CN113912770A - Star-shaped polymer for drilling fluid, preparation method and application thereof - Google Patents
Star-shaped polymer for drilling fluid, preparation method and application thereof Download PDFInfo
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- CN113912770A CN113912770A CN202010656340.5A CN202010656340A CN113912770A CN 113912770 A CN113912770 A CN 113912770A CN 202010656340 A CN202010656340 A CN 202010656340A CN 113912770 A CN113912770 A CN 113912770A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 77
- 238000005553 drilling Methods 0.000 title claims abstract description 51
- 239000012530 fluid Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000006085 branching agent Substances 0.000 claims abstract description 26
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 23
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims abstract description 11
- 239000004005 microsphere Substances 0.000 claims abstract description 10
- 125000005189 alkyl hydroxy group Chemical group 0.000 claims abstract description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000012071 phase Substances 0.000 claims description 40
- 239000000178 monomer Substances 0.000 claims description 33
- 239000003921 oil Substances 0.000 claims description 32
- 239000003995 emulsifying agent Substances 0.000 claims description 27
- 239000000839 emulsion Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 19
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- 239000002199 base oil Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 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 7
- 238000000034 method Methods 0.000 claims description 7
- 150000000703 Cerium Chemical class 0.000 claims description 6
- 229920000136 polysorbate Polymers 0.000 claims description 6
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 239000008186 active pharmaceutical agent Substances 0.000 abstract description 9
- 230000032683 aging Effects 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 239000002002 slurry Substances 0.000 abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 7
- 239000011780 sodium chloride Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 10
- 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 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 7
- 229920000053 polysorbate 80 Polymers 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical group [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 230000001804 emulsifying effect Effects 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000012688 inverse emulsion polymerization Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- 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 description 2
- 230000009471 action Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000281 calcium bentonite Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- 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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
-
- 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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a star polymer for drilling fluid, a preparation method and application thereof, wherein the star polymer is prepared by performing emulsion polymerization on an acrylamide monomer, 2-acrylamido-2-methylpropanesulfonic acid and a branching agent; the branching agent structure comprises a plurality of alkylhydroxy groups; the star polymer for the drilling fluid has a branched structure and a nano-scale polymer microsphere shape. The molecular chain of the star polymer can adopt a more extended conformation due to the mutual repulsion between the arms, the bridging filtration-reducing capacity is strong, and the star polymer has better effects of temperature resistance and the like than a linear polymer. The experimental result shows that the apparent viscosity of the 1.0% solution of the star polymer fluid loss agent at room temperature is less than or equal to 35.0mPa & s; when the addition of the product is 3.0%, the API of the composite saline slurry is less than 5.0mL after aging at 165 ℃/16h, and the API is less than 30mL after aging at 180 ℃/16 h.
Description
Technical Field
The invention belongs to the technical field of preparation methods of synthetic water-soluble high polymer materials for oil fields, and particularly relates to a star polymer for drilling fluid, and a preparation method and application thereof.
Background
The drilling fluid is an important fluid in drilling engineering, and the quality of the performance of the drilling fluid is directly related to the quality of drilling. The drilling fluid mainly comprises base slurry and various treating agents, wherein the treating agents comprise a filtrate reducer, a pH regulator and the like. With the continuous deepening of exploration and development, the requirements of high-temperature deep wells and special complex wells on the treating agent for the drilling fluid are higher and higher, and particularly the high-temperature deep wells in the north and south regions put higher requirements on the temperature resistance of the treating agent.
At present, synthetic polymer treating agents such as polyacrylamide filtrate reducers used on site are basically linear polymers, and the high-temperature stability of drilling fluid is reduced due to the fact that the molecular chain is long, the chain is easy to break after high-temperature shearing and the viscosity is greatly reduced.
Therefore, research on polymers with special structures, change of molecular conformations of treating agents, and improvement of comprehensive effects of high temperature resistance and the like of the existing polymer filtrate reducers are a main development trend.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a star polymer for drilling fluid, a preparation method and application thereof.
The invention provides a star polymer for drilling fluid, which is prepared by performing emulsion polymerization on acrylamide monomers, 2-acrylamido-2-methylpropanesulfonic acid and a branching agent;
the branching agent structure comprises a plurality of alkylhydroxy groups;
the star polymer for the drilling fluid has a branched structure and a nano-scale polymer microsphere shape.
Preferably, the branching agent is pentaerythritol.
Preferably, the apparent viscosity of the 1.0% star polymer solution for the drilling fluid at room temperature is less than or equal to 35.0 mPas.
The invention provides a preparation method of a star polymer for drilling fluid, which comprises the following steps:
s1, adding the water phase material into the oil phase material for emulsification to obtain monomer emulsion; the water phase material comprises acrylamide monomers, 2-acrylamide-2-methyl propane sulfonic acid and a branching agent; the branching agent structure comprises a plurality of alkylhydroxy groups;
s2, carrying out polymerization reaction on the monomer emulsion in the presence of an initiator to obtain the star polymer in the form of nano-scale polymer microspheres.
Preferably, the water phase material comprises 390 to 420 parts by mass of water, 147.50 to 172.50 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid, 152.00 to 177.50 parts by mass of acrylamide monomer, 0.15 to 0.175 part by mass of branching agent and 2.00 to 3.50 parts by mass of hydrophilic emulsifier.
Preferably, the oil phase material comprises 208-224 parts by mass of base oil and 18.50-30.50 parts by mass of lipophilic emulsifier; the kinematic viscosity of the base oil at 40 ℃ is preferably 1.5mm2/s～3.0mm2/s。
Preferably, the hydrophilic emulsifier is selected from the tween series; the lipophilic emulsifier is selected from span series.
Preferably, the initiator is one or more of a cerium salt initiator and a persulfate initiator.
Preferably, the monomer emulsion is placed in a water bath at the temperature of 30-65 ℃, inert gas is preferably introduced, an initiator is added, and the polymerization reaction is carried out at a low speed for 3-5 hours, so as to obtain the star polymer.
The invention also provides the application of the star polymer for the drilling fluid as a fluid loss additive in the drilling fluid.
Compared with the prior art, the star polymer with the branched structure can be used as a fluid loss additive for drilling fluid, is mainly prepared from an acrylamide monomer, 2-acrylamido-2-methylpropanesulfonic acid and a branching agent containing a plurality of alkyl hydroxyl groups through emulsion polymerization, and is a nano-scale polymer microsphere. In the invention, the molecular chain of the star polymer can adopt a more extended conformation due to the mutual repulsion between arms, the bridging filtration loss reducing capability is strong, and the effects of temperature resistance and the like are better than those of a linear polymer. The experimental result shows that the apparent viscosity of the 1.0% solution of the star polymer fluid loss agent at room temperature is less than or equal to 35.0mPa & s; when the addition of the product is 3.0%, the API of the composite saline slurry is less than 5.0mL after aging at 165 ℃/16h, and the API is less than 30mL after aging at 180 ℃/16h (the filtration loss reduction rate of the linear polymer fluid loss additive with the same ratio of groups and groups is more than 50 percent).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other examples, which may be modified or appreciated by those of ordinary skill in the art based on the examples given herein, are intended to be within the scope of the present invention.
The invention provides a star polymer for drilling fluid, which is prepared by performing emulsion polymerization on acrylamide monomers, 2-acrylamido-2-methylpropanesulfonic acid and a branching agent;
the branching agent structure comprises a plurality of alkylhydroxy groups;
the star polymer for the drilling fluid has a branched structure and a nano-scale polymer microsphere shape.
The polymer provided by the invention can be used as a fluid loss additive with the functions of temperature resistance, salt resistance and the like, is convenient to use, low in dosage and outstanding in fluid loss reduction effect, and can be widely used for drilling fluid.
The polymer provided by the invention is a star polymer prepared by emulsion polymerization of an acrylamide monomer, a 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) monomer and a branching agent containing a plurality of alkyl hydroxyl groups, and has a branching structure (also called as a star structure). Among them, the acrylamide-based monomer such as acrylamide and methacrylamide is preferably Acrylamide (AM).
The star-shaped structure polymer has a three-dimensional structure, a molecular chain is in a more extended conformation due to mutual repulsion among arms, the density of groups in the molecular structure is increased, the performances of reducing the fluid loss capacity, improving the shear and the like in the drilling fluid are improved, and the suspension stability of the drilling fluid can be greatly improved. Meanwhile, the star-shaped three-dimensional structure can increase the steric hindrance effect among molecules, is beneficial to improving the temperature resistance and the salt resistance of the drilling fluid, has better action effect than a linear polymer, and has certain advantages in improving the long-term stability, the shearing dilution property and the suspension stability of the drilling fluid at high temperature.
In addition, pentaerythritol is preferably used as a branching agent, so that a four-arm star polymer for drilling fluid can be obtained; the molecular structure of pentaerythritol contains four-CH which is easy to generate oxidation reduction reaction2OH groups are oriented in four directions in space and have symmetrical structures, so that the branched structure is suitable for forming, the molecular conformation of the existing polymer is changed, and the comprehensive effect of the existing polymer is improved.
The embodiment of the invention can adopt an inverse emulsion polymerization mode to form the polymer emulsion, wherein the star polymer is in a nanometer polymer microsphere shape, which is beneficial to the stability, the application simplicity and the like of the drilling fluid. In the embodiment of the invention, the apparent viscosity of the star polymer 1.0% solution for the drilling fluid at room temperature is less than or equal to 35.0 mPas.
Correspondingly, the embodiment of the invention provides a preparation method of a star polymer for drilling fluid, which comprises the following steps:
s1, adding the water phase material into the oil phase material for emulsification to obtain monomer emulsion; the water phase material comprises acrylamide monomers, 2-acrylamide-2-methyl propane sulfonic acid and a branching agent; the branching agent structure comprises a plurality of alkylhydroxy groups;
s2, carrying out polymerization reaction on the monomer emulsion in the presence of an initiator to obtain the star polymer in the form of nano-scale polymer microspheres.
The embodiment of the invention adopts an inverse emulsion polymerization mode to form the nano-scale polymer microsphere treating agent, which is applied to the drilling fluid, has the advantages of outstanding fluid loss reduction effect, good temperature resistance and salt resistance and convenient use.
Inverse emulsion polymerization refers to a process method in which water-soluble monomers are prepared into an aqueous solution, the aqueous solution and an organic phase form a water-in-oil emulsion under the action of an oil-soluble surfactant, and then a polymerization reaction is initiated by an initiator to form water-in-oil (water/oil) type polymer latex.
In a reaction kettle, firstly adding pure water, acrylamide monomers, 2-acrylamido-2-methylpropanesulfonic acid and a branching agent, preferably adding a hydrophilic emulsifier, and then adjusting the pH value of the system to be alkaline (for example, the pH value is 9-10) to obtain a water phase.
Specifically, the water phase material comprises 390-420 parts by mass of water, 147.50-172.50 parts by mass of 2-acrylamide-2-methyl propanesulfonic acid, 152.00-177.50 parts by mass of acrylamide monomers, 0.15-0.175 part by mass of a branching agent and 2.00-3.50 parts by mass of a hydrophilic emulsifier.
Wherein, the acrylamide monomer is preferably acrylamide and N, N-dimethylacrylamide; the branching agent is preferably pentaerythritol. The hydrophilic emulsifier can be selected from Tween series, preferably Tween 80 or Tween 60. Ethoxylated fatty acid glycidyl esters are the Tween series (Tween series). The glycidyl esters of different fatty acids are known as Span (Span) series and are generally oil soluble; span80 is a sorbitan monooleate, oily at room temperature, with an HLB value of 4.3. The HLB value range of the products of span series and Tween series is 1.8-16.7, and the products can be used in a compounding way.
In addition, the base oil and the lipophilic emulsifier are added into the reaction kettle, and stirred until the base oil and the lipophilic emulsifier are completely dissolved, so that the oil phase is obtained. Specifically, the oil phase material comprises 208-224 parts by mass of base oil and 18.50-30.50 parts by mass of lipophilic emulsifier. The kinematic viscosity of the base oil at 40 ℃ is preferably 1.5mm2/s～3.0mm2And s. For example, 2# or 3# white oil. The lipophilic emulsifier may be selected from the span series, preferably span80 or span 60, which are commercially available.
In the invention, the water phase material preferably comprises 390 to 420 parts by mass of water, 147.86 to 172.50 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid, 152.14 to 177.50 parts by mass of acrylamide monomer, 2.08 to 3.36 parts by mass of tween 80 emulsifier or tween 60, and 0.15 to 0.175 part by mass of branching agent. The oil phase material preferably comprises 208-224 parts by mass of white oil, 18.72-30.24 parts by mass of span-80 or span-60 emulsifier.
According to the invention, the water phase is preferably slowly added into the oil phase under the stirring condition, and the high-speed emulsification can be carried out for 20min to obtain the monomer emulsion. The monomer emulsion is placed in a water bath at the temperature of 30-65 ℃, inert gas is preferably introduced, 1-1.5 parts by mass of initiator can be added, and the mixture is stirred at a low speed for polymerization reaction for 3-5 hours to obtain the star polymer for the drilling fluid.
In the present invention, the initiator is preferably one or more of a cerium salt initiator and a persulfate initiator. The cerium salt initiator is preferably cerium ammonium nitrate; the persulfate initiator is preferably ammonium persulfate or potassium persulfate. In the embodiment of the invention, 1.006-1.173 parts by mass of cerium salt or a cerium salt and persulfate composite initiation system is preferably adopted, and the star polymer is polymerized under the protection of high-purity nitrogen.
In the preparation process of the star polymer fluid loss additive emulsion, pentaerythritol is used as a branching agent (the molecular structure of the pentaerythritol contains four-CH which is easy to generate oxidation-reduction reaction)2OH groups, sterically tetra-oriented and structurally symmetrical, suitable for forming branched structures); one or two of sodium hydroxide and potassium hydroxide are adopted to compositely adjust the pH value of the system and balanceThe system heat dissipation capacity avoids the potential safety hazard of the process flow caused by too large heat at a certain stage; the pH value of the system is controlled, the reactivity ratio among monomers is balanced, the reaction time of different initiation stages is adjusted, the monomer conversion rate of each stage is balanced, the heat dissipation capacity of the system of each stage is balanced, and the reaction is ensured to be carried out stably. The invention preferably adopts low-temperature initiation of 30-45 ℃ water bath, the temperature is uniformly raised in the whole reaction process, the monomer conversion rate can reach 50% when the system temperature reaches 40 ℃, and the maximum temperature of the system in the whole polymerization process does not exceed 60 ℃.
The star polymer prepared by the method has the advantages that the molecular chain adopts a more extended conformation due to the mutual repulsion between the arms, the bridging filtrate reducer has strong capability, and the effect is better than that of a linear polymer. The preparation method is simple and convenient, and the obtained product has good temperature resistance and salt resistance, can be used for high-temperature and high-salt formations, and reduces the filtration loss of the drilling fluid.
The invention also provides the application of the star polymer for the drilling fluid as a fluid loss additive in the drilling fluid. Wherein, the components such as base slurry and the like in the drilling fluid are not particularly limited; the addition amount of the star polymer fluid loss additive product can be 1.0-3.0%.
Experiments show that when the addition of the product is 3.0%, the API of the composite saline slurry is less than 5.0mL after aging at 165 ℃/16h, and the API is less than 30mL after aging at 180 ℃/16h (compared with the same type of linear polymer fluid loss additive, the fluid loss reduction rate is more than 50%). The star polymer filtrate reducer has high comprehensive effects of high temperature resistance and the like, and has important significance for solving the problem of controlling the performance of high-salt and high-temperature deep well drilling fluid in north and the like and promoting the technical progress of the drilling fluid.
In order to further understand the invention, the star polymer for drilling fluid provided by the application, the preparation method and the application thereof are specifically described in the following with reference to the examples. It should be understood, however, that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention, which is defined by the following examples.
In the following examples: the white oil is 2# or 3# white oil, and the kinematic viscosity is 2.0-3.0 mm2/s。
Example 1:
adding 420g of water into a reaction kettle, starting stirring, adding 152g of 2-acrylamide-2-methylpropanesulfonic acid, 156g of acrylamide, 0.15g of pentaerythritol and 2.8g of tween-80 emulsifier, and then adjusting the pH of the system to 9.0 by using 30% potassium hydroxide to obtain a water phase;
adding 224g of 2# white oil and 25.2g of span-80 emulsifier into a reaction kettle, and stirring until the materials are completely dissolved to obtain an oil phase;
slowly adding the water phase into the oil phase under stirring, stirring for 20min, and emulsifying at high speed for 20min to obtain monomer emulsion; and (3) placing the monomer emulsion in a constant-temperature water bath at 35 ℃, introducing nitrogen for 30min, adding 1.006g of ammonium ceric nitrate, and reacting for 5h under low-speed stirring to obtain the target polymer emulsion.
Example 2:
adding 390g of water into a reaction kettle, starting stirring, adding 172.5g of 2-acrylamide-2-methylpropanesulfonic acid, 177.5g of acrylamide, 0.175g of pentaerythritol and 2.6g of tween-80 emulsifier, and then adjusting the pH value of the system to 10.0 by using 30% sodium hydroxide to obtain a water phase;
adding 208g of 2# white oil and 23.4g of span-80 emulsifier into a reaction kettle, and stirring until the mixture is completely dissolved to obtain an oil phase;
slowly adding the water phase into the oil phase under stirring, and emulsifying at high speed for 20min to obtain monomer emulsion; and (3) placing the monomer emulsion in a constant-temperature water bath at 40 ℃, introducing nitrogen for 30min, adding 1.173g of ammonium persulfate, and reacting for 3h under low-speed stirring to obtain the target product.
Example 3:
adding 408g of water into a reaction kettle, stirring, adding 158g of 2-acrylamido-2-methylpropanesulfonic acid, 162g N, N-methacrylamide, 0.16g of pentaerythritol, 1.125g of ceric ammonium nitrate and 3.264g of tween-80 emulsifier, and adjusting the pH value of the system to 9.0 by using 30% potassium hydroxide to obtain a water phase;
adding 217g of 2# white oil and 29.38g of span-80 emulsifier into a reaction kettle, and stirring until the materials are completely dissolved to obtain an oil phase;
slowly adding the water phase into the oil phase under stirring, stirring for 20min, and emulsifying at high speed for 20min to obtain monomer emulsion; and (3) placing the monomer emulsion in a constant-temperature water bath at 35 ℃, introducing nitrogen for 30min, adding 0.833g of ammonium ceric nitrate and 0.173g of ammonium persulfate, and reacting for 5h under low-speed stirring to obtain the target product.
Example 4:
adding 390g of water into a reaction kettle, starting stirring, adding 172.5g of 2-acrylamide-2-methylpropanesulfonic acid, 177.5g of acrylamide, 0.175g of pentaerythritol and 2.6g of tween-80 emulsifier, and then adjusting the pH value of the system to 10.0 by using 30% sodium hydroxide to obtain a water phase;
adding 208g of 3# white oil and 23.4g of span-80 emulsifier into a reaction kettle, and stirring until the mixture is completely dissolved to obtain an oil phase;
slowly adding the water phase into the oil phase under stirring, and emulsifying at high speed for 20min to obtain monomer emulsion; and (3) placing the monomer emulsion in a constant-temperature water bath at 40 ℃, introducing nitrogen for 30min, adding 0.971g of ammonium ceric nitrate and 0.202g of ammonium persulfate, and reacting for 3h under low-speed stirring to obtain the target product.
Example 5:
adding 420g of water into a reaction kettle, starting stirring, adding 152g of 2-acrylamido-2-methylpropanesulfonic acid, 156g N g of N-methacrylamide, 0.175g of pentaerythritol, 1.173g of ceric ammonium nitrate and 2.8g of tween-80 emulsifier, mixing 30% of potassium hydroxide and sodium hydroxide in a mass ratio of 2:1, and adjusting the pH value of the system to 10 to obtain a water phase;
adding 224g of 3# white oil and 25.2g of span-80 emulsifier into a reaction kettle, and stirring until the materials are completely dissolved to obtain an oil phase;
slowly adding the water phase into the oil phase under stirring, stirring for 20min, and emulsifying at high speed for 20min to obtain monomer emulsion; and (3) placing the monomer emulsion in a constant-temperature water bath at 35 ℃, introducing nitrogen for 30min, adding 1.006g of ammonium persulfate initiator, and reacting for 5h under low-speed stirring to obtain the target product.
The drilling fluid performance evaluation was carried out on the products obtained in examples 1 to 5: the composite saline water-based slurry and 3.0% polymer emulsion are adopted, rolling aging is carried out for 16h at 165 ℃ and 180 ℃, and then the medium pressure filtration loss of the drilling fluid is measured according to the specification of 7.2 in GB/T16783.1-2006, the temperature is 24 ℃ plus or minus 3 ℃, and the pressure is 690 KPa. The results are shown in Table 1.
Wherein, the composite saline water base slurry: 350mL of distilled water, 4.5% of sodium chloride, 0.5% of calcium chloride, 1.3% of magnesium chloride, 0.9% of anhydrous sodium carbonate and 15% of calcium bentonite.
TABLE 1 Performance index of the products prepared in examples 1-5
As can be seen from Table 1, the 1.0% emulsion has an apparent viscosity of less than 35.0 mPas, and when the amount of the emulsion added to the composite salt slurry is 3.0%, after aging at a high temperature of 165 ℃/16h, the API fluid loss is less than 5.0mL, after aging at a high temperature of 180 ℃/16h, the API fluid loss is less than 30.0mL, and the apparent viscosity is reduced for linear polymers with the same ratio groups and proportion, and the API fluid loss is less than 50% after high temperature. Therefore, the star polymer product has better temperature resistance and salt resistance, can be used for high-temperature and high-salt formations, and reduces the filtration loss of the drilling fluid.
The above description is only a preferred embodiment of the present invention, and it should be noted that various modifications to these embodiments can be implemented by those skilled in the art without departing from the technical principle of the present invention, and these modifications should be construed as the scope of the present invention.
Claims (10)
1. A star polymer for drilling fluid is characterized in that the star polymer is prepared by an acrylamide monomer, 2-acrylamido-2-methylpropanesulfonic acid and a branching agent through emulsion polymerization;
the branching agent structure comprises a plurality of alkylhydroxy groups;
the star polymer for the drilling fluid has a branched structure and a nano-scale polymer microsphere shape.
2. The star polymer for drilling fluids of claim 1, wherein the branching agent is pentaerythritol.
3. The star polymer for drilling fluid as claimed in claim 1, wherein the apparent viscosity of 1.0% solution of the star polymer for drilling fluid is less than or equal to 35.0 mPas at room temperature.
4. The preparation method of the star polymer for the drilling fluid comprises the following steps:
s1, adding the water phase material into the oil phase material for emulsification to obtain monomer emulsion; the water phase material comprises acrylamide monomers, 2-acrylamide-2-methyl propane sulfonic acid and a branching agent; the branching agent structure comprises a plurality of alkylhydroxy groups;
s2, carrying out polymerization reaction on the monomer emulsion in the presence of an initiator to obtain the star polymer in the form of nano-scale polymer microspheres.
5. The method according to claim 4, wherein the aqueous phase material comprises 390 to 420 parts by mass of water, 147.50 to 172.50 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid, 152.00 to 177.50 parts by mass of an acrylamide monomer, 0.15 to 0.175 part by mass of a branching agent, and 2.00 to 3.50 parts by mass of a hydrophilic emulsifier.
6. The preparation method according to claim 5, wherein the oil phase material comprises 208-224 parts by mass of base oil and 18.50-30.50 parts by mass of lipophilic emulsifier; the kinematic viscosity of the base oil at 40 ℃ is preferably 1.5mm2/s～3.0mm2/s。
7. The method according to claim 6, wherein the hydrophilic emulsifier is selected from the group consisting of Tween series; the lipophilic emulsifier is selected from span series.
8. The method of claim 4, wherein the initiator is one or more of a cerium salt initiator and a persulfate initiator.
9. The preparation method of the star polymer, wherein the monomer emulsion is placed in a water bath at the temperature of 30-65 ℃, preferably inert gas is introduced, an initiator is added, and the star polymer is obtained after the polymerization reaction is carried out for 3-5 hours under low-speed stirring.
10. The use of the star polymer for the drilling fluid as a fluid loss additive in the drilling fluid according to any one of claims 1 to 3.
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