CN115073673B - Polymer and double water phase preparation method and application thereof - Google Patents

Polymer and double water phase preparation method and application thereof Download PDF

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CN115073673B
CN115073673B CN202110267439.0A CN202110267439A CN115073673B CN 115073673 B CN115073673 B CN 115073673B CN 202110267439 A CN202110267439 A CN 202110267439A CN 115073673 B CN115073673 B CN 115073673B
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acrylamide
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sodium
phase preparation
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CN115073673A (en
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薛俊杰
孙粉锦
陈艳鹏
管保山
东振
陈姗姗
张梦媛
陈浩
张金华
郑元超
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/04—Azo-compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
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    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

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Abstract

The invention provides a polymer and a double water phase preparation method and application thereof. The invention also provides a polymer which is prepared by the preparation method. The invention further provides application of the polymer in fracturing of coal-bed gas wells and shale gas wells. The preparation method provided by the invention does not need to introduce an organic solvent, can control the polymerization reaction at one time by utilizing the polymerization initiation mode of ultraviolet irradiation, has simple process and low cost, and the prepared polymer has higher hydration capacity, solubility and salt resistance.

Description

Polymer and double water phase preparation method and application thereof
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a polymer and a double water phase preparation method and application thereof.
Background
In petroleum development resources in China, a large part of oil fields cannot be established with special large-scale injection and polymerization workstations and space-free pendulum amplification type injection allocation equipment, such as offshore oil fields or long-day oil fields, due to the limitations of platform space, operation environment, hoisting capacity and the like. Therefore, mature polymer injection allocation process technology and equipment which are similar to those which are widely popularized in Daqing are difficult to be applied to oil fields with relatively limited land areas. In order to realize smooth polymer injection work of long-day oil fields and offshore oil fields, through technical attack, a double-aqueous-phase polymer material without constructing an injection allocation system is developed, and the material can realize co-injection, maximally compress the quantity of ground equipment, reduce the equipment construction cost and effectively utilize the space occupation area.
On the other hand, most of the traditional online mixed polymers are inverse emulsion polymers, namely water-in-oil emulsion polymers, which take an oil phase as a continuous phase, wrap polyacrylamide dissolved in water as a disperse phase, and have the appearance of milk-like milky flowing liquid. Compared with the traditional dry powder polymer, the emulsion polymer has the characteristics of high dissolution speed, high conversion rate and the like. However, in the hypersalinity operation, calcium and magnesium ions greatly reduce the oil-water interfacial tension of the emulsifier, so that the stability of the emulsion is greatly reduced, the emulsion is obviously layered, the emulsion is represented by an upper oil/emulsion layer and a lower polymer layer, and the stratum is seriously blocked, so that secondary injury is caused.
Disclosure of Invention
In order to solve the above problems, the present invention is directed to a polymer, and a method for preparing a double aqueous phase and an application thereof. The polymer is synthesized in the water phase through ultraviolet ion polymerization without adding an organic solvent in the preparation process of the polymer, and the prepared polymer has good solubility and salt resistance, and has higher viscosity retention rate and hydration capacity under the condition of high mineralization.
In order to achieve the above object, the present invention provides a method for preparing a polymer, which comprises mixing a water-soluble anionic dispersion stabilizer, polyethylene glycol, a propionamide monomer, an acrylamide n-alkyl sulfonate, a chelating agent, a photoinitiator and a composite initiator in water in an oxygen-isolated atmosphere to obtain a reaction solution, and reacting the reaction solution by ultraviolet irradiation to obtain the polymer.
In a specific embodiment of the present invention, the molar ratio of the water-soluble anionic dispersion stabilizer, polyethylene glycol, propionamide monomer, acrylamide n-alkyl sulfonate, chelating agent, photoinitiator and composite initiator is (30-50): (30-70): (20-50): (20-50): (0.1-0.5): (1-5): (0.1-0.2).
In a specific embodiment of the present invention, the temperature of the reaction is generally controlled to be 15-20 ℃, the time of the illumination is generally controlled to be 10-20min, and the irradiation wave band of the illumination is generally selected to be UVA-340 (), namely, 340nm ultraviolet is adopted for irradiation).
In a specific embodiment of the present invention, the sum of the mass concentration of the photoinitiator and the mass concentration of the chelating agent in the reaction solution is generally 0.05 to 0.1%, and the mass concentration of the complex initiator in the reaction solution is generally 0.05 to 0.1%.
In particular embodiments of the present invention, the water-soluble anionic dispersion stabilizer may include an anionic oligomer. The weight average molecular weight of the anionic oligomer may be 200-600 Da.
In particular embodiments of the present invention, the anionic oligomer is generally formed from the copolymerization of nonionic monomers with anionic monomers. The molar ratio of the nonionic monomer to the anionic monomer can be controlled to be 2:8 to 5:5, e.g., 3:7, 4:6, etc. The nonionic monomer may be an acrylamide-based monomer, for example, including one or a combination of two or more of acrylamide, methacrylamide, N-butoxymethacrylamide, (NBMA) N-isobutoxymethyl acrylamide (IBMA). The anionic monomers may include sodium acrylate and/or sodium 2-acrylamido-2-methylpropanesulfonate.
In a specific embodiment of the invention, the polyethylene glycol generally has a weight average molecular weight of 200Da to 4000Da. For example, the polyethylene glycol may comprise one or a combination of two or more of PEG-200, PEG-600, PEG-1000, PEG-1500, PEG-2000, PEG-4000.
In a specific embodiment of the present invention, the chelating agent preferably comprises ethylenediamine tetraacetic acid and/or disodium edetate.
In a specific embodiment of the present invention, the acrylamide-based monomer may include one or a combination of two or more of acrylamide, methacrylamide, N-butoxymethacrylamide, N-isobutoxymethyl acrylamide.
In a specific embodiment of the present invention, the acrylamido n-alkyl sulfonate may be acrylamido n-alkyl sodium sulfonate, and may include, for example, one or a combination of two or more of sodium 2-acrylamido-2-methylpropane sulfonate, sodium 2-acrylamidodecyl sulfonate (or: sodium 2-acrylamido 12-alkyl sulfonate), and sodium 2-acrylamido hexadecane sulfonate (or: sodium 2-acrylamido 16-alkane sulfonate).
The molecular formula of the 2-acrylamide-2-methylpropanesulfonic acid sodium is as follows:
the molecular formula of the 2-acrylamide-sodium dodecyl sulfonate is as follows:
the molecular formula of the 2-acrylamido hexadecane sodium sulfonate is as follows:
in a specific embodiment of the present invention, the preparation method of the sodium 2-acrylamido hexadecane sulfonate may be: sequentially adding 1-16 alkene and acrylonitrile in the same molar ratio (1:1), and dropwise adding fuming sulfuric acid in the same molar ratio through an addition funnel, wherein the temperature in the dropwise adding process is observed to be not higher than 5 ℃; stirring slowly for 45min at a stirring speed of 40rad/min, maintaining the temperature to room temperature, standing at a constant temperature for reaction for 25h, repeatedly flushing with anhydrous diethyl ether, and vacuum drying at 25 ℃ for 40h to obtain 2-sodium acrylamido hexadecane sulfonate.
In particular embodiments of the present invention, the photoinitiator may comprise one or a combination of two or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, alpha-hydroxyalkyl-benzophenone, alpha-aminoalkylacetophenone.
In a specific embodiment of the present invention, the composite initiator may include a molar ratio of (10-30): (20-40): (10-40): the persulfate, the bisulfite, the tertiary amine compound and the azo initiator of (1-40).
In the composite initiator, the persulfate can comprise ammonium persulfate [ (NH) 4 ) 2 S 2 O 8 ]Sodium persulfate (Na) 2 S 2 O 8 ) And potassium persulfate (K) 2 S 2 O 8 ) One or a combination of two or more of them; the bisulphite may comprise ammonium bisulphite (NH) 4 HSO 3 ) Sodium bisulphite (NaHSO) 3 ) And potassium hydrogen sulfite (KHSO) 3 ) One or a combination of two or more of them; the azo initiator can comprise azobisisobutyronitrile, azobisisobutyronitrile hydrochloride and dollOne or a combination of more than two of azodiisoheptonitrile and dimethyl azodiisobutyrate; the tertiary amine compound may include one or a combination of two or more of N, N-diethyl ethylenediamine, diethylenetriamine, N, N, N ', N' -tetraethylethylenediamine, N, N-diisopropyl ethylenediamine, N, N, N ', N' -tetramethyl ethylenediamine, N, N, N ', N' -tetraallyl ethylenediamine.
In a specific embodiment of the present invention, the pH of the reaction solution is generally controlled to 7.5 to 9. In some embodiments, the pH of the reaction solution may be adjusted using pH adjusting agents including sodium hydroxide, potassium carbonate, sodium bicarbonate, potassium bicarbonate, monoethanolamine [ HOCH ] 2 CH 2 NH 2 ]Diethanolamine [ (HOCH) 2 CH 2 ) 2 NH]Triethanolamine [ (HOCH) 2 CH 2 ) 3 N]And ammonia water (NH) 3 ·H 2 O) or a combination of two or more thereof.
In particular embodiments of the present invention, the oxygen barrier atmosphere may include nitrogen or the like.
In a specific embodiment of the present invention, the above preparation method may be:
1. mixing a water-soluble anionic dispersion stabilizer (which can be an anionic oligomer formed by copolymerizing a nonionic monomer and an anionic monomer) and polyethylene glycol in an oxygen-barrier atmosphere to form an intermediate solution;
2. maintaining an oxygen-isolation atmosphere, adding a photoinitiator, a chelating agent, a composite initiator, a propionamide monomer and acrylamide n-alkyl sodium sulfonate into the intermediate solution in the step 1, and initiating a reaction in a temperature environment of 15-20 ℃ by 340nm ultraviolet irradiation to obtain the polymer.
The invention also provides a polymer which is prepared by the preparation method. The weight average molecular weight of the polymer is typically 50-800 Da. The polymer is a polyacrylamide copolymer with a core-shell structure, and the core and the shell are both water phase components, namely a water-in-water system. In some embodiments, the outer coating of the polymer may be a water-soluble anionic dispersion stabilizer and polyethylene glycol, and the inner core may be an acrylamide-based copolymer. The above polymer has a high hydration ability as an acrylamide polymer under high mineralization conditions.
The invention further provides application of the polymer in fracturing of coal-bed gas wells and shale gas wells. The viscosity retention rate of the polymer under the hypersalinity can reach more than 85%, the dissolution time is within 1min, and the polymer has good salt resistance and solubility.
The invention has the beneficial effects that:
1. the dissolution time of the polymer provided by the invention under the condition of high mineralization is basically within 1min, and compared with the conventional emulsion acrylamide polymer, the dissolution speed of the polymer provided by the invention is greatly improved; in addition, the viscosity retention rate of the polymer under the high mineralization condition can reach more than 85%, and the polymer has good salt resistance.
2. Compared with the conventional preparation method of the water-in-oil acrylamide emulsion polymer, the preparation method of the polymer provided by the invention does not need to introduce an organic solvent, can greatly reduce the water treatment cost in the later period of production, and can avoid crude oil emulsification and stratum secondary pollution.
3. Compared with the conventional synthesis method of the dispersed acrylamide polymer, the preparation method of the polymer double-aqueous phase provided by the invention can control the copolymerization reaction at one time by utilizing the polymerization initiation mode of ultraviolet irradiation, does not need to add an initiator, adopts the process technologies of sectional temperature control and the like, and has the advantages of simple process operation, low cost and high safety.
Drawings
FIG. 1 is a graph showing the results of the infrared spectrum test in test example 1.
FIG. 2 is a TEM image of the product SX-I of test example 2.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
The present embodiment provides a polymer, the preparation method of which comprises:
1. in terms of mole parts, 30 parts of an oligomer of acrylamide and sodium acrylate (the weight average molecular weight of the oligomer is 300 Da, the mole ratio of the acrylamide to the sodium acrylate is 3:7) and 50 parts of polyethylene glycol (PEG-200) are put into a four-necked round bottom flask which is provided with mechanical stirring and nitrogen protection, distilled water is used for dissolution to obtain an intermediate solution, the solute mass concentration of the intermediate solution is controlled to be 30 wt%, the pH value of the intermediate solution is regulated to be 7.5, and the intermediate solution is stirred for 30 minutes under the condition of isolating oxygen.
2. 1 part of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone, 0.2 part of chelating agent ethylenediamine tetraacetic acid, stirring for 30min at an oxygen-isolation time, and then adding 20 parts of acrylamide monomer, 20 parts of 2-acrylamide-2-methylpropanesulfonic acid sodium and 0.1 part of compound initiator to obtain a reaction solution, wherein the total weight of the photoinitiator and the chelating agent accounts for 0.05wt% of the total weight of the reaction solution, the weight of the compound initiator accounts for 0.05wt% of the total weight of the reaction solution, and the compound initiator consists of N, N-diethyl ethylenediamine, azo diisoheptanenitrile, ammonium persulfate and sodium bisulphite in a molar ratio of 4:4:3:4.
3. The reaction solution is put into a constant temperature water bath with the temperature of 15 ℃, and is irradiated for 10 minutes at the temperature of 15 ℃ by utilizing 340nm ultraviolet light with the radiation wave band of UVA-340, and the obtained off-white emulsion is a polymer which is marked as a product SX-I.
Example 2
The present embodiment provides a polymer, the preparation method of which comprises:
1. 50 parts of an oligomer of methacrylamide and sodium 2-acrylamide-2-methylpropanesulfonate (the weight average molecular weight of the oligomer is 600 Da, the molar ratio of the methacrylamide to the sodium 2-acrylamide-2-methylpropanesulfonate is 2:8) and 50 parts of polyethylene glycol (PEG-4000) are put into a four-port round-bottom flask which is provided with mechanical stirring and nitrogen protection, and dissolved by distilled water to obtain an intermediate solution, the solute mass concentration of the intermediate solution is controlled to be 30 wt%, the pH value of the intermediate solution is regulated to be 9, and the intermediate solution is stirred for 60 minutes under oxygen isolation.
2. 1 part of photoinitiator alpha-aminoalkylacetophenone, 0.2 part of chelating agent ethylenediamine tetraacetic acid and stirring for 60 minutes in an oxygen-isolated manner are added into the intermediate solution, then 20 parts of N-butoxymethylacrylamide, 50 parts of acrylamide-based 12-alkyl sodium sulfonate and 0.2 part of compound initiator are added, and a reaction solution is obtained, wherein the total weight of the photoinitiator and the chelating agent accounts for 0.1wt% of the total weight of the reaction solution, the total weight of the compound initiator accounts for 0.1wt% of the total weight of the reaction solution, and the compound initiator consists of N, N-diisopropyl ethylenediamine, azobisisobutyronitrile, ammonium persulfate and potassium hydrogen sulfite in a molar ratio of 3:2:1:2.
3. The reaction solution is put into a constant temperature water bath with the temperature of 20 ℃, and is irradiated for 20 minutes at the temperature of 20 ℃ by utilizing 340nm ultraviolet light with the radiation wave band of UVA-340, and the obtained off-white emulsion is a polymer which is marked as a product SX-II.
Example 3
The present embodiment provides a polymer, the preparation method of which comprises:
1. in terms of mole parts, 40 parts of an oligomer of N-isobutoxymethyl acrylamide and sodium acrylate having a weight average molecular weight of 450 Da and a molar ratio of N-isobutoxymethyl acrylamide to sodium acrylate of 4:6 and 50 parts of polyethylene glycol (PEG-2000) were charged into a four-necked round bottom flask equipped with mechanical stirring and nitrogen protection, and dissolved with distilled water to obtain an intermediate solution having a solute mass concentration of 20wt.%, the intermediate solution was adjusted to pH 8 and stirred for 45 minutes under oxygen-exclusion.
2. 3 parts of photoinitiator alpha-aminoalkylacetophenone, 0.3 part of chelating agent ethylene diamine tetraacetic acid, stirring for 45min in an oxygen-isolated manner, and then adding 40 parts of N-isobutoxy methacrylamide, 40 parts of 2-acrylamide hexadecyl sodium sulfonate and 0.15 part of compound initiator to obtain a reaction solution, wherein the total weight of the photoinitiator and the chelating agent accounts for 0.07wt% of the total weight of the reaction solution, the total weight of the compound initiator accounts for 0.07wt% of the total weight of the reaction solution, and the compound initiator consists of N, N, N ', N' -tetramethyl ethylenediamine, dimethyl azodiisobutyrate, ammonium persulfate and potassium hydrogen sulfite in a molar ratio of 3:3:1:3.
3. The reaction solution is put into a constant temperature water bath with the temperature of 18 ℃, and is irradiated for 18 minutes at the temperature of 18 ℃ by utilizing 340nm ultraviolet light with the radiation wave band of UVA-340, and the obtained off-white emulsion is a polymer which is marked as a product SX-III.
Test example 1
The product SX-I prepared in example 1 was subjected to an infrared spectrum test, and the test results are shown in FIG. 1. In FIG. 1, 3442cm -1 Is free-NH 2 Characteristic absorption peaks; 3232cm -1 Is associated with-NH 2 Characteristic absorption peaks; 1666cm -1 At the characteristic absorption peak of carbonyl group, corresponding to amide I (c=o stretching vibration); 1089cm -1 Is sulfonic-SO 3 The S-O stretching vibration; 1241cm -1 The stretching vibration of C=O bond in the chain link of 2-acrylamide-2-methylpropanesulfonic acid sodium (AMPS-Na); 1489cm -1 Characteristic absorption peak for methylene deformation, 1417cm -1 The telescopic vibration of the C-OH bond of the alcohol hydroxyl is adopted. From the above infrared test results, it can be seen that the synthetic samples provided in example 1 are the copolymerization products of acrylamide, sodium 2-acrylamido-2-methylpropanesulfonate, acrylic acid, and polyethylene glycol.
Test example 2
TEM test was performed on the product SX-I prepared in example 1, and the results are shown in FIG. 2. As can be seen from fig. 2, the product is a spherical encapsulating polymer, with a thin shell outside, a solid core inside, and a spherical core-shell structure as a whole.
Test example 3
The basic physical properties such as weight average molecular weight, solid content and solubility of the products of examples 1 to 3 were measured by using a full-automatic molecular weight meter RPV-1 (2) -RA, julabo technology, germany, and the results are summarized in Table 1.
The method for testing the dissolution time and the solubility is carried out according to the national standard GB 12005.8-89 method for measuring the dissolution rate of powdery polyacrylamide.
TABLE 1
As can be seen from Table 1, the polymer obtained by the preparation method provided by the invention can be rapidly dissolved, the dissolution time is controlled within 1min, the polymer has good solubility, and the weight average molecular weight is between 50 and 800 Da.
Test example 4
The test example uses a Brookfield company LVDV-11 fully automatic viscometer, U.S.A., to simulate a total degree of mineralization of 4.5X10 for the products of examples 1-3 5 Apparent viscosity was tested in mg/L formation water.
The test conditions were: the polymer dissolved concentration was 0.5%, the mineralization was 20%, the stirring rate was 400rad/min, and the test temperature was 40 ℃. The test results are summarized in table 2. The viscosity retention in table 2 is the ratio of the apparent viscosity of the product in mineralized water to the apparent viscosity of the product in deionized water.
TABLE 2
Product(s) Apparent viscosity under deionized water/mPa . s Mineralized underwater apparent viscosity/mPa . s Viscosity retention/%
SX-I 23 20 86.9
SX-II 51 45 88.2
SX-III 38 34 89.5
As can be seen from Table 2, the retention rate of apparent viscosity of the polymers prepared in examples 1-3 in mineralized water is basically above 85%, which proves that the polymers provided by the invention have good salt resistance.

Claims (19)

1. The preparation method comprises the steps of mixing a water-soluble anionic dispersion stabilizer, polyethylene glycol, an acrylamide monomer, acrylamide n-alkyl sulfonate, a chelating agent, a photoinitiator and a composite initiator in water in an oxygen-isolated atmosphere to obtain a reaction solution, and carrying out a reaction through ultraviolet irradiation to obtain the polymer;
the mole ratio of the water-soluble anionic dispersion stabilizer, polyethylene glycol, propionamide monomer, acrylamide n-alkyl sulfonate, chelating agent, photoinitiator and composite initiator is (30-50): (30-70): (20-50): (20-50): (0.1-0.5): (1-5): (0.1-0.2);
the water-soluble anionic dispersion stabilizer comprises an anionic oligomer; the weight average molecular weight of the anionic oligomer is 200-600 Da;
the anionic oligomer is formed by copolymerizing a nonionic monomer and an anionic monomer; the molar ratio of the nonionic monomer to the anionic monomer is 2:8-5:5; the nonionic monomer comprises one or more than two of acrylamide, methacrylamide, N-butoxy methacrylamide and N-isobutoxy methacrylamide; the anionic monomer comprises sodium acrylate and/or sodium 2-acrylamide-2-methylpropanesulfonate;
the acrylamide n-alkyl sulfonate comprises one or more than two of sodium 2-acrylamide-2-methylpropanesulfonate, sodium 2-acrylamide dodecyl sulfonate and sodium 2-acrylamide hexadecyl sulfonate.
2. The aqueous two-phase preparation method according to claim 1, wherein the reaction temperature is 15-20 ℃, the illumination time is 10-20min, and the radiation wave band of the illumination is UVA-340.
3. The aqueous two-phase preparation method according to claim 1, wherein the sum of the mass concentration of the photoinitiator and the mass concentration of the chelating agent in the reaction solution is 0.05% -0.1%, and the mass concentration of the composite initiator in the reaction solution is 0.05% -0.1%.
4. The aqueous two-phase preparation method according to claim 1, wherein the polyethylene glycol has a weight average molecular weight of 200Da to 4000Da.
5. The method for preparing a two-aqueous phase according to claim 4, wherein the polyethylene glycol comprises one or more of PEG-200, PEG-600, PEG-1000, PEG-1500, PEG-2000, and PEG-4000.
6. The aqueous two-phase preparation method according to claim 1, wherein the chelating agent comprises ethylenediamine tetraacetic acid and/or ethylenediamine tetraacetic acid tetrasodium salt.
7. The aqueous two-phase production method according to claim 1, wherein the acrylamide-based monomer comprises one or a combination of two or more of acrylamide, methacrylamide, N-butoxymethacrylamide, and N-isobutoxymethyl acrylamide.
8. The aqueous two-phase preparation method according to claim 1, wherein the photoinitiator comprises one or a combination of more than two of 2-hydroxy-2-methyl-1-phenyl-1-propanone, alpha-hydroxyalkyl benzophenone and alpha-aminoalkylacetophenone.
9. The aqueous two-phase preparation method according to claim 1, wherein the complex initiator comprises a molar ratio of (10-30): (20-40): (10-40): the persulfate, the bisulfite, the tertiary amine compound and the azo initiator of (1-40).
10. The aqueous two-phase production method according to claim 9, wherein the persulfate includes one or a combination of two or more of ammonium persulfate, sodium persulfate, and potassium persulfate.
11. The aqueous two-phase production method according to claim 9, wherein the hydrogen sulfite comprises one or a combination of two or more of ammonium hydrogen sulfite, sodium hydrogen sulfite and potassium hydrogen sulfite.
12. The aqueous two-phase process according to claim 9, wherein the tertiary amine compound comprises N, N-diethyl ethylenediamine, diethylenetriamine, N, N, N ', N' -tetraethylethylenediamine, N, N-diisopropylethylenediamine, N, N, N ', N' -tetramethylethylenediamine, N, N, N ', N' -tetraallylethylenediamine, or a combination of two or more thereof.
13. The aqueous two-phase preparation method according to claim 9, wherein the azo initiator comprises one or a combination of two or more of azobisisobutyronitrile, azobisisobutyronitrile hydrochloride, azobisisoheptonitrile and dimethyl azobisisobutyrate.
14. The aqueous two-phase preparation method according to claim 1, wherein the reaction solution has a pH of 7.5 to 9.
15. The aqueous two-phase preparation method according to claim 14, wherein the pH adjustor for adjusting the pH of the reaction solution comprises one or a combination of two or more of sodium hydroxide, potassium carbonate, sodium bicarbonate, potassium bicarbonate, monoethanolamine, diethanolamine, triethanolamine and aqueous ammonia.
16. The aqueous two-phase preparation method according to claim 1, wherein the oxygen-barrier atmosphere comprises nitrogen.
17. A polymer prepared by the aqueous two-phase preparation method of any one of claims 1-16.
18. The polymer of claim 17, wherein the weight average molecular weight of the polymer is 782-800 Da.
19. Use of the polymer of claim 17 or 18 in coal-bed gas well, shale gas well fracturing construction.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104403054A (en) * 2014-11-27 2015-03-11 胜利油田胜利化工有限责任公司 Hydrophobic associated anionic polyacrylamide water-in-water emulsion and preparation method thereof
CN104974308A (en) * 2014-04-10 2015-10-14 中国石油化工股份有限公司 Resistance reducing agent for fracture and preparation method thereof
CN106749885A (en) * 2015-11-19 2017-05-31 北京熠海能源科技有限公司 A kind of preparation method and applications of nano-micro level water-in-water type microballoon profile control agent
CN107880212A (en) * 2017-11-02 2018-04-06 中国石油集团渤海钻探工程有限公司 A kind of water-in-water type emulsion for acid fracturing and preparation method thereof
CN110698605A (en) * 2019-10-22 2020-01-17 陕西科技大学 Preparation method of high-strength double-network hydrogel
CN111909306A (en) * 2020-08-14 2020-11-10 西安石油大学 Double-aqueous-phase PAM/AMPS nano microsphere latex as well as preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104974308A (en) * 2014-04-10 2015-10-14 中国石油化工股份有限公司 Resistance reducing agent for fracture and preparation method thereof
CN104403054A (en) * 2014-11-27 2015-03-11 胜利油田胜利化工有限责任公司 Hydrophobic associated anionic polyacrylamide water-in-water emulsion and preparation method thereof
CN106749885A (en) * 2015-11-19 2017-05-31 北京熠海能源科技有限公司 A kind of preparation method and applications of nano-micro level water-in-water type microballoon profile control agent
CN107880212A (en) * 2017-11-02 2018-04-06 中国石油集团渤海钻探工程有限公司 A kind of water-in-water type emulsion for acid fracturing and preparation method thereof
CN110698605A (en) * 2019-10-22 2020-01-17 陕西科技大学 Preparation method of high-strength double-network hydrogel
CN111909306A (en) * 2020-08-14 2020-11-10 西安石油大学 Double-aqueous-phase PAM/AMPS nano microsphere latex as well as preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
双水相共聚法制备阴离子聚丙烯酰胺稠化剂的研究;呼早霞;中国优秀硕士学位论文全文数据库 工程科学Ⅰ辑(第12期);B016-80 *

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