CN114075430B - Polymer modified rubber plugging material for plugging oil-based drilling fluid and preparation method thereof - Google Patents
Polymer modified rubber plugging material for plugging oil-based drilling fluid and preparation method thereof Download PDFInfo
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- CN114075430B CN114075430B CN202010824806.8A CN202010824806A CN114075430B CN 114075430 B CN114075430 B CN 114075430B CN 202010824806 A CN202010824806 A CN 202010824806A CN 114075430 B CN114075430 B CN 114075430B
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 107
- 239000005060 rubber Substances 0.000 title claims abstract description 107
- 229920000642 polymer Polymers 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 69
- 238000005553 drilling Methods 0.000 title claims abstract description 59
- 239000012530 fluid Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 229920006037 cross link polymer Polymers 0.000 claims abstract description 18
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
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- 239000005062 Polybutadiene Substances 0.000 claims abstract description 8
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 8
- 239000003921 oil Substances 0.000 claims description 81
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 19
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000010920 waste tyre Substances 0.000 claims description 9
- 244000043261 Hevea brasiliensis Species 0.000 claims description 8
- 229920003052 natural elastomer Polymers 0.000 claims description 8
- 229920001194 natural rubber Polymers 0.000 claims description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 7
- -1 azodiisoheptonitrile Chemical compound 0.000 claims description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 239000002283 diesel fuel Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 abstract description 13
- 230000000903 blocking effect Effects 0.000 abstract description 6
- 239000011435 rock Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
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- 125000000217 alkyl group Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
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- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 3
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- 239000008206 lipophilic material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000375 suspending agent Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000005489 elastic deformation Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
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- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
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- 229920002748 Basalt fiber Polymers 0.000 description 1
- CGKQZIULZRXRRJ-UHFFFAOYSA-N Butylone Chemical compound CCC(NC)C(=O)C1=CC=C2OCOC2=C1 CGKQZIULZRXRRJ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/44—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing organic binders only
-
- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention provides a preparation method of a high polymer modified rubber plugging material for plugging an oil-based drilling fluid, which comprises the following steps: mixing a polymer containing active groups, rubber, a solvent, an oil-soluble cross-linking agent and an oil-soluble initiator, heating for reaction, and granulating to obtain a weakly cross-linked polymer for plugging oil-based drilling fluid; the high polymer containing active groups is one or more of polybutadiene, polyisoprene, polybutadiene-styrene, polyacrylonitrile-butadiene-styrene and the like. The invention adopts polymer modified common rubber containing active groups to form a core-shell structure product, and uses common rubber powder as a core and the polymer as a shell. The high polymer shell can absorb oil and become sticky in an oil phase environment at 80-120 ℃, has better cohesiveness, and improves the residence capacity of rubber by cohering the leakage layer rock and other leakage blocking materials. The modified rubber is solid at normal temperature, has small influence on rheological property of oil-based drilling fluid, and is convenient to pump to a leakage layer.
Description
Technical Field
The invention relates to the technical field of oilfield chemistry, in particular to a high polymer modified rubber plugging material for plugging an oil-based drilling fluid and a preparation method thereof.
Background
Along with the continuous increase of energy demand in China, unconventional oil and gas resource exploration and development are deeper and deeper, and at the moment, more complex stratum is drilled, and the demand on oil-based drilling fluid plugging technology is gradually increased. The development and application of the plugging material suitable for the oil-based drilling fluid are slow. At present, the plugging is carried out by conventional plugging materials such as rigid granular materials, fiber materials, deformation materials and the like with different particle diameters at home. However, most of the conventional plugging materials are hydrophilic, and have poor compatibility in oil-based drilling fluid, so that the plugging materials have poor residence property or the plugging layer has weak anti-damage capability, and the plugging effect is not ideal.
In order to improve the plugging performance of plugging materials in oil-based drilling fluids, many students have developed some lipophilic materials. The Oil Absorption Polymer (OAP) is prepared from monomer Methyl Methacrylate (MMA), butyl Acrylate (BA) and cetyl methacrylate (HMA) by adopting a suspension polymerization method, and can absorb oil and expand, so that the viscosity of the oil-based drilling fluid is effectively improved, and the high-temperature high-pressure fluid loss of the oil-based drilling fluid is reduced. US9366098B2 discloses an engineering plastic/inorganic fiber blend as a plugging material, mainly mixed with various plastic particles, basalt fibers (inorganic fibers) and other materials (such as calcium carbonate). Ivan C D describes a crosslinked polymer for plugging of oil-based drilling fluids for solving the problem of induced fracture loss. When the cross-linked polymer agent is extruded into an induced fracture, the fracture induction pressure increases, which helps the fracture to heal, thereby preventing leakage. SPE 121111-MS proposes to use fusible particles as plugging material to address severe leakage situations. The plugging material comprises molten particles, weighting materials with optimal particle size and various additives for controlling the material leakage rate and dispersibility. The plugging material has been used in ElkHills oil field of bekefir, california, usa and produced a significant plugging effect.
In summary, it can be seen that the development or addition of the lipophilic material into the conventional plugging material at the present stage improves the plugging performance of the oil-based drilling fluid through the oil absorption expansion, elastic deformation, partial dissolution or fusion bonding and other performances of the lipophilic material, which is a development trend. Rubber is a common oleophylic material, has good elastic deformability, is rich in source and low in price, is often used as a deformable filling plugging material, but is poor in plugging effect due to insufficient residence property of common rubber in an oil phase environment as a conventional inert material.
Therefore, the modified rubber has the filling effect of common rubber, has cohesiveness on the surface, can effectively improve the residence property of the rubber in an oil phase environment, can bond plugging materials into an integral slug, enhances the stability of a plugging layer, improves the plugging effect, and has important significance for plugging oil-based drilling.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide the high polymer modified rubber plugging material for plugging the oil-based drilling fluid, which has good residence property, good plugging property and good stability.
The invention provides a high polymer modified rubber plugging material for plugging an oil-based drilling fluid, which is a core-shell structure material taking a weak crosslinked high polymer with a structure shown in a formula (I) as a shell and rubber as a core;
wherein the molecular weight is 80,000-600,000, m, n, p is the polymerization degree, m: n: p= (200-6,000): 0-1,000): 0-6,000
R 1 An alkyl group of H, C to C10; r is R 2 One or more of H, C-C10 alkyl, C6-C20 aryl and C1-C10 alkyl ester; r is R 3 An alkyl group of H, C to C10; r is R 4 Is S or
Preferably, said R 1 Is H or CH 3 ；R 2 H, CH of a shape of H, CH 3 、(CH 2 ) n CH 3 、
COOCH 3 、COOCH 2 CH 3 Or OOCCH (OOCCH) 3 ；R 3 Is H or CH 3 。
Preferably, the weakly crosslinked polymer of the structure of the formula (I) is specifically of the structures shown in the formulas (I-1) to (I-3):
preferably, the weakly crosslinked polymer of the structure of formula (I) has a molecular weight of 80,000 ～ 600,000. The rubber is rubber powder; the rubber powder is one or more of natural rubber powder and waste tire rubber powder; the mesh number of the rubber powder is 0.047-125 mm.
The invention provides a preparation method of a high polymer modified rubber plugging material for plugging an oil-based drilling fluid, which comprises the following steps:
mixing a polymer containing active groups, rubber, a solvent, an oil-soluble cross-linking agent and an oil-soluble initiator, heating for reaction, and obtaining a weak cross-linked polymer for plugging oil-based drilling fluid by adopting a shearing granulation mode;
the high polymer containing active groups is one or more of polybutadiene, polyisoprene, polybutadiene-styrene, polyacrylonitrile-butadiene-styrene and the like.
Preferably, the solvent white oil, diesel, benzene, ethyl acetate, butyl acrylate or one or more of methylene chloride; the oil-soluble initiator is one or more of azodiisobutyronitrile, azodiisoheptonitrile, benzoyl peroxide, tert-butyl hydroperoxide and tert-butyl peroxybenzoate
Preferably, the lipophilic cross-linking agent is one or more of divinylbenzene, diisocyanate and sulfur; the rubber is rubber powder; the rubber powder is one or more of natural rubber powder and waste tire rubber powder; the mesh number of the rubber powder is 0.047-25 mm.
Preferably, the temperature of the heating reaction is 70-90 ℃; the heating reaction time is 6-10 h.
Preferably, the granulation is specifically a shearing granulation mode, and polymer particles with the particle size of 0.47-125 mm are obtained.
The invention provides an oil-based drilling fluid plugging product, which comprises the high polymer modified rubber plugging material for oil-based drilling fluid plugging with the structure of formula (I) in any one of the technical schemes or the high polymer modified rubber plugging material for oil-based drilling fluid plugging prepared by the preparation method of the high polymer modified rubber plugging material for oil-based drilling fluid plugging in any one of the technical schemes.
Compared with the prior art, the invention provides a preparation method of a high polymer modified rubber plugging material for plugging an oil-based drilling fluid, which comprises the following steps: mixing a polymer containing active groups, rubber, a solvent, an oil-soluble cross-linking agent and an oil-soluble initiator, heating for reaction, and granulating to obtain a weakly cross-linked polymer for plugging oil-based drilling fluid; the high polymer containing active groups is one or more of polybutadiene, polyisoprene, polybutadiene-styrene, polyacrylonitrile-butadiene-styrene and the like. The invention adopts polymer modified common rubber containing active groups to form a core-shell structure product, and uses common rubber powder as a core and the polymer as a shell. The high polymer shell can absorb oil and become sticky in an oil phase environment at 80-120 ℃, has better cohesiveness, and improves the residence capacity of rubber by cohering the leakage layer rock and other leakage blocking materials. The modified rubber is solid at normal temperature, has small influence on rheological property of oil-based drilling fluid, and is convenient to pump to a leakage layer; under the temperature (80-120 ℃) and pressure of a leakage layer, the polymer shell gradually absorbs oil and becomes sticky, so that the residence property of the plugging material is improved; the rubber core still has better elastic deformability, and is favorable for blocking pores with different particle diameters. The modified rubber can effectively solve the problems of difficult residence of common rubber particles in an oil phase environment and the like, improves the plugging performance of plugging materials, and meets the plugging requirement of oil-based drilling fluid.
Detailed Description
The invention provides a high polymer modified rubber plugging material for plugging an oil-based drilling fluid and a preparation method thereof, and the technical parameters can be properly improved by a person skilled in the art by referring to the content of the high polymer modified rubber plugging material. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and they are intended to be within the scope of the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the invention can be practiced and practiced with modification and alteration and combination of the methods and applications herein without departing from the spirit and scope of the invention.
The invention provides a high polymer modified rubber plugging material for plugging an oil-based drilling fluid, which is a core-shell structure material taking a weak crosslinked high polymer with a structure shown in a formula (I) as a shell and rubber as a core;
wherein, m, n and p are polymers, wherein, m is n, p= (200-6,000): (0-1,000): (0-6,000); m is 200-6,000; n is 0 to 1,000; p is 0 to 6,000. Wherein, m is n and p is preferably (200-6,000): (0-1,000): (0-6,000); more preferably (500 to 2,000): (0 to 800): (2,000 to 5,500).
R of the invention 1 An alkyl group of H, C to C10; an alkyl group of preferably H, C to C5; more preferably H, nailA group, ethyl, propyl or butyl, most preferably H or methyl.
R 2 H, C1 to C10 alkyl, C6 to C20 aryl, C1 to C10 alkyl ester; preferably, R 2 H, C1 to C5 alkyl, C6 to C15 aryl, C1 to C5 alkyl ester; more preferably, R 2 H, CH of a shape of H, CH 3 、(CH 2 ) n CH 3 、
COOCH 3 、COOCH 2 CH 3 Or OOCCH (OOCCH) 3 ；
R 3 An alkyl group of H, C to C10; an alkyl group of preferably H, C to C5; more preferably H, methyl, ethyl, propyl or butyl, most preferably H or methyl.
R 4 Is S or
The molecular weight of the weakly crosslinked polymer with the structure of the formula (I) is 80,000 ～ 600,000;
according to the invention, the weakly crosslinked polymer with the structure of the formula (I) is specifically a structure shown in the formulas (I-1) to (I-3):
wherein m, n, p are as defined above.
The rubber is rubber powder; the rubber powder is one or more of natural rubber powder and waste tire rubber powder; the mesh number of the rubber powder is 0.047-25 mm. The source of the present invention is not limited, and those skilled in the art can well know the source.
The invention provides a preparation method of a high polymer modified rubber plugging material for plugging an oil-based drilling fluid, which comprises the following steps:
mixing a polymer containing active groups, rubber, a solvent, an oil-soluble cross-linking agent and an oil-soluble initiator, heating for reaction, and shearing and granulating to obtain a weakly cross-linked polymer for plugging the oil-based drilling fluid;
the high polymer containing active groups is one or more of polybutadiene, polyisoprene, polybutadiene-styrene, polyacrylonitrile-butadiene-styrene and the like.
The preparation method of the high polymer modified rubber plugging material for plugging the oil-based drilling fluid provided by the invention mixes the high polymer containing active groups, rubber, solvent, oil-soluble cross-linking agent and oil-soluble initiator.
Firstly, the polymer containing active groups is dissolved in a solvent or heated and melted, and stirred.
The high polymer containing active groups is one or more of polybutadiene, polyisoprene, polybutadiene-styrene, polyacrylonitrile-butadiene-styrene and the like.
The solvent is one or more of white oil, diesel oil, benzene, ethyl acetate, butyl acrylate or methylene dichloride. The source of the present invention is not limited, and the present invention is commercially available, which is well known to those skilled in the art.
The heating temperature for heating and melting is preferably 70-100 ℃; the time is preferably 5-30 min;
after being dissolved or heated and melted, the mixture is mixed with rubber,
the rubber is rubber powder; the rubber powder is one or more of natural rubber powder and waste tire rubber powder; the particle size of the rubber powder is 0.047-125 mm.
The mass ratio of the polymer containing active groups to the rubber is (5-20): 1.
After mixing, stirring is uniform, and the specific mode of stirring is not limited in the invention, and the method is well known to those skilled in the art.
After the solution is stirred uniformly, mixing with the oil-soluble cross-linking agent, and stirring.
The oil-soluble initiator is preferably one or more of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, tert-butyl hydroperoxide and tert-butyl peroxybenzoate. The source of the present invention is not limited, and the present invention is commercially available, which is well known to those skilled in the art.
And then carrying out heating reaction with an oil-soluble initiator to obtain a reaction product. The method comprises the following steps: after mixing, heating and standing reaction are carried out.
The oil-soluble initiator is one or more of azodiisobutyronitrile, azodiisoheptonitrile, benzoyl peroxide, tert-butyl hydroperoxide and tert-butyl peroxybenzoate. The source of the present invention is not limited, and the present invention is commercially available, which is well known to those skilled in the art.
The mass ratio of the polymer containing active groups, the rubber, the oil-soluble cross-linking agent and the oil-soluble initiator is preferably 100 (0.5-5) to 0.6-6.
The mass ratio of the polymer containing active groups to the solvent is preferably 1: (2-10).
The temperature of the heating reaction is preferably 70-90 ℃; more preferably 75 to 85 ℃; most preferably 80 ℃; the heating reaction time is preferably 6 to 10 hours.
And shearing and granulating the material obtained by the reaction to obtain the weakly crosslinked polymer for plugging the oil-based drilling fluid.
The granulating is specifically carried out by adopting a shearing granulating mode, so that polymer particles with the particle size of 0.47-125 mm are obtained.
One or more polymers containing unsaturated bonds, rubber powder, a cross-linking agent, an initiator and the like are polymerized by a solution method to obtain a gel substance, and the gel substance is granulated to obtain the modified rubber plugging material.
The material of the invention is a core-shell structure product, which takes common rubber powder as a core and polymer as a shell.
The material is modified rubber, so that the surface cohesiveness of the rubber is improved by modification while the elastic deformation of the rubber is ensured, and the residence capacity of the rubber is enhanced; the polymer containing unsaturated bonds has better oil-soluble cohesiveness at a certain temperature, and the polymer wraps the common rubber through the crosslinking effect to form a shell of modified rubber, and has better cohesiveness at a certain temperature.
The product is solid at normal temperature, has small influence on the rheological property of the oil-based drilling fluid, and is convenient to pump to a leakage layer; under the temperature and pressure of the leakage layer, the high polymer shell can absorb oil and become sticky, the leakage layer rock and solid phase particles are bonded, the rubber core can elastically deform, the pores with different particle diameters can be plugged, and finally, the continuous sticky core-shell structure material is formed.
The plugging material can effectively solve the problems that conventional plugging materials such as common rubber are difficult to stay in an oil phase environment, a plugging layer is loose and the like, improve the plugging performance of the plugging material and meet the plugging requirement of oil-based drilling fluid.
The invention provides an oil-based drilling fluid plugging product, which comprises the high polymer modified rubber plugging material for oil-based drilling fluid plugging with the structure of formula (I) in any one of the technical schemes or the high polymer modified rubber plugging material for oil-based drilling fluid plugging prepared by the preparation method of the high polymer modified rubber plugging material for oil-based drilling fluid plugging in any one of the technical schemes.
The invention provides an oil-based drilling fluid plugging product which comprises plugging base slurry and the weak crosslinked polymer for plugging the oil-based drilling fluid with the structure of formula (I) in any one of the technical schemes or the weak crosslinked polymer for plugging the oil-based drilling fluid, which is prepared by the preparation method of the weak crosslinked polymer for plugging the oil-based drilling fluid in any one of the technical schemes.
The addition mass of the high polymer modified rubber plugging material for plugging the oil-based drilling fluid is 2-10%.
The invention is not limited to the plugging base slurry, and the plugging base slurry is well known to those skilled in the art, and is preferably specifically:
the plugging slurry formula comprises the following components: adding a certain amount of cutting agent (suspending agent) into diesel oil to serve as oil-based plugging base slurry;
the cutting agent (suspending agent) is organic soil, polypropylene fiber, emulsifying agent and the like, and the additive mass percentage is 0.2% -5%.
Preparing a sand bed: about 360g of quartz sand with the grain diameter of 40-60 meshes is preheated at 90 ℃ and then added into a visible sand bed medium-pressure plugging instrument;
the plugging experiment of the invention is preferably prepared according to the following method: and adding preheated quartz sand into the sand bed, adding the plugging slurry while the quartz sand is hot, slowly pressurizing, and measuring the pressure-bearing performance, the thickness of the plugging slurry immersed into the sand bed and the leakage condition.
The invention adopts a visual sand bed plugging instrument to evaluate the plugging effect of the high polymer modified rubber plugging material.
The high polymer modified rubber plugging material for plugging the oil-based drilling fluid is prepared from a high polymer containing active groups, has better safety and environmental protection, and has higher activity of conventional lipophilic monomers, and is flammable, explosive and toxic in most cases, so that the product is more beneficial to mass production.
According to the invention, the lipophilic high polymer is adopted to modify the rubber, and the modified rubber has the filling effect of common rubber at the temperature of a plugging layer, has cohesiveness on the surface, can effectively improve the residence property of the rubber in an oil phase environment, can bond plugging materials into an integral slug, enhances the stability of the plugging layer, improves the plugging effect, and has important significance for plugging oil-based drilling.
The invention provides a preparation method of a high polymer modified rubber plugging material for plugging an oil-based drilling fluid, which comprises the following steps: mixing a polymer containing active groups, rubber, a solvent, an oil-soluble cross-linking agent and an oil-soluble initiator, heating for reaction, and granulating to obtain a weakly cross-linked polymer for plugging oil-based drilling fluid; the high polymer containing active groups is one or more of polybutadiene, polyisoprene, polybutadiene-styrene, polyacrylonitrile-butadiene-styrene and the like. The invention adopts polymer modified common rubber containing active groups to form a core-shell structure product, and uses common rubber powder as a core and the polymer as a shell. The high polymer shell can absorb oil and become sticky in an oil phase environment at 80-120 ℃, has better cohesiveness, and improves the residence capacity of rubber by cohering the leakage layer rock and other leakage blocking materials. The modified rubber is solid at normal temperature, has small influence on rheological property of oil-based drilling fluid, and is convenient to pump to a leakage layer; under the temperature (80-120 ℃) and pressure of a leakage layer, the polymer shell gradually absorbs oil and becomes sticky, so that the residence property of the plugging material is improved; the rubber core still has better elastic deformability, and is favorable for blocking pores with different particle diameters. The modified rubber can effectively solve the problems of difficult residence of common rubber particles in an oil phase environment and the like, improves the plugging performance of plugging materials, and meets the plugging requirement of oil-based drilling fluid.
In order to further illustrate the invention, the following describes in detail the polymer modified rubber plugging material for plugging an oil-based drilling fluid and the preparation method thereof.
Example 1
Dissolving 20g of polybutadiene in ethyl acetate, fully dissolving, adding 2g of waste tire rubber powder, 0.8g of cross-linking agent divinylbenzene and 0.8g of initiator AIBN, uniformly stirring, heating to 80 ℃, polymerizing for 6 hours, and granulating to obtain a high polymer plugging material with a core-shell structure, wherein the weak cross-linking shell structural formula (left) and the whole core-shell structural formula (right) are respectively as follows:
wherein the molecular weight is 250,000-330,000, m, p is the degree of polymerization, the range is m: p= (450-560): (4100 to 5100).
Example 2
Dissolving 20g of polyisoprene in ethyl acetate, fully dissolving, adding 2g of natural rubber powder, adding 0.8g of cross-linking agent divinylbenzene and 0.8g of initiator BPO, uniformly stirring, heating to 80 ℃, polymerizing for 6 hours, and granulating to obtain a high polymer plugging material with a core-shell structure, wherein the weak cross-linking shell structure formula (left) and the whole core-shell structure formula (right) are respectively as follows:
wherein the molecular weight is 280,000-350,000, m, p is the degree of polymerization, the range is m: p= (400-750): (3400-4500).
Example 3
10g of polyisoprene and 10g of styrene-butadiene copolymer (copolymer of butadiene and styrene) are dissolved in ethyl acetate, 2g of natural rubber powder, 0.8g of cross-linking agent divinylbenzene and 0.8g of initiator BPO are added after the mixture is fully dissolved, the mixture is heated to 80 ℃ after being stirred uniformly, polymerization is carried out for 6 hours, and granulation is carried out, thus obtaining the high polymer plugging material with a core-shell structure, wherein the weak cross-linking shell structural formula (left) and the whole core-shell structural formula (right) are respectively:
wherein the molecular weight is 250,000-400,000, m, n, p is the degree of polymerization, the range is m: n: p= (800-1,200): (500-800): 3,000-4,000.
Comparative example 1
Dissolving 20g of styrene and 2g of waste tire rubber powder in ethyl acetate, adding 0.8g of cross-linking agent divinylbenzene and 0.8g of initiator azodiisobutyronitrile after fully dissolving, heating to 80 ℃ after fully dissolving, polymerizing for 6 hours, and granulating to obtain the weakly cross-linked high polymer for plugging oil-based drilling fluid, wherein the molecular weight is 50,000 ～ 300,000, and the polymerization degree is 500-3,000.
Comparative example 2
Dissolving 20g of styrene, butyl acrylate and 2g of waste tire rubber powder in ethyl acetate, adding 0.8g of cross-linking agent divinylbenzene and 0.8g of initiator azodiisobutyronitrile after fully dissolving, heating to 80 ℃ after fully dissolving, polymerizing for 6 hours, and granulating to obtain the weakly cross-linked polymer for plugging oil-based drilling fluid, wherein the molecular weight is 80,000 ～ 300,000, and the polymerization degree of the styrene and the butyl acrylate is (500-2,500): (500-1,000).
Comparative example 3
Dissolving 20g of styrene and 2g of waste tire rubber powder in ethyl acetate, adding 0.8g of cross-linking agent oligosiloxane and 0.8g of initiator azodiisobutyronitrile after fully dissolving, heating to 80 ℃ after fully dissolving, polymerizing for 6 hours, and granulating to obtain the weakly cross-linked polymer for plugging oil-based drilling fluid, wherein the molecular weight is 50,000 ～ 300,000, and the polymerization degree is 500-3,000.
The product of the invention is subjected to relevant performance evaluation, and the result is as follows:
(1) Oil absorption multiple test
2g of the products of example 1, example 2, example 3 and comparative examples 1,2 and 3 were respectively added into 40mL of diesel oil, the mixture was placed in a beaker, the mixture was heated under sealing at 90 ℃ for 6 hours, the mixture was filtered while the mixture was still hot, the diesel oil around the product was adsorbed by filter paper, the mass of the product was measured, and the oil absorption multiple was calculated, and the results were shown in Table 1.
TABLE 1
As shown in Table 1, the oil absorption times of the products of the examples are all more than 4.5 times, and the surfaces of the products show better cohesiveness; while the comparative examples hardly absorbed oil, and the surface adhesion was poor.
(2) Evaluation of blocking Property
The visual sand bed plugging instrument is adopted to evaluate the plugging effect of the high polymer modified rubber plugging material.
And (3) preparation of plugging slurry: diesel oil containing 0.3% of cutting agent (suspending agent) is used as plugging base slurry; respectively adding 2% -10% of different products into 150mL of plugging base slurry, uniformly stirring, sealing, and standing for 6h at 90 ℃;
360g of 40-60 mesh quartz sand, and preheating for 1-2h at 90 ℃;
plugging experiment: adding the preheated visible sand bed, adding the plugging slurry while the visible sand bed is hot, slowly pressurizing, and measuring the pressure-bearing performance, the thickness of the plugging slurry immersed in the sand bed, the leakage condition and the leakage speed.
To better illustrate the effect of the plugging material, a comparative experiment was performed using natural rubber particles as a substitute for the product, as comparative example 4.
TABLE 2 results of drop-out measurements
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (3)
1. A high polymer modified rubber plugging material for plugging oil-based drilling fluid is characterized in that:
the preparation method of the high polymer modified rubber plugging material for plugging the oil-based drilling fluid comprises the following steps: mixing a polymer containing active groups, rubber, a solvent, an oil-soluble cross-linking agent and an oil-soluble initiator, heating for reaction, and obtaining a weak cross-linked polymer for plugging oil-based drilling fluid by adopting a shearing granulation mode;
the high polymer containing active groups is one or more of polybutadiene, polyisoprene, polybutadiene-styrene, polyacrylonitrile-butadiene-styrene and the like;
one or more of the solvent white oil, diesel oil, benzene, ethyl acetate, butyl acrylate or methylene dichloride; the oil-soluble initiator is one or more of azodiisobutyronitrile, azodiisoheptonitrile, benzoyl peroxide, tert-butyl hydroperoxide and tert-butyl peroxybenzoate;
the lipophilic cross-linking agent is divinylbenzene;
the rubber is rubber powder; the rubber powder is one or more of natural rubber powder and waste tire rubber powder; the mesh number of the rubber powder is 0.047-125 mm;
the temperature of the heating reaction is 70-90 ℃; the heating reaction time is 6-10 h.
2. The material according to claim 1, wherein the granulation is specifically a shearing granulation method, and polymer particles with a particle size of 0.47-125 mm are obtained.
3. An oil-based drilling fluid plugging product, which is characterized by comprising the high polymer modified rubber plugging material for plugging the oil-based drilling fluid according to any one of claims 1-2.
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