diisobutyl amidine hydrochloride, azo diisobutyronitrile and azo diisoheptonitrile.
15. The preparation method of the semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent according to any one of claims 1 to 14, which is characterized by comprising the following steps:
(a) Uniformly mixing the oil-soluble solvent and the lipophilic surfactant in the composite emulsifier system to form a continuous oil phase;
(b) The components of a polymeric monomer required for preparing microsphere core parts, a hydrophilic surfactant, a coemulsifier and a cross-linking agent in a composite emulsifier system are dissolved in water and stirred uniformly to form a water phase I; in addition, the components including the polymerization monomer, the auxiliary emulsifier and the cross-linking agent required by the microsphere shell part preparation are dissolved in water and stirred uniformly to form a water phase II; wherein the aqueous phase I and the aqueous phase II do not simultaneously contain amphiphilic hydrophobic monomers; one of the water phase I or the water phase II comprises an amphiphilic hydrophobic monomer;
(c) Slowly adding the water phase I into the continuous oil phase, shearing to form emulsion, and putting the emulsion into a reaction kettle; the temperature in the reaction kettle is controlled to be 5-30 ℃, oxygen is removed, then an oxidant is added, stirring is carried out uniformly, then a reducing agent is added to initiate polymerization, the polymerization reaction is controlled to release heat according to the adding speed of the reducing agent, the heating speed is controlled to be less than or equal to 2 ℃/min, the final reaction temperature is kept to be 30-60 ℃, and after the temperature reaches the highest peak, heat preservation is carried out for continuous reaction for 0.5-1 hour, so that the nuclear emulsion of the semi-interpenetrating network yin-yang core-shell polymer microsphere flooding agent is obtained;
(d) Adding azo initiator into water phase II, stirring, dropping into the nuclear emulsion of polymer microsphere, polymerizing, cooling, dropping phase inversion agent and stirring.
16. The method for preparing the semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent according to claim 15, which is characterized by comprising the following steps:
in the step (d) of the above-mentioned method,
when the polymerization reaction is carried out, the reaction temperature is controlled to be between 40 and 70 ℃ and the reaction time is 4 to 8 hours; and/or the number of the groups of groups,
the dosage of the phase inversion agent is equivalent to 5-95% of the weight of the composite emulsifier;
the phase inversion agent is selected from hydrophilic surfactants; the HLB value of the phase inversion agent is 10-20.
17. The method for preparing the semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent according to claim 16, which is characterized by comprising the following steps:
the dosage of the phase inversion agent is 20-80% of the weight of the composite emulsifier;
the phase inversion agent is at least one selected from fatty acid polyoxyethylene ester, alkyl acid polyoxyethylene ether and fatty alcohol polyoxyethylene ether.
18. Use of the semi-interpenetrating network yin-yang core-shell polymer microsphere profile control agent according to any one of claims 1-14 or prepared by the preparation method according to any one of claims 15-17 in deep profile control and oil displacement for tertiary oil recovery of medium and high permeability reservoirs at high temperature and high mineralization.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015189060A1 (en) * | 2014-06-11 | 2015-12-17 | Basf Se | Amphiphilic macromonomers, method for producing amphiphilic macromonomers, copolymers comprising amphiphilic macromonomers and the use of such copolymers for tertiary petroleum production |
| CN108315003A (en) * | 2017-01-17 | 2018-07-24 | 中国石油化工股份有限公司 | Polyacrylamide microballoon in-depth profile control and its preparation method and application |
| CN109666096A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Interpenetrating networks association type polymer microballoon profile control agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015189060A1 (en) * | 2014-06-11 | 2015-12-17 | Basf Se | Amphiphilic macromonomers, method for producing amphiphilic macromonomers, copolymers comprising amphiphilic macromonomers and the use of such copolymers for tertiary petroleum production |
| CN108315003A (en) * | 2017-01-17 | 2018-07-24 | 中国石油化工股份有限公司 | Polyacrylamide microballoon in-depth profile control and its preparation method and application |
| CN109666096A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Interpenetrating networks association type polymer microballoon profile control agent and preparation method thereof |
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