CN117106129A - Clean environment-friendly self-degradation inverse emulsion polymer and preparation method thereof - Google Patents
Clean environment-friendly self-degradation inverse emulsion polymer and preparation method thereof Download PDFInfo
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- CN117106129A CN117106129A CN202311043357.3A CN202311043357A CN117106129A CN 117106129 A CN117106129 A CN 117106129A CN 202311043357 A CN202311043357 A CN 202311043357A CN 117106129 A CN117106129 A CN 117106129A
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- 239000004908 Emulsion polymer Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000007281 self degradation Effects 0.000 title claims abstract description 12
- 239000012071 phase Substances 0.000 claims abstract description 97
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- -1 ester compound Chemical class 0.000 claims abstract description 7
- 239000008346 aqueous phase Substances 0.000 claims abstract description 6
- 239000000839 emulsion Substances 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 11
- 230000009471 action Effects 0.000 claims description 11
- 238000003760 magnetic stirring Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- HVUMOYIDDBPOLL-XGKPLOKHSA-N [2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XGKPLOKHSA-N 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- PQLMXFQTAMDXIZ-UHFFFAOYSA-N isoamyl butyrate Chemical compound CCCC(=O)OCCC(C)C PQLMXFQTAMDXIZ-UHFFFAOYSA-N 0.000 claims description 6
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 6
- 229920000053 polysorbate 80 Polymers 0.000 claims description 6
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 4
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 4
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 4
- MDHYEMXUFSJLGV-UHFFFAOYSA-N phenethyl acetate Chemical compound CC(=O)OCCC1=CC=CC=C1 MDHYEMXUFSJLGV-UHFFFAOYSA-N 0.000 claims description 4
- 229940094941 isoamyl butyrate Drugs 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 239000002562 thickening agent Substances 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- LRMHFDNWKCSEQU-UHFFFAOYSA-N ethoxyethane;phenol Chemical compound CCOCC.OC1=CC=CC=C1 LRMHFDNWKCSEQU-UHFFFAOYSA-N 0.000 claims description 2
- 229940095102 methyl benzoate Drugs 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 239000001587 sorbitan monostearate Substances 0.000 claims description 2
- 235000011076 sorbitan monostearate Nutrition 0.000 claims description 2
- 229940035048 sorbitan monostearate Drugs 0.000 claims description 2
- 229950004959 sorbitan oleate Drugs 0.000 claims description 2
- 229950011392 sorbitan stearate Drugs 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 10
- 239000012530 fluid Substances 0.000 abstract description 8
- 230000006378 damage Effects 0.000 abstract description 6
- 150000002148 esters Chemical class 0.000 abstract description 6
- 238000012688 inverse emulsion polymerization Methods 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 229920002401 polyacrylamide Polymers 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 238000011161 development Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 239000004530 micro-emulsion Substances 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 230000002269 spontaneous effect Effects 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 31
- 235000019198 oils Nutrition 0.000 description 29
- 239000000243 solution Substances 0.000 description 13
- 230000001276 controlling effect Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000010008 shearing Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013618 yogurt Nutrition 0.000 description 1
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- 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
- C09K8/62—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
- 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
- C08F2/32—Polymerisation in water-in-oil emulsions
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- 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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- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to the field of oil-gas field development, in particular to a clean environment-friendly self-degradation inverse emulsion polymer and a preparation method thereof. The technical proposal is as follows: dissolving a water-soluble monomer into water to prepare a water phase, and regulating the pH of the water phase to be neutral; adding an emulsifier into the environment-friendly dispersing agent to serve as a continuous phase; mixing the aqueous phase and the continuous phase, stirring at high speed to form inverse microemulsion, introducing nitrogen to remove oxygen, and slowly adding an initiator to initiate polymerization to obtain the clean environment-friendly self-degrading emulsion polymer. The clean environment-friendly self-degradation type inverse emulsion polymer prepared by adopting the inverse emulsion polymerization method realizes the spontaneous gel breaking of polyacrylamide, reduces the application of solvent oil and is cleaner and more environment-friendly. The continuous phase is applied with a degradable ester compound, the ester can be automatically degraded into alcohol and acid, and the application of the ester compound as fracturing fluid can be used for helping polymer gel breaking and reducing the water locking damage of external fluid to a reservoir.
Description
Technical Field
The invention relates to the field of oil-gas field development, in particular to a clean environment-friendly self-degradation inverse emulsion polymer and a preparation method thereof.
Background
Inverse emulsion polymerization is one of the ideal methods for obtaining high molecular weight polymers, playing an irreplaceable role in the preparation and application of polymeric materials. The liquid drop nucleation is a main mechanism of acrylamide inverse emulsion polymerization, and forms free radicals by utilizing monomers on an oil-water interface, diffuses and transfers the free radicals into a reaction core, and wraps hydrogel formed by polymerization in oily liquid drops to form inverse emulsion.
The quality of the emulsifier and the oil phase in the inverse emulsion polymerization process directly affects the size of the polymer particles and the polymerization efficiency, and thus the product quality. In the application document with publication number of CN101805423A, a preparation method of a polyacrylamide nano microsphere system is disclosed, which is characterized in that: the first step, mixing the oil-soluble solvent and the emulsifier uniformly, adding the water phase containing the acrylamide monomer, the cross-linking agent and the oxidant, fully stirring, introducing N2 to deoxidize, adding the reducing agent into the mixed system to initiate reaction, and continuing to react for 0.5-2 hours after the exothermic peak; and secondly, continuously adding a water phase containing acrylamide monomers, a cross-linking agent and an oxidant into the system, fully stirring, introducing N2 for deoxidization, adding a reducing agent into the system for initiating reaction, and obtaining the transparent or semitransparent polyacrylamide nanoparticle system after the exothermic peak passes. The oil-soluble solvent used in the invention is gasoline, kerosene, diesel oil, white oil, paraffin, vegetable oil, toluene, cyclohexane or isooctane. Wherein the oil-soluble solvents such as white oil are produced from fossil raw materials, and the consumption of raw materials is unavoidable, so that the cost is high; since a large amount of oil-soluble solvents have the problem of damaging the environment in use, the product is not environment-friendly; because the gel breaking effect of the inverse emulsion polymer is not ideal, the external fluid can cause water-locking damage to the reservoir.
In summary, the continuous optimization of inverse emulsion polymerization and its preparation method is an important research direction for the scientific researchers in the field.
Disclosure of Invention
The invention provides a clean environment-friendly self-degradable inverse emulsion polymer and a preparation method thereof, which are used for solving the problems of environmental protection, difficult self-degradation and water lock injury in the prior art.
In order to achieve the purpose of the invention, the invention provides the following technical scheme: a clean and environment-friendly self-degrading inverse emulsion polymer comprising the steps of:
(1) Preparing an oil phase and a water phase:
adding 200-300 parts of oil phase disperse phase and 20-30 parts of emulsifier into a beaker, and stirring to completely and uniformly mix the oil phase disperse phase and the 20-30 parts of emulsifier to obtain an oil phase for standby;
dissolving 200-300 parts of water phase reaction monomers into 200-400 parts of water under the action of magnetic stirring, adding 1-3 parts of 1% ammonium persulfate after uniformly mixing, adjusting the pH to 8 by using NaOH solution, adding 1-3 parts of initiator, uniformly stirring, and cooling to room temperature to obtain a water phase for later use;
(2) Mixing the water phase and the oil phase, and stirring at a high speed to obtain water-in-oil pre-emulsion;
(3) Pouring the pre-emulsion into a flask, introducing nitrogen to remove oxygen, and controlling the temperature of the system to be 10-18 ℃;
(4) Slowly dripping initiator accounting for 0.5-1.5% of the mass of the water phase reaction monomer for polymerization reaction, reacting for 4-6 hours at the temperature of 10-40 ℃, adding phase inversion agent accounting for 3.5% of the total mass of the emulsion, and uniformly stirring to obtain the self-degradation reverse phase emulsion thickener.
Further, the oil phase disperse phase is one or a mixture of two or more of methyl methacrylate, isoamyl butyrate, phenethyl acetate and methyl benzoate in any proportion.
Further, the emulsifier is one or a mixture of two or more of sorbitan oleate Span80, sorbitan stearate Span60, polyoxyethylene sorbitan monooleate Tween80, sorbitan monostearate polyoxyethylene ether Tween60 and polyoxyethylene octyl phenol ether OP-10 in any proportion.
Further, the aqueous phase reaction monomers are Acrylamide (AM), acrylic Acid (AA) and 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) with the mass ratio of 13-17:5-8:2-5.
Further, the initiator is one or a mixture of two or more of ammonium persulfate, ascorbic acid and sodium silicate in any proportion.
Further, the phase inversion agent is one or a mixture of two or more than two of nonionic surfactants OP-10, TX-10, tween80, tween60 and FC-4430 in any proportion.
The clean environment-friendly self-degradation inverse emulsion polymer prepared by the preparation method.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the ester compound is used for replacing the traditional white oil as an oil phase disperse phase, and an inverse emulsion polymerization method is adopted to prepare the clean environment-friendly self-degradation inverse emulsion polymer, so that the self-breaking of polyacrylamide is realized, meanwhile, the application of solvent oil is reduced, and in the preparation process, a nonionic surfactant is selected as a system phase inversion agent, so that the emulsion has better solubility, and the prepared product is cleaner and environment-friendly.
2. The continuous phase is applied with a degradable ester compound, the ester can be automatically degraded into alcohol and acid, and the application of the ester compound as fracturing fluid can be helpful for polymer gel breaking, so that the water locking damage of an external fluid to a reservoir is effectively reduced.
Drawings
FIG. 1 is a graph of the 90℃rheology of the present invention;
FIG. 2 is a graph of 120℃rheology of the present invention;
FIG. 3 shows the molecular weight of the degradation liquid according to GPC test of the present invention;
FIG. 4 shows the particle size of the degradation liquid according to the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments.
The invention provides a clean environment-friendly self-degradable inverse emulsion polymer, which comprises the following steps:
(1) Preparing an oil phase and a water phase:
adding 200-300 parts of oil phase disperse phase and 20-30 parts of emulsifier into a beaker, and stirring to completely and uniformly mix the oil phase disperse phase and the emulsifier to obtain an oil phase (ester continuous phase) for standby;
dissolving 200-300 parts of water phase reaction monomers into 200-400 parts of water under the action of magnetic stirring, adding 1-3 parts of 1% ammonium persulfate after uniformly mixing, adjusting the pH to 8 by using NaOH solution, adding 1-3 parts of initiator, uniformly stirring, and cooling to room temperature to obtain a water phase for later use;
(2) Mixing the water phase and the oil phase, and stirring at high speed to obtain water-in-oil pre-emulsion which is in a yoghourt shape and has even wall hanging;
(3) Pouring the pre-emulsion into a flask, introducing nitrogen to remove oxygen, and controlling the temperature of the system to be 10-18 ℃;
(4) Slowly dripping initiator accounting for 0.5-1.5% of the mass of the water phase reaction monomer for polymerization reaction, reacting for 4-6 hours at the temperature of 10-40 ℃, adding phase inversion agent accounting for 3.5% of the total mass of the emulsion, and uniformly stirring to obtain the self-degradation reverse phase emulsion thickener.
The parts described in the examples below are parts by weight.
Example 1: a preparation method of a clean environment-friendly self-degradable inverse emulsion polymer comprises the following steps of
(1) Preparing an oil phase and a water phase:
130 parts of AM, 50 parts of AA and 20 parts of AMPS are dissolved in 200 parts of water under the action of magnetic stirring, 1 part of 1% ammonium persulfate is added after uniform mixing, the pH is regulated to 8 by using 48% NaOH solution, and after cooling to room temperature, a water phase is obtained for standby.
10 parts of Span80,5 parts of Tween80,5 parts of Span60 and 200 parts of isoamyl butyrate are uniformly mixed under the action of magnetic stirring, so as to obtain an oil phase for standby.
(2) Mixing the water phase and the oil phase, and stirring at high speed to obtain the reverse phase pre-emulsion.
(3) Pouring the pre-emulsion into a flask with a stirring kettle, a thermometer and a nitrogen inlet, introducing nitrogen to remove oxygen, and controlling the temperature of the system to be 10-18 ℃.
(4) Slowly dripping an initiator ascorbic acid solution with the mass of 0.5% of the water phase reaction monomer for polymerization reaction, controlling the temperature of the system at 30-40 ℃, keeping the reaction for 6 hours, reducing the temperature at the moment, completing the polymerization, adding a phase inversion agent TX-10 accounting for 3.5% of the total mass of the emulsion, and uniformly stirring to obtain the clean environment-friendly self-degrading inverse emulsion polymer.
Example 2: a preparation method of a clean environment-friendly self-degradable inverse emulsion polymer comprises the following steps of
(1) Preparing an oil phase and a water phase:
140 parts of AM, 60 parts of AA and 30 parts of AMPS are dissolved in 240 parts of water under the action of magnetic stirring, after the water phases are uniformly mixed, 1.5 parts of 1% ammonium persulfate is added, and then 48% NaOH solution is used for regulating the pH to 8. After cooling to room temperature, a water phase is obtained for standby.
10 parts of Span80,7 parts of Tween80,7 parts of Span60 and 240 parts of ester are uniformly mixed under the action of magnetic stirring, so as to obtain an oil phase for standby.
(2) Mixing the water phase and the oil phase, and stirring at high speed to obtain the reverse phase pre-emulsion.
(3) Pouring the pre-emulsion into a flask with a stirring kettle, a thermometer and a nitrogen inlet, introducing nitrogen to remove oxygen, and controlling the temperature of the system to be 10-18 ℃.
(4) Slowly dripping an initiator ascorbic acid solution with the mass of 0.5% of the aqueous phase reaction monomer for polymerization reaction, controlling the temperature of the system at 30-40 ℃, keeping the reaction for 4 hours, reducing the temperature at the moment, completing the polymerization, and adding a phase inversion agent TX-10 with the mass of 3.5% of the emulsion to obtain the clean environment-friendly self-degradation inverse emulsion polymer.
Example 3: a preparation method of a clean environment-friendly self-degradable inverse emulsion polymer comprises the following steps of
(1) Preparing an oil phase and a water phase:
160 parts of AM, 70 parts of AA and 40 parts of AMPS are dissolved in 300 parts of water under the action of magnetic stirring, after the water phases are uniformly mixed, 2 parts of 1% ammonium persulfate is added, and then 48% NaOH solution is used for regulating the pH to 8. After cooling to room temperature, a water phase is obtained for standby.
Uniformly mixing 20 parts of Span80,4 parts of Tween80,4 parts of Span60 and 280 parts of 8 ester under the action of magnetic stirring to obtain an oil phase for later use.
(2) Mixing the water phase and the oil phase, and stirring at high speed to obtain the reverse phase pre-emulsion.
(3) Pouring the pre-emulsion into a flask with a stirring kettle, a thermometer and a nitrogen inlet, introducing nitrogen to remove oxygen, and controlling the temperature of the system to be 10-18 ℃.
(4) Slowly dripping an initiator ascorbic acid solution with the mass of 0.5% of the aqueous phase reaction monomer for polymerization reaction, controlling the temperature of the system at 30-40 ℃, keeping the reaction for 6 hours, reducing the temperature at the moment, completing the polymerization, adding a phase inversion agent TX-10 with the mass of 3.5% of the emulsion, and uniformly stirring to obtain the clean environment-friendly self-degrading inverse emulsion polymer.
Example 4: a preparation method of a clean environment-friendly self-degradable inverse emulsion polymer comprises the following steps of
(1) Preparing an oil phase and a water phase:
170 parts of AM, 80 parts of AA and 50 parts of AMPS are dissolved in 400 parts of water under the action of magnetic stirring, 3 parts of 1% ammonium persulfate is added after the water phases are uniformly mixed, and then the pH is adjusted to 8 by using 48% NaOH solution. After cooling to room temperature, a water phase is obtained for standby.
20 parts of Span80,5 parts of Tween80,5 parts of Span60 and 300 parts of ester are uniformly mixed under the action of magnetic stirring, so as to obtain an oil phase for standby.
(2) Mixing the water phase and the oil phase, and stirring at high speed to obtain the reverse phase pre-emulsion.
(3) Pouring the pre-emulsion into a flask with a stirring kettle, a thermometer and a nitrogen inlet, introducing nitrogen to remove oxygen, and controlling the temperature of the system to be 10-18 ℃.
(4) Slowly dripping an initiator ascorbic acid solution with the mass of 0.5% of the aqueous phase reaction monomer for polymerization reaction, controlling the temperature of the system below 40 ℃, keeping the reaction for 6 hours, reducing the temperature at the moment, completing the polymerization, adding a phase inversion agent TX-10 with the mass of 3.5% of the emulsion, and uniformly stirring to obtain the clean environment-friendly self-degrading inverse emulsion polymer.
Performance testing
(1) Molecular weight test
The time of the polymer solution flowing through the undiluted capillary viscometer is tested by taking 1mol/L sodium chloride solution as a standard comparison solution, and the intrinsic viscosity [ eta ] of the polymer is calculated to obtain the molecular weight of the polymer as shown in Table 1, wherein the molecular weight of the synthesized polymer is more than 1500 ten thousand, and the polymer obtained in example 2 has the highest molecular weight and the best performance.
TABLE 1 clean Environment-friendly self-degrading inverse emulsion Polymer molecular weight
(2) Rheological Performance test
With the product obtained in the preferred example 2, the following tests were carried out: 1.0% clean environment-friendly self-degradable inverse emulsion polymer is prepared, and the temperature resistance and the shearing resistance are tested, and as can be seen from figure 1, the shearing rate of the fracturing fluid is 170s -1 After shearing for 1 hour at 90 ℃, the final viscosity is 92.45 mPas, and after shearing for 1 hour at 120 ℃, the final viscosity is 75.92 mPas, and the temperature and shearing resistance is excellent.
(3) Degradation properties
With the product obtained in the preferred example 2, the following tests were carried out: and (3) preparation of degradation liquid: preparing 0.5% clean environment-friendly self-degradable inverse emulsion polymer aqueous solution, and standing at 30 ℃ for 48 hours, wherein the polymer can degrade spontaneously.
Referring to fig. 3, it can be seen that the molecular weight of the degradation liquid was measured by GPC, the viscosity average molecular weight of the degradation liquid was about 3.5 Mo Zuo, the polymer was thoroughly broken, and the average particle size was measured with reference to fig. 4, and it can be seen that d50=825 nm.
(4) Waterproof Lock Effect evaluation
The clean environment-friendly self-degradable reverse emulsion is subjected to waterproof lock effect evaluation by adopting a simulated rock core and referring to a SY/T6540-2002 method, and the test results are shown in Table 2. The synthetic clean environment-friendly self-degrading reverse emulsion polymer has higher permeability restoration rate which is more than 80%, which indicates that the clean environment-friendly self-degrading reverse emulsion prepared by the invention can effectively reduce the water locking damage of the external fluid to the reservoir when being applied as the fracturing fluid.
Table 2 test results of waterproof lock effect of clean and environment-friendly self-degrading inverse emulsion
| Project | Example 1 | Example 2 | Example 3 | Example 4 |
| Core number | 1# | 2# | 3# | 4# |
| Injury liquid | 2％KCl | 2％KCl | 2％KCl | 2％KCl |
| Permeability repair rate% | 80.26 | 85.68 | 89.27 | 88.38 |
The present invention is not limited to the preferred embodiments, but can be modified in any way according to the technical principles of the present invention, and all such modifications, equivalent variations and modifications are included in the scope of the present invention.
Claims (7)
1. The clean environment-friendly self-degrading inverse emulsion polymer is characterized by comprising the following steps:
(1) Preparing an oil phase and a water phase:
adding 200-300 parts of oil phase disperse phase and 20-30 parts of emulsifier into a beaker, and stirring to completely and uniformly mix the oil phase disperse phase and the 20-30 parts of emulsifier to obtain an oil phase for standby;
dissolving 200-300 parts of water phase reaction monomers into 200-400 parts of water under the action of magnetic stirring, adding 1-3 parts of 1% ammonium persulfate after uniformly mixing, adjusting the pH to 8 by using NaOH solution, adding 1-3 parts of initiator, uniformly stirring, and cooling to room temperature to obtain a water phase for later use;
(2) Mixing the water phase and the oil phase, and stirring at a high speed to obtain water-in-oil pre-emulsion;
(3) Pouring the pre-emulsion into a flask, introducing nitrogen to remove oxygen, and controlling the temperature of the system to be 10-18 ℃;
(4) Slowly dripping initiator accounting for 0.5-1.5% of the mass of the water phase reaction monomer for polymerization reaction, reacting for 4-6 hours at the temperature of 10-40 ℃, adding phase inversion agent accounting for 3.5% of the total mass of the emulsion, and uniformly stirring to obtain the self-degradation reverse phase emulsion thickener.
2. The clean and environment-friendly self-degrading inverse emulsion polymer as claimed in claim 1, wherein the oil phase disperse phase in the first step is one or a mixture of two or more of methyl methacrylate, isoamyl butyrate, phenethyl acetate and methyl benzoate in any proportion.
3. The clean and environment-friendly self-degrading inverse emulsion polymer according to claim 1, wherein the emulsifier in the step (1) is one or a mixture of two or more of sorbitan oleate Span80, sorbitan stearate Span60, polyoxyethylene sorbitan monooleate Tween80, sorbitan monostearate polyoxyethylene ether Tween60 and polyoxyethylene octyl phenol ether OP-10 in any proportion.
4. A clean and environment-friendly self-degrading inverse emulsion polymer according to any of claims 1-3, wherein the aqueous phase reaction monomers in the step (1) are Acrylamide (AM), acrylic Acid (AA) and 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) with a mass ratio of 13-17:5-8:2-5.
5. The clean and environment-friendly self-degrading inverse emulsion polymer according to claim 4, wherein the initiator in the step (1) is one or a mixture of two or more of ammonium persulfate, ascorbic acid and sodium silicate.
6. The clean environment-friendly self-degrading inverse emulsion polymer according to any claim 5, wherein the phase inversion agent in the step (4) is one or a mixture of two or more of nonionic surfactants OP-10, TX-10, tween80, tween60 and FC-4430 in any proportion.
7. A clean and environment-friendly self-degrading inverse emulsion polymer prepared by the preparation method of claim 1.
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