CN106589232B - Hydrophobic association acrylamide copolymer and preparation method thereof - Google Patents
Hydrophobic association acrylamide copolymer and preparation method thereof Download PDFInfo
- Publication number
- CN106589232B CN106589232B CN201510684113.2A CN201510684113A CN106589232B CN 106589232 B CN106589232 B CN 106589232B CN 201510684113 A CN201510684113 A CN 201510684113A CN 106589232 B CN106589232 B CN 106589232B
- Authority
- CN
- China
- Prior art keywords
- monomer
- acrylamide copolymer
- resistant
- salt
- acrylamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention provides a hydrophobically associating acrylamide copolymer and a preparation method thereof, and mainly solves the problems of poor temperature resistance, salt resistance, aging resistance and displacement effect of the conventional polymer oil displacement agent in the prior art. The invention adopts a copolymer of acrylamide, a temperature-resistant and salt-resistant monomer and a hydrophobic monomer shown in a structure as formula (I), wherein R is1、R2Each independently from a hydrogen atom, a methyl group or an ethyl group; r3、R4、R5、R6、R7Each independently of the other being derived from a hydrogen atom, C1～C16The fat base can be directly prepared by clean water, saline water or field produced water according to the application, and can be used as an oil displacement agent in harsh oil reservoirs after being used alone or being compounded with other oil field chemicals to improve the crude oil recovery rate.
Description
Technical Field
The invention relates to the field of tertiary oil recovery, in particular to a novel hydrophobically associating acrylamide copolymer and a preparation method thereof.
Background
The general performance requirements of the water-soluble polymer for oil and gas field exploitation mainly comprise: the water solubility, the thickening property, the suspension property, the shearing dilution property, the thixotropy, the stability and the seepage characteristic meet the requirements of oil and gas exploitation engineering and the like. Although the ultrahigh molecular weight polyacrylamide can still improve the oil recovery rate at a higher temperature (such as 120 ℃) in an oxygen-free and divalent ion-free environment, the water-soluble polymer commonly used in tertiary oil recovery at present has a plurality of problems when used for oil displacement. Such as severe polyacrylamide hydrolysis at higher temperatures; after the formation temperature exceeds 75 ℃, the formation of the ultra-high molecular weight polyacrylamide precipitate is accelerated along with the rise of the formation temperature; the phenomenon that the ultrahigh molecular weight polyacrylamide is easily precipitated from an aqueous solution due to high temperature and high salt is more remarkable when the hydrolysis degree is higher; the solution viscosity is very sensitive to temperature and salinity, and the retained viscosity of the solution is very low in a high-temperature and high-salinity environment.
For example, the thermal stability of the polymer is improved by introducing large side groups or rigid side groups into the main chain of the polymer, and hydrolysis-inhibiting monomers or salt-insensitive monomers are introduced for copolymerization to improve the hydrolysis resistance and salt resistance of the polymer, or the temperature and salt resistance of the polymer is improved by hydrophobic association of hydrophobic groups.
The hydrophobic association water-soluble polymer refers to a water-soluble polymer with a small amount of hydrophobic groups on a hydrophilic macromolecular chain of the polymer. In the water solution of the hydrophobic association water-soluble polymer, hydrophobic groups on molecular chains of the polymer are clustered due to hydrophobic effect, macromolecular chains generate intramolecular and intermolecular association, the hydrodynamic volume is increased, and the viscosity of an aqueous medium is improved, so that the polymer has the unique performances of good thickening, temperature resistance, salt resistance and the like; in addition, the larger side group plays a role in shielding the main chain of the polymer molecule, the influence of salt ions on carboxylate ion groups is weakened, and the larger side group also has a certain steric hindrance effect, so that the rigidity of the chain is enhanced. The hydrophobic association polymer has unique solution properties of viscosity increasing, salt resistance, shear resistance and the like, so that the hydrophobic association polymer can be used as a novel polymer oil displacement agent to be applied to the development of high-salt and high-shear oil reservoirs, and has good application prospects.
Researchers at home and abroad carry out a great deal of research on the aspect of the hydrophobic association polymer and obtain better progress and results. The hydrophobically associative polymers are usually prepared by aqueous solution polymerization, but due to the water insolubility of the hydrophobic monomersChina patent CN1891725A reports that acrylonitrile and diisobutylene are catalyzed by concentrated sulfuric acid to synthesize dendritic hydrophobic monomer N- (1, 1, 3, 3-tetramethylbutyl) acrylamide, then a micelle polymerization method is adopted to prepare a hydrophobic associated polyacrylamide oil displacement agent, and the hydrophobic associated polyacrylamide oil displacement agent has good tackifying effect in saline water with mineralization degree of 30000 mg/L at 85 ℃, but the concentrated sulfuric acid adopted in the reaction for preparing the hydrophobic monomer is too strong in oxidability and severe in catalytic reaction process<100000mg/L、CaC12Concentration of<1000 mg/L salt resistance, the literature (synthesis of a new family of hydrophobically associating polyacrylamides and rheological properties of aqueous solutions thereof, 2007 paper) successfully prepares copolymer NaAMC with hydrophobic block structure in aqueous solution by homogeneous copolymerization14S/AM, through adjusting the consumption of the additional electrolyte to control the length of the hydrophobic micro-block, and overcome the tedious disadvantage of post-treatment of micelle copolymerization, but the work is focused on theoretical research, and analysis and evaluation are not carried out under the actual oil field mineral deposit condition, especially under the conditions of high temperature (above 85 ℃) and high mineralization degree (above 100000 mg/L).
The inverse microemulsion polymerization technology is characterized by that under the action of water-in-oil emulsifier, the water-soluble monomer and hydrophobic monomer are used as continuous phase to form W/O microemulsion, then the oil-soluble and/or water-soluble initiator is used to initiate polymerization. The hydrophobic units in the polymer prepared by the method are distributed in a polymer molecular chain in a random or micro-block structure, the association of hydrophobic groups is better, intermolecular association is easy, and the tackifying effect is better. When the hydrophobic association polymer microemulsion prepared by the method is used as an oil displacement agent of an oil field, the emulsifier in the latex can generate a 'synergistic' effect with the hydrophobic association polymer, and can also be used as a surfactant in compound flooding, so that a good emulsification effect is achieved, the oil-water interfacial tension is reduced, and the crude oil recovery rate is improved. From the industrial point of view, the polymer microemulsion system can play the function of 'one dose for multiple purposes', thereby greatly reducing the production cost.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the conventional polymer oil displacement agent in the prior art has poor temperature resistance, salt resistance, ageing resistance and displacement effect, and provides a novel hydrophobically associating acrylamide copolymer, wherein the molecular weight of the hydrophobically associating acrylamide copolymer is 50000-15000000, and the hydrophobically associating acrylamide copolymer has excellent temperature resistance, salt resistance, ageing resistance, shearing resistance and good displacement effect.
The second technical problem to be solved by the invention is to provide a corresponding preparation method of the hydrophobic association acrylamide copolymer for solving the first technical problem, firstly selecting a proper catalyst and reactant ratio, reacting under mild conditions to prepare a hydrophobic monomer shown in a formula (I) structure, then adopting a reverse microemulsion polymerization method, and selecting a proper emulsifier and/or co-emulsifier and an oily solvent, so that the polymerization reaction of the microemulsion is stable, and the process is relatively controlled.
The invention also provides an application of the hydrophobic association acrylamide copolymer in oil field oil recovery.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a hydrophobic association acrylamide copolymer is obtained by copolymerizing acrylamide, a temperature-resistant salt-resistant monomer and a hydrophobic monomer; the structure of the hydrophobic monomer is shown as the formula (I):
wherein R is1、R2Each independently from a hydrogen atom, a methyl group or an ethyl group; r3、R4、R5、R6、R7Each independently of the other being derived from a hydrogen atom, C1～C16The fatty group of (2).
In the above technical scheme, R3、R4、R5、R6、R7Each independently of the other being derived from a hydrogen atom, C1～C16A hydrocarbon group or an alkoxy group of (a).
In the technical scheme, the molecular weight of the hydrophobically associating acrylamide copolymer is 50000-15000000, and the mass ratio of the hydrophobic monomer, the temperature-resistant salt-resistant monomer and the acrylamide is 0-2: 0 to 18: 80-99 parts.
In the above technical solution, the amount of the substance of the hydrophobic monomer is greater than 0.
In the technical scheme, the temperature-resistant and salt-resistant monomer is selected from methacrylamide, N-isopropyl acrylamide, N-hydroxymethyl acrylamide, N-N-dimethyl acrylamide, N-vinylpyridine, N-vinylpyrrolidone, acrylic acid, methacrylic acid, maleic acid, fumaric acid and vinylsulfonic acid, at least one of vinylbenzenesulfonic acid, allylsulfonic acid, allylbenzenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and/or alkali metal salts and ammonium salts thereof, dimethylethylallylammonium chloride, dimethyldiallylammonium chloride, acryloyloxyethyltrimethylammonium chloride, acryloyloxyethyldimethylethylammonium bromide, methacryloyloxyethyltrimethylammonium chloride, and 2-acrylamido-2-methylpropyltrimethylammonium chloride.
In the technical scheme, the acrylamide, the temperature-resistant and salt-resistant monomer and the hydrophobic monomer are subjected to polymerization reaction in reverse microemulsion under the action of a redox initiator to prepare the hydrophobically associating acrylamide copolymer; the reverse microemulsion comprises the following components in parts by weight: 1) 15-70 parts of an oily solvent; 2) 2-20 parts of an emulsifier and/or a co-emulsifier; 3) 0.001-10 parts of a hydrophobic monomer; 4) 10-70 parts of acrylamide; 5) 1-50 parts of a temperature-resistant salt-resistant monomer; 6) 10-60 parts of water
In the above technical solution, the oil-soluble solvent is at least one selected from cyclohexane, hexane, heptane, octane, isooctane, benzene, toluene, ethylbenzene, xylene, cumene, liquid paraffin, vegetable oil, white oil, gasoline, diesel oil and kerosene. The emulsifier is selected from at least one of span, tween, alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ether, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, dodecyl trimethyl quaternary ammonium salt, didodecyl dimethyl quaternary ammonium salt, hexadecyl trimethyl quaternary ammonium salt, dihexadecyl dimethyl quaternary ammonium salt, octadecyl trimethyl quaternary ammonium salt and dioctadecyl dimethyl quaternary ammonium salt; the quaternary ammonium salt is ammonium chloride salt or ammonium bromide salt; the auxiliary emulsifier is selected from ethanol, propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol, hexanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, glycerol, sodium formate, potassium formate, ammonium formate, sodium acetate, potassium acetate, ammonium acetate, sodium adipate, sodium malonate and the like, and the dosage of the auxiliary emulsifier is 0.01-10 wt% of the dosage of the emulsifier.
In the technical scheme, the redox initiator consists of an oxidant and a reducing agent, wherein the mass ratio of the oxidant to the reducing agent is 0.1-8: 1, the total amount of the monomer is 0.001-2% of the weight of the monomer. Wherein the oxidant is at least one of ammonium persulfate, potassium persulfate, sodium persulfate and hydrogen peroxide; the reducing agent is at least one selected from sodium bisulfite, potassium bisulfite, sodium sulfite, potassium sulfite, sodium thiosulfate and ferrous chloride.
To solve the second technical problem, the invention adopts the following technical scheme: a preparation method of a hydrophobic association acrylamide copolymer is characterized by comprising the following steps:
1) preparation of hydrophobic monomer: reacting acrylonitrile with C1～C16Uniformly dispersing aliphatic substituted phenyl olefin in a mixed solution of sulfur trioxide, pyridine and glacial acetic acid, and reacting for 0.5-6 hours at 10-50 ℃ to prepare a hydrophobic monomer shown in a structure of a formula (I);
2) preparation of a water phase: dissolving acrylamide, a temperature-resistant salt-resistant monomer and an oxidant in water, fully stirring until the solution is clear and free of insoluble substances, and adjusting the pH value of the solution to 7-12 by using an alkali liquor; dissolving a reducing agent in the balance of water separately for later use;
3) preparing a microemulsion system: dissolving an emulsifier and/or a co-emulsifier and a hydrophobic monomer in an oil-soluble solvent, stirring and dissolving uniformly, adding the water phase prepared in the step 2) into the oil phase, and stirring to obtain a transparent or semitransparent reverse microemulsion system;
4) reverse microemulsion polymerization: introducing inert gas into the reversed-phase microemulsion system obtained in the step 3) to remove oxygen, adding the reducing agent aqueous solution prepared in the step 2), uniformly mixing, initiating a polymerization reaction at 5-45 ℃, and continuing the reaction for 0.5-6 hours after the exothermic peak temperature appears to obtain a transparent or semitransparent hydrophobic association acrylamide copolymer microemulsion; the hydrophobic association acrylamide copolymer is obtained by the post-treatment methods of demulsification, precipitation, washing, drying and the like.
In the above technical scheme, C1～C16The aliphatic-substituted phenylolefin is more preferably C1～C16Hydrocarbyl or alkoxy substituted phenyl alkenes.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the application of the hydrophobic association acrylamide copolymer in the technical scheme of the technical method in oil recovery in oil fields.
In the above technical solutions, those skilled in the art can utilize the above methods according to the prior art, for example, in the field operations, the application of the hydrophobically associating acrylamide copolymer in oil field oil recovery requires that the hydrophobically associating acrylamide copolymer is directly prepared with clean water, high salinity saline water or field produced water of the oil field, and the hydrophobically associating acrylamide copolymer is applied to tertiary oil recovery of the oil field as an oil displacement agent to improve the recovery rate of crude oil alone or after being compounded with other field chemicals.
The key point of the method is that a special hydrophobic monomer and a reverse microemulsion polymerization method are adopted, a hydrophobic monomer unit with a special structure is introduced into a conventional water-soluble polyacrylamide macromolecular chain, intermolecular association can be generated in saline water with high salinity of 150000 mg/L at a high temperature of 95 ℃, the tackifying effect is obvious (the viscosity of the solution reaches 182.6mPa & s when the concentration of the polymer is 1800 mg/L), the viscosity retention rate reaches more than 92.5 percent after aging for 45 days under the anaerobic condition, the polymer shows excellent temperature resistance, salt resistance and ageing resistance, in addition, the shear resistance of the polymer can be obviously improved by a cross-linked net structure existing in macromolecules, when the concentration of the polymer is 1800 mg/L, the viscosity retention rate is still more than 95.6 percent after the polymer is subjected to shearing for 24 hours after being subjected to shearing for half an hour under 2000 rpm, the oil-water interfacial tension between the hydrophobic association acrylamide copolymer and oil produced from 2 to 529 is as low as 0.108mN/m, the good technical effect can be obtained by directly using the polymer microemulsion as a clear water, or a chemical oil displacement agent which is independently prepared to be applied to oil field oil recovery efficiency after being independently compounded with the oil field oil and chemical oil displacement agent and the field oil recovery efficiency of the field.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
1. Synthesis of hydrophobic monomer:
under the protection of nitrogen, 8.5g of sulfur trioxide and 6m of L pyridine are stirred at room temperature and uniformly dissolved in a glass reaction kettle filled with 85m of L glacial acetic acid, 8.2g of acrylonitrile is slowly added dropwise into the mixed solution, 25g of p-N-butylstyrene is added dropwise, the mixture is continuously stirred and reacted for 4 hours at the temperature of 33 ℃, 300m of L deionized water is introduced, standing is carried out after uniform stirring, and the hydrophobic monomer N- (1-p-N-butylphenyl) ethyl acrylamide is obtained after filtration, washing and drying, wherein the yield is 94.1%.
2. Synthesis of hydrophobic association type acrylamide polymer:
75g of n-heptane, 27.5g of lauryl alcohol polyoxyethylene ether (3), 7.5g of octyl phenol polyoxyethylene ether (4) and 0.49g N- (1-n-butyl phenyl) ethyl acrylamide monomer are added into a reaction kettle, stirred and mixed uniformly, the temperature in the kettle is controlled at 25 ℃, and the stirring speed is 255 revolutions per minute. Adding 42g of deionized water, 55g of acrylamide, 10g of 2-acrylamido-2-methylpropanesulfonic acid, 0.15g of disodium ethylene diamine tetraacetate, 0.88g of tert-butyl alcohol and 1.5g of sodium persulfate into a batching kettle, stirring to dissolve the materials uniformly, and adjusting the pH value to 7.9 by using NaOH; in addition, 2g of sodium sulfite was dissolved in 15g of deionized water for use. Introducing the water phase into a reaction kettle, stirring to fully emulsify the water phase, adding 5g of sodium sulfite aqueous solution, raising the temperature of the system to 71 ℃, setting the temperature of the reaction kettle to be 60 ℃, continuing to react for 3 hours, and performing emulsion breaking, precipitation, washing, drying and other post-treatment methods after the reaction is ended to obtain the hydrophobic association ternary acrylamide copolymer.
The structure and performance of the hydrophobically associating acrylamide copolymer are tested by the following method or standard, namely, the solid content of the polymer is measured according to the solid content method of GB/T12005.2-89 polyacrylamide, the intrinsic viscosity of the polymer is measured according to the molecular weight (viscosity method) of GB/T12005.10-92 polyacrylamide, and the intrinsic viscosity is measured according to [ η ]]＝3.73×10-4Mw 0.66Calculating molecular weight, and testing polymer saline solution (total mineralization degree 150000 mg/L, calcium and magnesium ion concentration 8000 mg/L) with concentration of 1800 mg/L by Haake rheometer at 95 deg.C for 7.34s-1The apparent viscosity at 95 ℃ after aging for 45 days in the absence of oxygen as measured by Q/SH1020 for an aqueous polymer salt solution at a concentration of 1800 mg/L, the apparent viscosity of an aqueous polymer salt solution at a concentration of 1800 mg/L after shearing at 2000 rpm for half an hour and then allowing the solution to stand for 24 hours as measured by a Haake rheometer, the interfacial tension between the hydrophobically associative acrylamide copolymer and the oils produced by Pu 2-529 was measured by a TX-500 rotary drop interfacial tension tester, a university of Texas USA, and the results of the above analyses are shown in Table 1.
[ example 2 ]
The synthesis of the hydrophobic monomer and the preparation of the hydrophobically associating acrylamide copolymer were the same as in example 1 except that the amount of N- (1-p-butylphenyl) ethyl acrylamide monomer was increased to 0.97 g. By the following methods or marksThe structure and performance of the hydrophobically associating acrylamide copolymer obtained by quasi test are that the solid content of the polymer is measured according to the GB/T12005.2-89 polyacrylamide solid content method, the intrinsic viscosity of the polymer is measured according to the GB/T12005.10-92 polyacrylamide molecular weight (viscosity method), and the intrinsic viscosity is measured according to [ η ]]＝3.73×10-4Mw 0.66Calculating molecular weight, and testing polymer saline solution (total mineralization degree 150000 mg/L, calcium and magnesium ion concentration 8000 mg/L) with concentration of 1800 mg/L by Haake rheometer at 95 deg.C for 7.34s-1The apparent viscosity at 95 ℃ after aging for 45 days in the absence of oxygen as measured by Q/SH1020 for an aqueous polymer salt solution at a concentration of 1800 mg/L, the apparent viscosity of an aqueous polymer salt solution at a concentration of 1800 mg/L after shearing at 2000 rpm for half an hour and then allowing the solution to stand for 24 hours as measured by a Haake rheometer, the interfacial tension between the hydrophobically associative acrylamide copolymer and the oils produced by Pu 2-529 was measured by a TX-500 rotary drop interfacial tension tester, a university of Texas USA, and the results of the above analyses are shown in Table 1.
[ example 3 ]
The synthesis of hydrophobic monomers and the preparation of hydrophobically associating acrylamide copolymers were performed as described in example 2, except that the amount of N- (1-p-butylphenyl) ethyl acrylamide monomer was increased to 1.91g, and the structure and properties of the hydrophobically associating acrylamide copolymers were measured by the following method or standard, i.e., the solid content of the polymer was measured by the GB/T12005.2-89 polyacrylamide solid content method, the intrinsic viscosity of the polymer was measured by the GB/T12005.10-92 polyacrylamide molecular weight measurement (viscosity method), and the intrinsic viscosity of the polymer was measured by the method of [ η ]]＝3.73×10-4Mw 0.66Calculating molecular weight, and testing polymer saline solution (total mineralization degree 150000 mg/L, calcium and magnesium ion concentration 8000 mg/L) with concentration of 1800 mg/L by Haake rheometer at 95 deg.C for 7.34s-1The apparent viscosity at this time, the thermal stability of an aqueous polymer salt solution of 1800 mg/L concentration after aging for 45 days at 95 ℃ in the absence of oxygen as measured by Q/SH1020, the apparent viscosity of an aqueous polymer salt solution of 1800 mg/L concentration after shearing at 2000 rpm for half an hour and standing for 24 hours as measured by a Haake rheometer, the hydrophobic association being measured by a model TX-500 rotameter, produced by the university of Texas USAInterfacial tension between type acrylamide copolymer and Pu 2-529 produced oil. The results of the above analysis are shown in table 1.
[ example 4 ]
1. Synthesis of hydrophobic monomer:
under the protection of nitrogen, 8.5g of sulfur trioxide and 6m of L pyridine are stirred and uniformly dissolved in a glass reaction kettle filled with 85m of L glacial acetic acid at room temperature, 8.2g of acrylonitrile is slowly added dropwise into the mixed solution, 25g of 2, 6-dimethyl-4-dodecyl- α -methyl styrene is added dropwise, the mixture is continuously stirred and reacts for 4 hours at the temperature of 33 ℃, 300m of L deionized water is introduced, the mixture is stirred uniformly, kept stand, filtered, washed and dried to obtain the hydrophobic monomer N- (2- (2 ', 6 ' -dimethyl-4 ' -dodecylphenyl)) isopropylacrylamide, and the yield is 94.1%.
2. Synthesis of hydrophobic association type acrylamide polymer:
72g of white oil, 27.5g of sorbitan monooleate, 12g of octylphenol polyoxyethylene ether (10) and 1.59g N- (2- (2 ', 6 ' -dimethyl-4 ' -dodecylphenyl)) isopropylacrylamide monomer were added to the reaction kettle and stirred to be mixed uniformly, the temperature in the kettle was controlled to 36 ℃ and the stirring rate was 310 rpm. Adding 58g of water, 72g of acrylamide, 5g of N-vinyl pyrrolidone, 0.2g of ethylene diamine tetraacetic acid, 0.25g of isopropanol and 2.2g of ammonium persulfate into a batching kettle, stirring to dissolve the materials uniformly, and adjusting the pH value to 9.8 by using NaOH; in addition, 1.2g of sodium thiosulfate was dissolved in 10g of deionized water for use. Introducing the water phase into a reaction kettle, stirring to fully emulsify the water phase, adding 6g of sodium thiosulfate aqueous solution, raising the temperature of the system to 65 ℃, setting the temperature of the reaction kettle to be 70 ℃, continuing to react for 2 hours, and performing emulsion breaking, precipitation, washing, drying and other post-treatment methods after the reaction is ended to obtain the hydrophobic association ternary acrylamide copolymer.
The structure and performance of the hydrophobically associating acrylamide copolymer are tested by the following method or standard, namely, the solid content of the polymer is measured according to the solid content method of GB/T12005.2-89 polyacrylamide, the intrinsic viscosity of the polymer is measured according to the molecular weight (viscosity method) of GB/T12005.10-92 polyacrylamide, and the intrinsic viscosity is measured according to [ η ]]＝3.73×10-4Mw 0.66Calculating molecular weight, and testing polymer saline solution (total mineralization degree 150000 mg/L, calcium and magnesium ion concentration 8000 mg/L) with concentration of 1800 mg/L by Haake rheometer at 95 deg.C for 7.34s-1The apparent viscosity at 95 ℃ after aging for 45 days in the absence of oxygen as measured by Q/SH1020 for an aqueous polymer salt solution at a concentration of 1800 mg/L, the apparent viscosity of an aqueous polymer salt solution at a concentration of 1800 mg/L after shearing at 2000 rpm for half an hour and then allowing the solution to stand for 24 hours as measured by a Haake rheometer, the interfacial tension between the hydrophobically associative acrylamide copolymer and the oils produced by Pu 2-529 was measured by a TX-500 rotary drop interfacial tension tester, a university of Texas USA, and the results of the above analyses are shown in Table 1.
[ example 5 ]
The procedure for the synthesis of the hydrophobic monomer and the preparation of the hydrophobically associating acrylamide copolymer were the same as in example 4 except that the amount of N- (2- (2 ', 6 ' -dimethyl-4 ' -dodecylphenyl)) isopropylacrylamide monomer was reduced to 0.89g, and the structure and properties of the hydrophobically associating acrylamide copolymer were determined by measuring the solid content of the polymer by the method of GB/T12005.2-89 polyacrylamide solid content, measuring the intrinsic viscosity of the polymer by the method of GB/T12005.10-92 polyacrylamide molecular weight (viscometry), and determining the intrinsic viscosity of the polymer by the method of [ η ]]＝3.73×10-4Mw 0.66Calculating molecular weight, and testing polymer saline solution (total mineralization degree 150000 mg/L, calcium and magnesium ion concentration 8000 mg/L) with concentration of 1800 mg/L by Haake rheometer at 95 deg.C for 7.34s-1The apparent viscosity at 95 ℃ after aging for 45 days in the absence of oxygen as measured by Q/SH1020 for an aqueous polymer salt solution at a concentration of 1800 mg/L, the apparent viscosity of an aqueous polymer salt solution at a concentration of 1800 mg/L after shearing at 2000 rpm for half an hour and then allowing the solution to stand for 24 hours as measured by a Haake rheometer, the interfacial tension between the hydrophobically associative acrylamide copolymer and the oils produced by Pu 2-529 was measured by a TX-500 rotary drop interfacial tension tester, a university of Texas USA, and the results of the above analyses are shown in Table 1.
[ example 6 ]
Synthesis reaction process of hydrophobic monomer and hydrophobic associationAcrylamide copolymers were prepared as in example 4 except that the amount of N- (2- (2 ', 6 ' -dimethyl-4 ' -dodecylphenyl)) isopropylacrylamide monomer was reduced to 1.24g and the resulting hydrophobically associating acrylamide copolymers were tested for structure and properties by measuring the solids content of the polymer using the GB/T12005.2-89 polyacrylamide solids content method, by measuring the intrinsic viscosity of the polymer using the GB/T12005.10-92 polyacrylamide molecular weight (viscometry), and by measuring the intrinsic viscosity of the polymer using the η standard]＝3.73×10-4Mw 0.66Calculating molecular weight, and testing polymer saline solution (total mineralization degree 150000 mg/L, calcium and magnesium ion concentration 8000 mg/L) with concentration of 1800 mg/L by Haake rheometer at 95 deg.C for 7.34s-1The apparent viscosity at 95 ℃ after aging for 45 days in the absence of oxygen as measured by Q/SH1020 for an aqueous polymer salt solution at a concentration of 1800 mg/L, the apparent viscosity of an aqueous polymer salt solution at a concentration of 1800 mg/L after shearing at 2000 rpm for half an hour and then allowing the solution to stand for 24 hours as measured by a Haake rheometer, the interfacial tension between the hydrophobically associative acrylamide copolymer and the oils produced by Pu 2-529 was measured by a TX-500 rotary drop interfacial tension tester, a university of Texas USA, and the results of the above analyses are shown in Table 1.
[ COMPARATIVE EXAMPLE 1 ]
110g of acrylamide and 20g of 2-acrylamido-2-methylpropanesulfonic acid are dissolved in 260g of deionized water, adding 0.30g of disodium ethylene diamine tetraacetate, stirring and dissolving uniformly, adjusting the pH value to 7.7 by using a sodium hydroxide aqueous solution with the mass concentration of 1% and a hydrochloric acid solution with the mass concentration of 1%, adjusting the temperature of a constant-temperature water bath to 28 ℃, introducing high-purity nitrogen to remove oxygen, adding 20g of an ammonium persulfate aqueous solution with the mass concentration of 0.3% and 24g of sodium bisulfite with the mass concentration of 0.25% after 30 minutes, stirring and initiating a polymerization reaction, reacting for 3 hours, heating the water bath to 46 ℃, continuing to react for 2 hours to obtain a gel-like polymerization product, cutting the gel, adding 50g of sodium hydroxide aqueous solution with the mass concentration of 8 percent, hydrolysis reaction at 90 deg.c for 2 hr, vacuum drying at 75 deg.c for 8 hr, crushing, sieving and sampling for analysis.
The structure and properties of the resulting acrylamide copolymers were tested using the following methods or standards: according to GB-Measuring solid content of polymer by T12005.2-89 polyacrylamide solid content method, measuring intrinsic viscosity of polymer by GB/T12005.10-92 polyacrylamide molecular weight (viscosity method), and measuring by [ η ]]＝3.73×10-4Mw 0.66Calculating molecular weight, and testing polymer saline solution (total mineralization degree 150000 mg/L, calcium and magnesium ion concentration 8000 mg/L) with concentration of 1800 mg/L by Haake rheometer at 95 deg.C for 7.34s-1The apparent viscosity at 95 ℃ after aging for 45 days in the absence of oxygen as measured by Q/SH1020 for an aqueous polymer salt solution at a concentration of 1800 mg/L, the apparent viscosity of an aqueous polymer salt solution at a concentration of 1800 mg/L after shearing at 2000 rpm for half an hour and then allowing the solution to stand for 24 hours as measured by a Haake rheometer, the interfacial tension between the hydrophobically associative acrylamide copolymer and the oils produced by Pu 2-529 was measured by a TX-500 rotary drop interfacial tension tester, a university of Texas USA, and the results of the above analyses are shown in Table 1.
[ COMPARATIVE EXAMPLE 2 ]
72g of acrylamide, 5g N-vinylpyrrolidone, 1.59g of N- (2- (2 ', 6 ' -dimethyl-4 ' -dodecylphenyl)) isopropylacrylamide prepared in example 4, 23g of sodium dodecylbenzenesulfonate and 0.6g of disodium ethylenediaminetetraacetate were dissolved in 180g of deionized water, and after stirring and dissolving them uniformly, the pH was adjusted to 8.0 with a 1% by mass aqueous solution of sodium hydroxide and a 1% by mass hydrochloric acid solution, the temperature of a constant-temperature water bath was adjusted to 30 ℃, high-purity nitrogen gas was introduced to remove oxygen, after 30 minutes, 20g of a 0.28% by mass aqueous solution of ammonium persulfate and 20g of 0.2% by mass sodium bisulfite were added, and polymerization was initiated with stirring for 4 hours, the temperature of the water bath was raised to 50 ℃, and the reaction was continued for 1.5 hours to obtain a gel-like polymer product, cutting, vacuum drying at 75 deg.C for 10 hr, pulverizing, sieving, and sampling for analysis.
The structure and performance of the hydrophobically associating acrylamide copolymer are tested by the following method or standard, namely, the solid content of the polymer is measured according to the solid content method of GB/T12005.2-89 polyacrylamide, the intrinsic viscosity of the polymer is measured according to the molecular weight (viscosity method) of GB/T12005.10-92 polyacrylamide, and the intrinsic viscosity is measured according to [ η ]]＝3.73×10-4Mw 0.66Calculating molecular weight, and testing polymer saline solution (total mineralization degree 150000 mg/L, calcium and magnesium ion concentration 8000 mg/L) with concentration of 1800 mg/L by Haake rheometer at 95 deg.C for 7.34s-1The apparent viscosity at 95 ℃ after aging for 45 days in the absence of oxygen as measured by Q/SH1020 for an aqueous polymer salt solution at a concentration of 1800 mg/L, the apparent viscosity of an aqueous polymer salt solution at a concentration of 1800 mg/L after shearing at 2000 rpm for half an hour and then allowing the solution to stand for 24 hours as measured by a Haake rheometer, the interfacial tension between the hydrophobically associative acrylamide copolymer and the oils produced by Pu 2-529 was measured by a TX-500 rotary drop interfacial tension tester, a university of Texas USA, and the results of the above analyses are shown in Table 1.
[ COMPARATIVE EXAMPLE 3 ]
75g of n-heptane, 27.5g of dodecyl alcohol polyoxyethylene ether (3), 7.5g of octyl phenol polyoxyethylene ether (4) and 0.49g N- (1, 1, 3, 3-tetramethylbutyl) acrylamide monomer (prepared according to the method in CN 1891725A) are added into a reaction kettle and stirred to be uniformly mixed, the temperature in the kettle is controlled to be 25 ℃, and the stirring speed is 255 rpm. Adding 42g of deionized water, 55g of acrylamide, 10g of 2-acrylamido-2-methylpropanesulfonic acid, 0.15g of disodium ethylene diamine tetraacetate, 0.88g of tert-butyl alcohol and 1.5g of sodium persulfate into a batching kettle, stirring to uniformly dissolve the materials, and adjusting the pH value to 7.9 by using NaOH; in addition, 2g of sodium sulfite was dissolved in 15g of deionized water for use. Introducing the water phase into a reaction kettle, stirring to fully emulsify the water phase, adding 5g of sodium sulfite aqueous solution, raising the temperature of the system to 83 ℃, setting the temperature of the reaction kettle to be 60 ℃, continuing to react for 3 hours, and performing emulsion breaking, precipitation, washing, drying and other post-treatment methods after the reaction is ended to obtain the hydrophobic association ternary acrylamide copolymer.
The structure and performance of the hydrophobically associating acrylamide copolymer are tested by the following method or standard, namely, the solid content of the polymer is measured according to the solid content method of GB/T12005.2-89 polyacrylamide, the intrinsic viscosity of the polymer is measured according to the molecular weight (viscosity method) of GB/T12005.10-92 polyacrylamide, and the intrinsic viscosity is measured according to [ η ]]＝3.73×10-4Mw 0.66Calculating molecular weight, and measuring 1800 mg/L concentration polymer saline solution (total mineralization 150000 mg/L, calcium magnesium) by Haake rheometerIon concentration 8000 mg/L) at 95 deg.C for 7.34s-1The apparent viscosity at 95 ℃ after aging for 45 days in the absence of oxygen as measured by Q/SH1020 for an aqueous polymer salt solution at a concentration of 1800 mg/L, the apparent viscosity of an aqueous polymer salt solution at a concentration of 1800 mg/L after shearing at 2000 rpm for half an hour and then allowing the solution to stand for 24 hours as measured by a Haake rheometer, the interfacial tension between the hydrophobically associative acrylamide copolymer and the oils produced by Pu 2-529 was measured by a TX-500 rotary drop interfacial tension tester, a university of Texas USA, and the results of the above analyses are shown in Table 1.
[ COMPARATIVE EXAMPLE 4 ]
75g of n-heptane, 27.5g of lauryl alcohol polyoxyethylene ether (3), 7.5g of octyl phenol polyoxyethylene ether (4) and 0.49g of n-butyl styrene are added into a reaction kettle and stirred to be uniformly mixed, the temperature in the kettle is controlled to be 25 ℃, and the stirring speed is 255 revolutions per minute. Adding 42g of deionized water, 55g of acrylamide, 10g of 2-acrylamido-2-methylpropanesulfonic acid, 0.15g of disodium ethylene diamine tetraacetate, 0.88g of tert-butyl alcohol and 1.5g of sodium persulfate into a batching kettle, stirring to uniformly dissolve the materials, and adjusting the pH value to 7.9 by using NaOH; in addition, 2g of sodium sulfite was dissolved in 15g of deionized water for use. Introducing the water phase into a reaction kettle, stirring to fully emulsify the water phase, adding 5g of sodium sulfite aqueous solution, raising the temperature of the system to 80 ℃, setting the temperature of the reaction kettle to be 60 ℃, continuing to react for 3 hours, and performing emulsion breaking, precipitation, washing, drying and other post-treatment methods after the reaction is ended to obtain the hydrophobic association ternary acrylamide copolymer.
The structure and performance of the hydrophobically associating acrylamide copolymer are tested by the following method or standard, namely, the solid content of the polymer is measured according to the solid content method of GB/T12005.2-89 polyacrylamide, the intrinsic viscosity of the polymer is measured according to the molecular weight (viscosity method) of GB/T12005.10-92 polyacrylamide, and the intrinsic viscosity is measured according to [ η ]]＝3.73×10-4Mw 0.66Calculating molecular weight, and testing polymer saline solution (total mineralization degree 150000 mg/L, calcium and magnesium ion concentration 8000 mg/L) with concentration of 1800 mg/L by Haake rheometer at 95 deg.C for 7.34s-1Apparent viscosity at 95 ℃ and thermal stability after aging for 45 days at an oxygen-free temperature of 1800 mg/L concentration in an aqueous polymer salt solution according to Q/SH1020Properties, apparent viscosity of an aqueous polymer salt solution having a concentration of 1800 mg/L after shearing at 2000 rpm for half an hour and standing for 24 hours, measured by a Hack rheometer, interfacial tension between the hydrophobically-associating acrylamide copolymer and the Pu 2-529 produced oil was measured by a TX-500 type rotary drop interfacial tension meter, produced by the university of Texas, the results of the above analyses are shown in Table 1.
TABLE 1
Claims (8)
1. A hydrophobic association acrylamide copolymer oil displacement agent is obtained by copolymerizing acrylamide, a temperature-resistant salt-resistant monomer and a hydrophobic monomer;
the temperature-resistant salt-resistant monomer is selected from at least one of N-isopropylacrylamide, N-methylolacrylamide, N-N-dimethylacrylamide, N-vinylpyridine, N-vinylpyrrolidone, vinylsulfonic acid, vinylbenzenesulfonic acid, allylsulfonic acid, allylbenzenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and/or alkali metal salts and ammonium salts thereof, dimethylethylallylammonium chloride, dimethyldiallylammonium chloride, acryloyloxyethyltrimethyl ammonium chloride, acryloyloxyethyldimethylethylammonium bromide, methacryloyloxyethyltrimethylammonium chloride and 2-acrylamido-2-methylpropyltrimethyl ammonium chloride;
the molecular weight of the hydrophobically associating acrylamide copolymer is 50000-15000000, and the mass ratio of the hydrophobic monomer, the temperature-resistant salt-resistant monomer and the acrylamide is 0-2: 0 to 18: 80-99, wherein the amount of the hydrophobic monomer and the temperature-resistant salt-resistant monomer is not 0;
the acrylamide, the temperature-resistant salt-resistant monomer and the hydrophobic monomer are subjected to polymerization reaction in a reverse microemulsion under the action of a redox initiator to prepare the hydrophobic association acrylamide copolymer;
and (3) synthesizing the hydrophobic monomer:
under the protection of nitrogen, stirring 8.5g of sulfur trioxide and 6m of L pyridine at room temperature, uniformly dissolving in a glass reaction kettle filled with 85m of L glacial acetic acid, slowly dropwise adding 8.2g of acrylonitrile into the mixed solution, dropwise adding 25g of 2, 6-dimethyl-4-dodecyl- α -methylstyrene, continuously stirring and reacting for 4 hours at 33 ℃, introducing 300m of L deionized water, uniformly stirring, standing, filtering, washing with water, and drying to obtain the hydrophobic monomer.
2. The hydrophobically associative acrylamide copolymer according to claim 1, wherein the inverse microemulsion comprises the following components in parts by weight: 1) 15-70 parts of an oily solvent; 2) 2-20 parts of an emulsifier and/or a co-emulsifier; 3) 0.001-10 parts of a hydrophobic monomer; 4) 10-70 parts of acrylamide; 5) 1-50 parts of a temperature-resistant salt-resistant monomer; 6) 10-60 parts of water.
3. The hydrophobically associative acrylamide copolymer according to claim 2, wherein the oily solvent is at least one selected from cyclohexane, hexane, heptane, octane, isooctane, benzene, toluene, ethylbenzene, xylene, cumene, liquid paraffin, white oil, gasoline, diesel oil and kerosene.
4. The hydrophobically associating acrylamide copolymer according to claim 2, wherein the emulsifier is at least one selected from span, tween, alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ethers, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, dodecyl trimethyl quaternary ammonium salt, didodecyl dimethyl quaternary ammonium salt, hexadecyl trimethyl quaternary ammonium salt, dihexadecyl dimethyl quaternary ammonium salt, octadecyl trimethyl quaternary ammonium salt, and dioctadecyl dimethyl quaternary ammonium salt.
5. The hydrophobically associating acrylamide copolymer according to claim 2, wherein the co-emulsifier is selected from ethanol, propanol, isopropanol, n-butanol, isobutanol, t-butanol, pentanol, hexanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, glycerol, sodium formate, potassium formate, ammonium formate, sodium acetate, potassium acetate, ammonium acetate, sodium adipate, sodium malonate in an amount of 0.01 to 10wt% based on the amount of emulsifier.
6. The hydrophobically associative acrylamide copolymer according to claim 1, characterized in that the redox initiator is composed of an oxidizing agent and a reducing agent; the oxidant is at least one of ammonium persulfate, potassium persulfate, sodium persulfate and hydrogen peroxide; the reducing agent is selected from at least one of sodium bisulfite, potassium bisulfite, sodium sulfite, potassium sulfite, sodium thiosulfate and ferrous chloride; the mass ratio of the oxidant to the reducing agent is 0.1-8: 1, the total amount of the monomer is 0.001-2% of the total weight of the monomer.
7. A method for preparing the hydrophobically associating acrylamide copolymer as described in any one of claims 1 to 6, which comprises the steps of:
1) preparing a hydrophobic monomer, namely stirring 8.5g of sulfur trioxide and 6m L pyridine at room temperature under the protection of nitrogen, uniformly dissolving the sulfur trioxide and the 6m L pyridine in a glass reaction kettle filled with 85m L glacial acetic acid, slowly dropwise adding 8.2g of acrylonitrile into the mixed solution, dropwise adding 25g of 2, 6-dimethyl-4-dodecyl- α -methylstyrene, continuously stirring at 33 ℃ and reacting for 4 hours, introducing 300m L deionized water, stirring uniformly, standing, filtering, washing with water, and drying to obtain the hydrophobic monomer;
2) preparation of a water phase: dissolving acrylamide, a temperature-resistant salt-resistant monomer and an oxidant in water accounting for 90-99.9% of the total weight of the water, and adjusting the pH value of the solution to 7-12 by using an alkaline solution; dissolving a reducing agent separately in the balance of water;
3) preparing the microemulsion: dissolving an emulsifier and/or a co-emulsifier and a hydrophobic monomer in an oily solvent, adding the water phase prepared in the step 2) into the oil phase, and stirring to obtain a transparent or semitransparent reverse microemulsion;
4) inverse microemulsion polymerization: introducing inert gas into the reverse-phase microemulsion obtained in the step 3) to remove oxygen, adding the reducing agent aqueous solution prepared in the step 2), uniformly mixing, initiating a polymerization reaction at 5-45 ℃, and continuing the reaction for 0.5-6 hours after the exothermic peak temperature appears to obtain a transparent or semitransparent hydrophobic association acrylamide copolymer microemulsion; and carrying out post-treatment to obtain the hydrophobically associating acrylamide copolymer.
8. Use of the hydrophobically associating acrylamide copolymer according to any one of claims 1 to 6 in oil recovery in oil fields.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510684113.2A CN106589232B (en) | 2015-10-20 | 2015-10-20 | Hydrophobic association acrylamide copolymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510684113.2A CN106589232B (en) | 2015-10-20 | 2015-10-20 | Hydrophobic association acrylamide copolymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106589232A CN106589232A (en) | 2017-04-26 |
| CN106589232B true CN106589232B (en) | 2020-08-07 |
Family
ID=58555200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510684113.2A Active CN106589232B (en) | 2015-10-20 | 2015-10-20 | Hydrophobic association acrylamide copolymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106589232B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108676120B (en) * | 2018-05-30 | 2020-08-18 | 四川奥赛德材料科技有限公司 | Reverse microemulsion thickening agent for online fracturing construction and preparation method thereof |
| CN109369841A (en) * | 2018-10-26 | 2019-02-22 | 天津大港油田滨港集团博弘石油化工有限公司 | A kind of multifunction surface active polyacrylamide and its synthetic method |
| CN115772243B (en) * | 2021-09-06 | 2024-02-13 | 中国石油化工股份有限公司 | Tackifier for solid-free drilling fluid and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4727110A (en) * | 1984-04-19 | 1988-02-23 | Union Carbide Corporation | Process for the polymerization of shear-stable water-in-oil emulsions |
| CN1861654A (en) * | 2006-04-27 | 2006-11-15 | 西南石油学院 | Water soluble amphoteric ion copolymer and preparation process thereof |
| CN103539946A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Hydrophobic polymer graft modified acrylamide polymer and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1256650B (en) * | 1965-08-07 | 1967-12-21 | Dr Dieter Arlt | Process for the preparation of N-acylated 2-amino-alkane-sulfonic acid- (1) or of 2-amino-alkane-sulfonic acid- (1) |
| US3506707A (en) * | 1968-02-01 | 1970-04-14 | Lubrizol Corp | Preparation of acrylamidoalkanesulfonic acids |
| WO2012061147A1 (en) * | 2010-10-25 | 2012-05-10 | Isp Investments Inc. | Salt-tolerant, thermally-stable rheology modifiers |
| CN104558403B (en) * | 2013-10-28 | 2016-09-07 | 中国石油化工股份有限公司 | Crosslinking gradual change swellable polymer microballoon and preparation method thereof |
-
2015
- 2015-10-20 CN CN201510684113.2A patent/CN106589232B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4727110A (en) * | 1984-04-19 | 1988-02-23 | Union Carbide Corporation | Process for the polymerization of shear-stable water-in-oil emulsions |
| CN1861654A (en) * | 2006-04-27 | 2006-11-15 | 西南石油学院 | Water soluble amphoteric ion copolymer and preparation process thereof |
| CN103539946A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Hydrophobic polymer graft modified acrylamide polymer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106589232A (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106866881B (en) | hydrophobic association acrylamide polymer emulsion and preparation method thereof | |
| CN106589227B (en) | High-temperature high-salinity oil reservoir polyacrylamide oil displacement agent and preparation method thereof | |
| CN106867496B (en) | Online injection type oil displacement agent containing hydrophobically associating polymer emulsion and preparation method thereof | |
| CN109705834B (en) | Composition, temperature-resistant salt-resistant fracturing fluid thickening agent prepared from composition and preparation method of thickening agent | |
| KR100668023B1 (en) | Method for Making Hydrophobically Associative Polymers, Methods of Use and Compositions | |
| US4709759A (en) | Enhanced oil recovery with hydrophobically associating polymers containing N-vinyl-pyrrolidone functionality | |
| CN101492515B (en) | Acrylic amide modified graft copolymer, preparation method and application thereof | |
| CN101463116A (en) | Non-linear associating water-soluble quadripolymer, and preparation and use thereof | |
| CN103666433B (en) | Oil-displacing agent composition used for improving recovery ratio of high-temperature reservoir and preparation method of composition | |
| CN112898488B (en) | Polysaccharide modified salt-resistant resistance-reducing agent for shale gas fracturing fluid and preparation method thereof | |
| CN106589232B (en) | Hydrophobic association acrylamide copolymer and preparation method thereof | |
| CN104650301A (en) | Acrylamide copolymer and its preparation method and use | |
| CN113321764A (en) | Acid liquor thickener and preparation method and application thereof | |
| CN115572347A (en) | High-temperature-resistant high-salt-resistant tackifying and shearing-improving agent for water-based drilling fluid and preparation method and application thereof | |
| CN106590597A (en) | High-temperature high-mineralization-degree oil displacement agent composition for oil reservoirs and preparation method thereof | |
| CN106590591A (en) | Oil displacement agent composition used for oil recovery, and preparation method thereof | |
| CA2842705A1 (en) | Amphiphilic macromolecule and use | |
| CN104628940A (en) | Acrylamide copolymer, as well as preparation method and application thereof | |
| CN106589224A (en) | Hydrophobically associating polymer for oil displacement in high temperature and salinity reservoir and synthetic method | |
| CN110790862B (en) | Acrylamide copolymer and preparation method and application thereof | |
| CN110790859B (en) | Acrylamide copolymer and preparation method and application thereof | |
| CN105566515A (en) | Structure-oriented composite initiator system and acrylamide polymer and preparation method and application thereof | |
| CN104628943A (en) | Acrylamide copolymer, as well as preparation method and application thereof | |
| CN110790861B (en) | Acrylamide copolymer and preparation method and application thereof | |
| CN110790860B (en) | Acrylamide copolymer and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |