CN108546315B - Amphiphilic polymer oil displacement agent and preparation method and application thereof - Google Patents
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Abstract
The invention discloses an amphiphilic polymer oil-displacing agent, and a preparation method and application thereof. The preparation method of the amphiphilic polymer oil-displacing agent comprises the following steps: acrylamide, acrylic acid alkali metal salt, dimethyl diallyl ammonium chloride, methyl acryloyl oxyethyl dimethyl dodecyl ammonium bromide and an amphiphilic dendritic unsaturated monomer shown in a formula (1) or a formula (2) are subjected to free radical copolymerization reaction to obtain the acrylic acid modified dendritic unsaturated monomer. The amphiphilic polymer oil displacement agent is suitable for the field of thickened oil recovery, can obviously reduce the viscosity of thickened oil after being mixed with the thickened oil, and is beneficial to improving the fluidity of the thickened oil in a stratum.
Description
Technical Field
The invention relates to an oil-displacing agent, a preparation method and application thereof, in particular to an amphiphilic polymer oil-displacing agent, a preparation method and application thereof, and belongs to the technical field of tertiary oil recovery.
Background
With the extensive and deep progress of the offshore heavy oil chemical flooding mine test, chemical flooding has some new problems to be solved urgently in the large-scale application process. In order to widen the application range of chemical flooding in the development of thick oil, a thick oil displacement agent which can reduce the viscosity of crude oil, increase the viscosity of a water phase and greatly improve the water-oil fluidity ratio needs to be developed aiming at the flowable thick oil with higher formation viscosity of an offshore oil field.
For the traditional partially hydrolyzed polyacrylamide oil displacement agent, the displacement mechanism is that the viscosity of polymer displacement fluid is increased, the water-oil fluidity ratio is improved, and the longitudinal and transverse swept volumes in an oil reservoir are increased, so that the crude oil recovery rate and the oil recovery speed are increased. However, as the temperature of the oil field and the mineralization degree of the injection water are increased, the hydrodynamic radius of macromolecules in the displacement fluid is reduced, and the tackifying performance of the solution is obviously reduced. On the other hand, the partially hydrolyzed polyacrylamide does not have the performance of reducing the tension of an oil-water interface, residual oil is difficult to effectively start, and crude oil is easy to re-adsorb in the migration process, so that the displacement efficiency of the oil displacement fluid is reduced. In addition, the displacement fluid can not effectively and stably disperse the heavy oil, so that the viscosity of the oil-water front mixed phase is increased, and the injection pressure is increased and the injectability is reduced due to the adsorption effect of the displacement agent on the surface of the rock mineral of the oil reservoir.
Disclosure of Invention
The invention aims to provide an amphiphilic polymer oil-displacing agent which is prepared by carrying out copolymerization reaction on an amphiphilic dendritic unsaturated monomer and other monomers and is suitable for the field of thickened oil exploitation.
The preparation method of the amphiphilic polymer oil-displacing agent provided by the invention comprises the following steps:
acrylamide, acrylic acid alkali metal salt, dimethyl diallyl ammonium chloride, methyl acryloyl oxyethyl dimethyl dodecyl ammonium bromide and an amphiphilic dendritic unsaturated monomer shown in a formula (1) or a formula (2) are subjected to free radical copolymerization reaction to obtain the acrylic acid modified dendritic unsaturated monomer;
in the formulas (1) and (2), R is a straight chain or branched chain alkyl with 8-22 carbon atoms, and X is Cl or Br.
Specifically, R may be a linear or branched alkyl group having 8 carbon atoms, such as n-octane or 2-ethylhexane.
In the above preparation method, in the total monomers, the mol percentage of acrylamide may be 65 to 85%, the mol percentage of the acrylic acid alkali metal salt may be 5 to 25%, the mol percentage of dimethyldiallylammonium chloride may be 1 to 10%, the mol percentage of methacryloyloxyethyl dimethyldodecylammonium bromide may be 1 to 10%, and the mol percentage of the amphiphilic dendritic unsaturated monomer may be 0.1 to 3 mol%;
the total monomer refers to the sum of the acrylamide, the alkali metal acrylate, the dimethyldiallylammonium chloride, the methacryloyloxyethyl dimethyldodecylammonium bromide and the amphiphilic dendritic unsaturated monomer.
In the above preparation method, the acrylic acid alkali metal salt may be sodium acrylate or potassium acrylate.
In the above production method, the conditions of the radical copolymerization are as follows:
under inert gas;
the initial reaction temperature is 0-10 ℃, the pH value of the system is 7.2-8.0, and the pH value can be adjusted by a pH regulator, such as sodium hydroxide or sodium carbonate.
In the above-mentioned preparation method, after the completion of the radical copolymerization reaction, the reaction product needs to be cut, dried and pulverized.
The amphiphilic dendritic unsaturated monomer represented by formula (1) or formula (2) used in the method of the present invention can be prepared by a method comprising the steps of:
(1) reacting ethylenediamine with methyl acrylate to obtain 1.5 generation PAMAM dendritic molecules or 2.5 generation PAMAM dendritic molecules respectively;
(2) the 1.5 generation PAMAM dendritic molecule or the 2.5 generation PAMAM dendritic molecule sequentially reacts with N- (3-aminopropyl) acrylamide, N-dimethylethylenediamine and alkyl halide to obtain a 2.0 generation amphiphilic dendritic unsaturated monomer or a 3.0 generation amphiphilic dendritic unsaturated monomer, namely the amphiphilic dendritic unsaturated monomer shown in the formula (1) or the formula (2);
the molecular formula of the alkyl halide is RX, wherein R is a straight chain or branched chain alkyl with 8-22 carbon atoms, and X is Cl or Br.
In the preparation method, in the step (1), firstly, ethylenediamine and methyl acrylate are reacted to prepare the 0.5 generation PAMAM dendrimer, and the specific conditions are as follows:
the method is carried out under the nitrogen atmosphere;
the reaction temperature is 35-45 ℃, and the reaction time is 48-72 hours;
the molar ratio of the methyl acrylate to the ethylenediamine is 1.0: 4.5 to 6.0;
and after the reaction is finished, carrying out reduced pressure distillation to remove residual methyl acrylate and solvent.
Then, the 1.5 generation PAMAM dendritic molecule is prepared by adopting the 0.5 generation PAMAM dendritic molecule, and the specific process is as follows:
reacting 1 the 0.5 generation PAMAM dendrimer with the ethylenediamine to obtain a viscous liquid product A (the solvent and the residual ethylenediamine need to be removed by reduced pressure distillation); under the nitrogen atmosphere, reacting the viscous liquid product A with the methyl acrylate for 36-54 h at 35-45 ℃, supplementing the methyl acrylate, and continuing to react for 36-54 h (removing residual methyl acrylate and solvent by reduced pressure distillation);
the reaction temperature of the reaction 1 is 45-55 ℃, and the reaction time is 48-72 h;
the molar ratio of the 0.5-generation PAMAM dendrimer to the ethylenediamine to the methyl acrylate is 1.0: 4.5-6.0: 9.0 to 12.0.
In the preparation method, in the step (1), the 2.5 generation PAMAM dendrimer is prepared according to the following process:
reacting the 1.5 generation PAMAM dendrimer with the ethylenediamine to obtain a viscous liquid product B (the solvent and the residual ethylenediamine need to be removed by reduced pressure distillation); under the nitrogen atmosphere, reacting the viscous liquid product B with the methyl acrylate for 36-54 h at 35-45 ℃, and then supplementing the methyl acrylate to continue reacting for 72-96 h (removing residual methyl acrylate and solvent by reduced pressure distillation);
the molar ratio of the 1.5-generation PAMAM dendrimer to the ethylenediamine to the methyl acrylate is 1.0: 9.0-12.0: 18.0 to 24.0.
In the above preparation method, in the step (2), the reaction steps are as follows:
under the nitrogen atmosphere, reacting the 1.5 generation PAMAM dendrimer or the 2.5 generation PAMAM dendrimer with the N- (3-aminopropyl) acrylamide at 40-55 ℃, adding the N, N-dimethylethylenediamine after monitoring the reaction, and continuing the reaction at 40-55 ℃, and monitoring the reaction to obtain a product C (removing the solvent, and residual N- (3-aminopropyl) acrylamide and N, N-dimethylethylenediamine after the reaction is finished);
and (3) carrying out quaternary ammonium salination reaction on the product C and the alkyl halide under nitrogen atmosphere to obtain a 2.0 generation amphiphilic dendritic unsaturated monomer (shown in a formula (1)) or a 3.0 generation amphiphilic dendritic unsaturated monomer (shown in a formula (2)) (after the reaction is finished, carrying out reduced pressure distillation, recrystallization, separation and vacuum drying).
In the above preparation method, in the preparation method of the 2.0 generation amphiphilic dendritic unsaturated monomer, the molar ratio of the 1.5 generation PAMAM dendrimer, the N- (3-aminopropyl) acrylamide, the N, N-dimethylethylenediamine and the alkyl halide is 1.0: 1.1-1.5: 3.0-12.0: 3.0 to 12.0;
in the preparation method of the 3.0 generation amphiphilic dendritic unsaturated monomer, the molar ratio of the 2.5 generation PAMAM dendrimer to the N- (3-aminopropyl) acrylamide to the N, N-dimethylethylenediamine to the alkyl halide is 1.0: 1.1-4.0: 3.0-18.0: 3.0 to 18.0.
In the preparation method, in the step (1) and the step (2), the solvent adopted in the reaction is one or more of methanol, ethanol, propanol and acetone;
in the step (1), the adding amount of the solvent can be 30-70% of the mass of the system of the reaction;
in the step (2), the addition amount of the solvent can be 30-80% of the mass of the system of the reaction.
The amphiphilic polymer oil-displacing agent prepared by the method also belongs to the protection scope of the invention.
The amphiphilic polymer oil displacement agent is suitable for the field of thickened oil recovery, can obviously reduce the viscosity of thickened oil after being mixed with the thickened oil, and is beneficial to improving the fluidity of the thickened oil in a stratum.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
EXAMPLE 1, preparation of 2.0 Generation of amphiphilic dendritic unsaturated monomer (formula (1) -1)
(1) Preparation of 0.5 generation PAMAM dendrimer
Slowly adding 0.1mol of ethylenediamine and 0.5mol of methyl acrylate into a three-necked bottle containing 70g of absolute ethyl alcohol, introducing nitrogen to deoxidize for 1h under the condition of stirring, heating to 35 ℃, and continuing to react for 48 h. And distilling under reduced pressure to remove residual methyl acrylate and anhydrous methanol to obtain 0.5 generation PAMAM dendritic molecules.
(2) Preparation of 1.5 generation PAMAM dendrimers
Adding 0.05mol of 0.5 generation PAMAM dendritic molecule, 0.27mol of ethylenediamine and 40g of anhydrous methanol into a three-necked bottle, heating to 45 ℃ under the stirring condition, reacting for 48h, and monitoring the reaction process. After the reaction, the anhydrous methanol and the remaining ethylenediamine were distilled off under reduced pressure. Adding the obtained viscous liquid, 0.32mol of methyl acrylate and 90g of absolute ethyl alcohol into a three-neck flask, introducing nitrogen to deoxidize under the condition of stirring, heating to 35 ℃, reacting for 48 hours, adding 0.2mol of methyl acrylate, and continuing to react for 48 hours. After the reaction is finished, residual methyl acrylate and anhydrous methanol are removed through reduced pressure distillation, and the 1.5 generation PAMAM dendritic molecules are obtained.
(3) Preparation of 2.0 generation amphiphilic dendritic unsaturated monomer
0.01mol of 1.5-generation PAMAM dendrimer, 0.015mol of N- (3-aminopropyl) acrylamide and 35g of absolute ethyl alcohol are added into a three-necked flask, nitrogen is introduced for deoxidation, the mixture is heated to 40 ℃ under the stirring condition, and the reaction degree is monitored during the reaction. Then 0.1mol of N, N-dimethylethylenediamine was added thereto, and the reaction was continued at 40 ℃. After the reaction is finished, the absolute ethyl alcohol, the residual N- (3-aminopropyl) acrylamide and the N, N-dimethylethylenediamine are removed. Dissolving the obtained product and 0.11mol of bromo-n-octane in anhydrous methanol, introducing nitrogen to deoxidize for 1h, heating to 50 ℃ under the condition of stirring, and continuing to react for 96 h. After the reaction is finished, carrying out reduced pressure distillation, recrystallization, column chromatography separation and vacuum drying to obtain the 2.0 generation amphiphilic dendritic unsaturated monomer with the structural formula shown in formula (1) -1.
Example 2 preparation of amphiphilic Polymer oil-displacing agent
Acrylamide, sodium acrylate, dimethyl diallyl ammonium chloride, methyl acryloyl oxyethyl dimethyl dodecyl ammonium bromide and amphiphilic dendritic unsaturated monomer shown in the formula (1) -1 are subjected to copolymerization reaction.
Adding various monomers accounting for 25 wt% of the total weight of the reaction system and deionized water accounting for 75 wt% of the total weight of the reaction system into a reaction vessel, and stirring to completely dissolve the monomers. The molar percentages of all comonomers (acrylamide, sodium acrylate, dimethyl diallyl ammonium chloride, methacryloyloxyethyl dimethyl dodecyl ammonium bromide and the amphiphilic dendritic unsaturated monomer shown in the formula (1) -1) in sequence are 75 mol%, 16 mol%, 5.5 mol%, 2.5 mol% and 1.0 mol%, the comonomers are stirred to be completely dissolved, then a pH regulator sodium carbonate is added to adjust the pH of the reaction solution to about 7.2, the temperature of the reaction solution is reduced to 2 ℃, nitrogen is introduced for 60min to remove oxygen in the reaction solution. Adding an initiator under the protection of nitrogen, continuously introducing nitrogen for 20min, sealing and continuously reacting for 6 h. And cutting, drying and crushing the obtained product to obtain a powdery amphiphilic polymer oil-displacing agent product.
Example 3 preparation of amphiphilic Polymer oil displacing agent
Acrylamide, potassium acrylate, dimethyl diallyl ammonium chloride, methyl acryloyl oxyethyl dimethyl dodecyl ammonium bromide and amphiphilic dendritic unsaturated monomer shown in the formula (1) -1 are subjected to copolymerization reaction.
Various monomers accounting for 26 weight percent of the total weight of the reaction system and deionized water accounting for 74 weight percent of the total weight of the reaction system are added into a reaction vessel and stirred to ensure that the monomers are completely dissolved. The molar percentage of each comonomer (acrylamide, potassium acrylate, dimethyl diallyl ammonium chloride, methacryloyloxyethyl dimethyl dodecyl ammonium bromide and the amphiphilic dendritic unsaturated monomer shown in the formula (1) -1) in sequence to all the comonomers is 73 mol%, 20 mol%, 5.0 mol%, 1.5 mol% and 0.5 mol%, the comonomers are stirred to be completely dissolved, then a pH regulator sodium hydroxide is added to regulate the pH of the reaction solution to about 7.5, the temperature of the reaction solution is reduced to 5 ℃, and nitrogen is introduced for 60min to remove oxygen in the reaction solution. Adding an initiator under the protection of nitrogen, continuously introducing nitrogen for 20min, sealing and continuously reacting for 6 h. And cutting, drying and crushing the obtained product to obtain a powdery amphiphilic polymer oil-displacing agent product.
Example 4 preparation of amphiphilic Polymer oil displacing agent
Acrylamide, potassium acrylate, dimethyl diallyl ammonium chloride, methyl acryloyl oxyethyl dimethyl dodecyl ammonium bromide and amphiphilic dendritic unsaturated monomer shown in the formula (1) -1 are subjected to copolymerization reaction.
Various monomers accounting for 22 wt% of the total weight of the reaction system and deionized water accounting for 78 wt% of the total weight of the reaction system are added into a reaction vessel, and the monomers are completely dissolved by stirring. The molar percentages of all comonomers (acrylamide, potassium acrylate, dimethyl diallyl ammonium chloride, methacryloyloxyethyl dimethyl dodecyl ammonium bromide and the amphiphilic dendritic unsaturated monomer shown in the formula (1) -1) in sequence are 70 mol%, 22 mol%, 4.0 mol%, 3.0 mol% and 1.0 mol%, the comonomers are stirred to be completely dissolved, then a pH regulator sodium hydroxide is added to regulate the pH of the reaction solution to about 8.0, the temperature of the reaction solution is reduced to 10 ℃, and nitrogen is introduced for 50min to remove oxygen in the reaction solution. Adding an initiator under the protection of nitrogen, continuously introducing nitrogen for 25min, sealing and continuously reacting for 7 h. And cutting, drying and crushing the obtained product to obtain a powdery amphiphilic polymer oil-displacing agent product.
Example 5, preparation of 3.0 Generation amphiphilic dendritic unsaturated monomer (formula (2) -1)
(1) Preparation of 2.5 generation PAMAM dendrimers
Adding 0.05mol of 1.5 generation PAMAM dendritic molecule, 0.5mol of ethylenediamine and 110g of anhydrous methanol into a three-necked bottle, heating to 45 ℃ under the stirring condition, reacting for 48h, and monitoring the reaction process. After the reaction, the anhydrous methanol and the remaining ethylenediamine were distilled off under reduced pressure. Adding the obtained viscous liquid, 0.65mol of methyl acrylate and 180g of absolute ethyl alcohol into a three-neck flask, introducing nitrogen to deoxidize under the condition of stirring, heating to 35 ℃, reacting for 48 hours, adding 0.4mol of methyl acrylate, and continuing to react for 72 hours. After the reaction is finished, removing residual methyl acrylate and anhydrous methanol by reduced pressure distillation to obtain 2.5-generation PAMAM dendritic molecules.
(2) Preparation of 3.0 generation amphiphilic dendritic unsaturated monomer
0.01mol of 2.5-generation PAMAM dendrimer, 0.015mol of N- (3-aminopropyl) acrylamide and 55g of absolute ethyl alcohol are added into a three-necked flask, nitrogen is introduced for deoxidation, the mixture is heated to 40 ℃ under the stirring condition, and the reaction degree is monitored during the reaction. Then 0.2mol of N, N-dimethylethylenediamine was added thereto, and the reaction was continued at 40 ℃. After the reaction is finished, the absolute ethyl alcohol, the residual N- (3-aminopropyl) acrylamide and the N, N-dimethylethylenediamine are removed. Dissolving the obtained product and 0.22mol of bromo-isooctane in anhydrous methanol, introducing nitrogen to deoxidize for 1h, heating to 50 ℃ under the condition of stirring, and continuing to react for 96 h. After the reaction is finished, carrying out reduced pressure distillation, recrystallization, column chromatography separation and vacuum drying to obtain the 3.0 generation amphiphilic dendritic unsaturated monomer with the structural formula shown in formula (2) -1.
Example 6 preparation of amphiphilic Polymer oil displacing agent
Acrylamide, sodium acrylate, dimethyl diallyl ammonium chloride, methacryloyloxyethyl dimethyl dodecyl ammonium bromide and an amphiphilic dendritic unsaturated monomer shown in a formula (2) -1 are subjected to copolymerization reaction.
Adding various monomers accounting for 25 wt% of the total weight of the reaction system and deionized water accounting for 75 wt% of the total weight of the reaction system into a reaction vessel, and stirring to completely dissolve the monomers. The molar percentages of all comonomers (acrylamide, sodium acrylate, dimethyl diallyl ammonium chloride, methacryloyloxyethyl dimethyl dodecyl ammonium bromide and the amphiphilic dendritic unsaturated monomer shown in the formula (2) -1) in sequence are 75 mol%, 20 mol%, 2.5 mol%, 2.0 mol% and 0.5 mol%, the comonomers are stirred to be completely dissolved, then a pH regulator sodium hydroxide is added to regulate the pH of the reaction solution to about 7.5, the temperature of the reaction solution is reduced to 5 ℃, and nitrogen is introduced for 50min to remove oxygen in the reaction solution. Adding an initiator under the protection of nitrogen, continuously introducing nitrogen for 25min, sealing and continuously reacting for 7 h. And cutting, drying and crushing the obtained product to obtain a powdery amphiphilic polymer oil-displacing agent product.
Example 7 preparation of amphiphilic Polymer oil displacing agent
Acrylamide, potassium acrylate, dimethyl diallyl ammonium chloride, methyl acryloyl oxyethyl dimethyl dodecyl ammonium bromide and amphiphilic dendritic unsaturated monomer shown in the formula (2) -1 are subjected to copolymerization reaction.
Various monomers accounting for 28 weight percent of the total weight of the reaction system and deionized water accounting for 72 weight percent of the total weight of the reaction system are added into a reaction vessel and stirred to ensure that the monomers are completely dissolved. The mole percentages of all comonomers (acrylamide, sodium acrylate, dimethyl diallyl ammonium chloride, methacryloyloxyethyl dimethyl dodecyl ammonium bromide and the amphiphilic dendritic unsaturated monomer shown in the formula (2) -1) in sequence are 80 mol%, 15 mol%, 2.5 mol%, 2.0 mol% and 0.5 mol%, the comonomers are stirred to be completely dissolved, then a pH regulator is added to adjust the pH of the reaction solution to be about 8.0, the temperature of the reaction solution is reduced to 2 ℃, nitrogen is introduced for 60min to remove oxygen in the reaction solution. Adding an initiator under the protection of nitrogen, continuously introducing nitrogen for 20min, sealing and continuously reacting for 7 h. And cutting, drying and crushing the obtained product to obtain a powdery amphiphilic polymer oil-displacing agent product.
Viscosity reducing Effect of the amphipathic Polymer oil-displacing agents prepared in example 8, examples 2 to 4 and examples 6 to 7
Sodium chloride 1.0 xl 0 was used4Preparing amphiphilic polymer oil-displacing agent solutions with different concentrations by mg/L saline water. At the temperature of 65 ℃, adding 25ml of an electro-dewatering crude oil sample of a certain oil field of Bohai sea into a 50ml test tube with a plug, continuously adding 25ml of an amphiphilic polymer oil displacement agent solution, tightly covering a test tube plug, oscillating manually or placing the test tube in an oscillation box, horizontally oscillating for 80-100 times, wherein the amplitude is larger than 20 cm. After being fully mixed, the viscosity of a mixed system after the viscosity reduction of the thick oil is measured by using a Brookfield viscometer at 65 ℃, and the viscosity reduction rate of the thick oil is calculated according to the following formula:
the experimental results are shown in table 1, and it can be seen from the data in table 1 that the amphiphilic polymer oil-displacing agent provided by the invention has an obvious viscosity reduction effect, wherein the viscosity reduction rate of thick oil is higher than 49% and up to 68.98% when the concentration is 400mg/L, and the viscosity reduction rate of thick oil is higher than 68% and up to 87.23% when the concentration is 1200 mg/L.
TABLE 1 viscosity reduction results for thickened oils for amphiphilic Polymer oil-displacing agents prepared in examples 2-4 and 6-7
Claims (6)
1. A preparation method of an amphiphilic polymer oil displacement agent comprises the following steps:
acrylamide, acrylic acid alkali metal salt, dimethyl diallyl ammonium chloride, methyl acryloyl oxyethyl dimethyl dodecyl ammonium bromide and an amphiphilic dendritic unsaturated monomer shown in a formula (1) or a formula (2) are subjected to free radical copolymerization reaction to obtain the acrylic acid modified dendritic unsaturated monomer;
in the formulas (1) and (2), R is a straight chain or branched chain alkyl with 8-22 carbon atoms, and X is Cl or Br.
2. The method of claim 1, wherein: in the total monomers, the molar percentage of acrylamide is 65-85%, the molar percentage of acrylic acid alkali metal salt is 5-25%, the molar percentage of dimethyl diallyl ammonium chloride is 1-10%, the molar percentage of methacryloyloxyethyl dimethyl dodecyl ammonium bromide is 1-10%, and the molar percentage of the amphiphilic dendritic unsaturated monomer is 0.1-3 mol%;
the total monomer refers to the sum of the acrylamide, the alkali metal acrylate, the dimethyldiallylammonium chloride, the methacryloyloxyethyl dimethyldodecylammonium bromide and the amphiphilic dendritic unsaturated monomer.
3. The production method according to claim 1 or 2, characterized in that: the conditions of the radical copolymerization are as follows:
under inert gas;
the initial reaction temperature is 0-10 ℃, and the pH value of the system is 7.2-8.0.
4. An amphiphilic polymer oil-displacing agent prepared by the method of any one of claims 1-3.
5. The use of the amphiphilic polymer oil-displacing agent according to claim 4 in heavy oil recovery.
6. Use according to claim 5, characterized in that: the amphiphilic polymer oil displacement agent reduces the viscosity of the thick oil.
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| CN106084142A (en) * | 2016-07-19 | 2016-11-09 | 西南石油大学 | It is applicable to nucleocapsid shape polymer of oil field produced water and preparation method thereof |
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| CN104672408A (en) * | 2015-02-06 | 2015-06-03 | 西南石油大学 | Rigid-core-shell-structure water-soluble oil-displacing polymer and preparation method thereof |
| CN106084142A (en) * | 2016-07-19 | 2016-11-09 | 西南石油大学 | It is applicable to nucleocapsid shape polymer of oil field produced water and preparation method thereof |
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