CN117965143B - Compression-resistant composite resin plugging agent and preparation method and application thereof - Google Patents
Compression-resistant composite resin plugging agent and preparation method and application thereof Download PDFInfo
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- CN117965143B CN117965143B CN202410390017.6A CN202410390017A CN117965143B CN 117965143 B CN117965143 B CN 117965143B CN 202410390017 A CN202410390017 A CN 202410390017A CN 117965143 B CN117965143 B CN 117965143B
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- resin
- composite resin
- plugging agent
- monomer
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- 239000000805 composite resin Substances 0.000 title claims abstract description 104
- 238000007906 compression Methods 0.000 title claims abstract description 40
- 230000006835 compression Effects 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 123
- 229920005989 resin Polymers 0.000 claims abstract description 68
- 239000011347 resin Substances 0.000 claims abstract description 68
- 239000011159 matrix material Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 18
- 238000005553 drilling Methods 0.000 claims abstract description 17
- 239000003607 modifier Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 40
- 239000000178 monomer Substances 0.000 claims description 36
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 26
- 239000003822 epoxy resin Substances 0.000 claims description 26
- 229920001568 phenolic resin Polymers 0.000 claims description 26
- 239000005011 phenolic resin Substances 0.000 claims description 26
- 229920000647 polyepoxide Polymers 0.000 claims description 26
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 22
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 19
- 230000000694 effects Effects 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 8
- 238000009849 vacuum degassing Methods 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 7
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 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 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 238000009491 slugging Methods 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 7
- 239000012530 fluid Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 27
- 238000012360 testing method Methods 0.000 description 17
- 239000002002 slurry Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 2
- 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 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 2
- 238000007344 nucleophilic reaction Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- -1 diphenyl glycols Chemical class 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- LADVLFVCTCHOAI-UHFFFAOYSA-N isocyanic acid;toluene Chemical compound N=C=O.CC1=CC=CC=C1 LADVLFVCTCHOAI-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- C09K8/426—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging
-
- 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
-
- 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
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
-
- 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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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mining & Mineral Resources (AREA)
- Geology (AREA)
- Physics & Mathematics (AREA)
- Geochemistry & Mineralogy (AREA)
- Fluid Mechanics (AREA)
- Environmental & Geological Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a compression-resistant composite resin plugging agent, a preparation method and application thereof, and belongs to the technical field of leakage prevention and plugging of drilling fluid. The compression-resistant composite resin plugging agent comprises the following raw materials in percentage by mass: 20-50% of composite resin matrix, 0.05-1.0% of modifier, 0.1-0.5% of tackifying polymer, 0.1-1.2% of cross-linking agent and the balance of water. The compression-resistant composite resin plugging agent is a resin composite plugging material, and compared with single thermosetting resin, multiple thermosetting resins are compounded, and the resin plugging agent has the advantages of all the resins through crosslinking modification, so that the strength and the comprehensive performance of the plugging agent can be greatly improved, and the polymer is tackified, so that the overall adhesion can be improved, the better adhesion of the multiple resins is facilitated, and the temperature resistance of the resin plugging agent can be improved.
Description
Technical Field
The invention relates to a compression-resistant composite resin plugging agent, a preparation method and application thereof, and belongs to the technical field of leakage prevention and plugging of drilling fluid.
Background
The lost circulation is a phenomenon that drilling and completion working fluid leaks into a stratum under the action of pressure difference in underground operations such as drilling, well cementation and testing, so that a large amount of drilling fluid can be lost, the drilling time is delayed, the oil and gas layer is damaged, a series of complex accidents such as blowout, well collapse and drilling sticking can be caused, even the well is scrapped, and great economic loss is caused, and the lost circulation is a worldwide difficult problem. In order to ensure downhole safety, improve drilling speed and save drilling cost, the lost circulation problem must be effectively solved.
The thermosetting resin material is a polymer material which has a three-dimensional crosslinked reticular structure and is insoluble and infusible, and the body type structure endows the material with good pressure resistance, heat resistance and excellent mechanical properties, and the thermosetting resin material is widely used as a high-strength composite material matrix, a coating, an adhesive and the like in various fields, and is one of common and efficient plugging agents. The materials are not consolidated at low temperature, so that the plugging slurry is conveniently pumped to reach a target leakage layer, and can be crosslinked to form a body type consolidated substance when reaching a certain temperature, so as to plug a leakage channel. At present, a single thermosetting resin plugging agent has good effect in field application, but with the deep expansion of oil and gas exploration and development, high temperature and high pressure become one of the main problems faced by drilling plugging, and higher requirements are also provided for the high temperature resistance and high pressure bearing plugging effect of the resin plugging agent.
The Chinese patent document CN110903815A discloses a high-strength plugging slurry which has stable performance, good fluidity and adjustable density, can meet the pressure-bearing requirements of different leakage stratum, has strong retention capacity, is easy to enter different types of leakage channels and retain, has very high plugging strength, has the compression strength reaching 15MPa, and is particularly suitable for high-pressure hard stratum and land parcel layer with high pressure-bearing capacity; however, the plugging slurry has poor temperature resistance, and can not realize long-term pressure-bearing plugging in high-temperature stratum. The Chinese patent document CN116948199A discloses a preparation method of an epoxy resin pressure-bearing plugging material, which comprises the steps of introducing a large number of rigid structures (benzene rings), and carrying out branching reaction in the polymerization process of polyhalogenated polyphenyl rings and diphenyl glycols in raw materials to ensure that the structure of an epoxy resin polymer is highly branched, and combining the epoxy resin with a silane coupling agent, so that the compressive strength of the plugging material is greatly improved by 1-2 times compared with that of the conventional epoxy resin plugging material; however, the preparation method of the plugging material is complicated, the temperature resistance is insufficient, the rigidity is improved, and meanwhile, certain flexibility is lacked, so that the plugging material is not suitable for plugging high-temperature complex stratum.
It can be seen that a single resin plugging agent cannot well meet the field requirements, so that it is necessary to develop a composite resin plugging agent, and the composite resin plugging agent combines the advantages of various resins, so that the composite resin plugging agent has the properties of strong deformation capability before curing, high strength after curing and certain temperature resistance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a compression-resistant composite resin plugging agent, and a preparation method and application thereof. The composite resin of the invention has certain fluidity, is easy to pump into a shaft, has strong deformability, can enter different stratum leakage channels, and can be crosslinked and modified under the action of a modifying crosslinking agent when reaching a certain temperature, so that single oligomeric linear resin is converted into a crosslinked reticular structure consolidation of a composite three-dimensional body, and the detention capability of the composite three-dimensional body in the leakage channels is enhanced, thereby blocking the leakage channels.
The technical scheme of the invention is as follows:
The compression-resistant composite resin plugging agent comprises the following raw materials in percentage by mass: 20-50% of a composite resin matrix, 0.05-1.0% of a modifier, 0.1-0.5% of a tackifying polymer, 0.1-1.2% of a crosslinking agent and the balance of water;
the composite resin matrix is a combination of two or more of epoxy resin, unsaturated polyester resin, urea-formaldehyde resin, phenolic resin, polyurethane resin and organic silicon resin;
The modifier is one or a combination of more of graphene oxide, epoxy terminated polyurethane, isocyanate terminated polyurethane prepolymer (ITPB), silane coupling agent KH550, silane coupling agent KH560 and silane coupling agent KH 570;
the tackifying polymer is copolymer PPAM or sodium polyacrylamide;
The cross-linking agent is one or a combination of more of Diethylenetriamine (DTA), styrene, isophorone diisocyanate, p-toluenesulfonic acid and trimethylolpropane.
According to the invention, the compression-resistant composite resin plugging agent comprises the following raw materials in percentage by mass: 30-45% of composite resin matrix, 0.1-0.5% of modifier, 0.2-0.4% of tackifying polymer, 0.3-0.9% of cross-linking agent and the balance of water.
According to a preferred embodiment of the present invention, the combination of the composite resin matrix is an epoxy resin, an unsaturated polyester resin and a phenolic resin.
Further preferably, in the combination of the composite resin matrix, the mass ratio of the epoxy resin, the unsaturated polyester resin and the phenolic resin is (4-5): (1-2): (1-2).
According to the invention, the modifier is an isocyanate-terminated polyurethane prepolymer (ITPB) with high-activity isocyanate-terminated (-NCO) on the surface, and the preparation method comprises the following steps:
(1) Adding hydroxyl-terminated polybutadiene into a three-neck flask, then adding tetrahydrofuran, stirring to fully dissolve the hydroxyl-terminated polybutadiene, then heating to 90-120 ℃, and carrying out vacuum degassing reaction for 20-40 min at constant temperature;
(2) And cooling the reaction system to 10-20 ℃, sequentially adding a complexing agent and a catalyst, slowly heating to 90-120 ℃, carrying out vacuum degassing reaction at constant temperature for 15-25 min, stopping the reaction, and vacuumizing to obtain the isocyanate-terminated polyurethane prepolymer (ITPB).
Further preferably, in the step (1), the molecular weight of the hydroxyl-terminated polybutadiene is 3000-3500, and the mass ratio of the hydroxyl-terminated polybutadiene to the tetrahydrofuran is 1:5.
It is further preferred that the reaction temperature in step (1) is 100℃and the time for the vacuum degassing reaction is 30 minutes.
It is further preferred that the complexing agent in step (2) is toluene diisocyanate, and the amount of the complexing agent toluene diisocyanate is such that the molar ratio of isocyanate groups (-NCO) in toluene diisocyanate to hydroxyl groups (-OH) in hydroxyl-terminated polybutadiene is 1.3:1, i.e., the mass ratio of complexing agent toluene isocyanate to hydroxyl-terminated polybutadiene is 0.075:1;
the catalyst is dibutyl tin dilaurate or dimethyl cyclohexylamine, and the addition amount of the catalyst is 2% of the mass of the hydroxyl-terminated polybutadiene.
Further preferably, in the step (2), the reaction system is cooled to 15 ℃, the reaction temperature is 100 ℃, and the time of vacuum degassing reaction is 20min.
According to the invention, the tackifying polymer is a copolymer PPAM containing sulfonate (-SO 3 -) acrylamide, acrylic acid and 2-acrylamido-2-sodium methylsulfonate, and the preparation method comprises the following steps:
1) Adding an acrylamide monomer, an acrylic acid monomer, a methacrylamide monomer and a 2-acrylamide-2-methylpropanesulfonic acid monomer into deionized water for full dissolution, and adjusting the pH value to 7-8 by using an alkaline regulator to obtain a mixed solution;
2) And introducing nitrogen into the obtained mixed solution to remove oxygen, heating the mixed solution to 75-85 ℃ under the protection of nitrogen, adding an initiator, reacting for 5-7 h, and washing, crushing and drying to obtain the copolymer PPAM.
Further preferably, in step 1), the mass concentration of the acrylamide monomer in the mixed solution is 15%, the mass concentration of the acrylic acid monomer is 20%, the mass concentration of the methacrylamide monomer is 10%, and the mass concentration of the 2-acrylamido-2-methylpropanesulfonic acid monomer is 30%;
The alkaline regulator is sodium hydroxide, potassium hydroxide or sodium bicarbonate.
Further preferably, in the step 2), the nitrogen introducing and deoxidizing time is 0.5 hour, the reaction temperature is 80 ℃, and the reaction time is 6 hours; the initiator is ammonium persulfate, and the use amount of the initiator, namely the use amount of the ammonium persulfate, is 1% of the total mass of an acrylamide monomer, an acrylic acid monomer, a methacrylamide monomer and a 2-acrylamide-2-methylpropanesulfonic acid monomer.
Further preferably, in the step 2), the washing is performed for 4-6 times by using absolute ethyl alcohol or acetone; the drying condition is that the drying is carried out for 4 hours at 60 ℃.
According to a preferred embodiment of the present invention, the crosslinking agent is a combination of styrene and trimethylolpropane.
Further preferably, the mass ratio of the styrene to the trimethylolpropane is (1-2): 1.
The preparation method of the compression-resistant composite resin plugging agent comprises the following steps:
(a) Heating the resin monomer to 95-105 ℃, vacuumizing for 20-40 min, cooling to 45-55 ℃, pumping in a modifier, heating to 75-85 ℃, and reacting for 1-3 h at constant temperature to obtain a modified resin monomer; finally, mixing the modified resin monomer and the unmodified resin monomer to obtain a composite resin matrix;
(b) Adding the composite resin matrix into water, sequentially adding the cross-linking agent and the tackifying polymer, stirring at 100-400 rpm until the cross-linking agent and the tackifying polymer are completely dissolved, drying and crushing the obtained mixed solution, and thus obtaining the compression-resistant composite resin plugging agent.
According to a preferred embodiment of the invention, in step (a), the heating is carried out to 100 ℃, the evacuation time is 0.5h, the cooling is carried out to 50 ℃, the heating is carried out to 80 ℃, and the isothermal reaction time is 2h.
Further preferably, the modified resin monomer is an epoxy resin, and the unmodified resin monomer is an unsaturated polyester resin and a phenolic resin.
According to the invention, preferably, the stirring rate in the step (b) is 200-300 rpm; the drying condition is that the drying is carried out for 12 hours at 60 ℃.
According to the invention, the application of the compression-resistant composite resin plugging agent is applied to plugging while drilling or plugging by slugging.
Specifically, the compression-resistant composite resin plugging agent is solid powder, can be added into drilling fluid and is used for plugging while drilling; the water-based plugging agent can also be mixed with water, a curing agent and other filling materials to prepare a plugging slurry for plugging the plug.
The invention has the technical characteristics and beneficial effects that:
1. The compression-resistant composite resin plugging agent provided by the invention comprises a composite resin matrix, a modifier, an adhesion-promoting polymer and a crosslinking agent. The modifier can carry out nucleophilic reaction with resin monomer under certain conditions to modify the resin, so that the toughness and strength of the composite resin matrix are effectively improved, and the compressive strength of the plugging agent is improved. For example, the polyurethane prepolymer with the terminal isocyanate groups (-NCO) and the high-activity terminal isocyanate groups on the surface has nucleophilic reaction with the hydroxyl groups (-OH) in the epoxy resin to form an interpenetrating network structure. The cross-linking agent can be subjected to copolymerization and cross-linking reaction with other unmodified resin monomers in the composite resin matrix, so that the physical properties of the composite resin matrix are effectively enhanced, and the compressive strength of the plugging agent is enhanced. For example, the cross-linking agent composed of styrene and trimethylolpropane has good compatibility with unsaturated polyester, and can be subjected to copolymerization and cross-linking reaction with unsaturated double bonds on the main chain of the unsaturated polyester. In addition, each resin monomer in the composite resin matrix can be crosslinked under certain conditions, for example, the hydroxymethyl in the phenolic resin and the hydroxyl and epoxy groups in the epoxy resin are subjected to chemical reaction, the phenolic hydroxyl in the phenolic resin and the epoxy groups in the epoxy resin are subjected to ring-opening reaction, and finally the phenolic hydroxyl and epoxy groups are crosslinked into a complex body structure, so that the compressive strength of the plugging agent is further enhanced, and the plugging effect of the plugging agent is improved.
2. The compression-resistant composite resin plugging agent is a resin composite plugging material, and compared with single thermosetting resin, a plurality of thermosetting resins are compounded, and the resin plugging agent has the advantages of all the resins through crosslinking modification, so that the strength and the comprehensive performance of the plugging agent are greatly improved.
3. The anti-compression composite resin plugging agent provided by the invention is added with the tackifying polymer, SO that the overall adhesion can be improved, multiple resins can be better adhered together, and meanwhile, the tackifying polymer (such as PPAM) contains sulfonate (-SO 3 -), SO that the temperature resistance of the resin plugging agent can be effectively improved.
4. The preparation method of the compression-resistant composite resin plugging agent provided by the invention is simple and easy to operate, and can be added into drilling fluid according to a certain proportion on a drilling site for plugging while drilling; the water-based plugging agent can also be mixed with water, a curing agent and other filling materials to prepare a plugging slurry for plugging the plug.
Detailed Description
The invention is further illustrated, but not limited, by the following examples. The raw materials used in the examples are all conventional raw materials and are commercially available; the methods are prior art unless specified otherwise.
The modifiers and tackifying polymers used in the examples and comparative examples were each prepared as follows.
A preparation method of a modifier-terminated isocyanate-based polyurethane prepolymer (ITPB) comprises the following steps:
(1) 5g of hydroxyl-terminated polybutadiene powder with a molecular weight of 3000 is added into a three-necked flask, 25g of tetrahydrofuran is then added, and stirring is carried out to fully dissolve the powder; then heating to 100 ℃, and vacuum degassing and reacting for 30 minutes at constant temperature;
(2) The reaction system is cooled to 15 ℃, then 0.375g of toluene diisocyanate and 0.1g of dimethyl cyclohexylamine are sequentially added, the temperature is slowly raised to 100 ℃, the vacuum degassing reaction is carried out for 20 minutes at constant temperature, and the vacuum pumping is carried out to obtain the isocyanate-terminated polyurethane prepolymer (ITPB).
A method for preparing an adhesion-promoting polymer copolymer PPAM, comprising the following steps:
1) Adding 7.5g of acrylamide monomer, 10g of acrylic acid monomer, 5g of methacrylamide monomer and 15g of 2-acrylamido-2-methylpropanesulfonic acid monomer into 50mL of deionized water for full dissolution, and adjusting the pH value to 7-8 by using potassium hydroxide to obtain a mixed solution;
2) Transferring the obtained mixed solution into a three-neck flask, sealing the flask, introducing nitrogen to remove oxygen for half an hour, heating, slowly dripping 0.375g ammonium persulfate into the three-neck flask through a constant pressure funnel after the temperature reaches 80 ℃, and reacting for 6 hours; the obtained product is washed by acetone for 5 times, crushed after the product is hardened, placed in a vacuum drying oven and dried for 4 hours at 60 ℃ to obtain the copolymer PPAM.
Example 1
The compression-resistant composite resin plugging agent comprises the following raw materials in percentage by mass: 25% of epoxy resin, 10% of unsaturated polyester resin, 10% of phenolic resin, 0.5% of isocyanate-terminated polyurethane prepolymer, 0.4% of PPAM, 0.6% of styrene, 0.3% of trimethylolpropane and the balance of water.
The preparation method of the compression-resistant composite resin plugging agent comprises the following steps:
(a) Adding epoxy resin into a three-neck flask with a stirrer and a thermometer, heating to 100 ℃, vacuumizing for 30min, cooling to 50 ℃, pumping into an isocyanate-terminated polyurethane prepolymer, heating to 80 ℃, and reacting at constant temperature for 2h to obtain modified epoxy resin; uniformly mixing modified epoxy resin, unsaturated polyester resin and phenolic resin to obtain a composite resin matrix;
(b) Adding the composite resin matrix into water, then sequentially adding styrene, trimethylolpropane and PPAM, and stirring at the speed of 250r/min until the composite resin matrix is completely dissolved to obtain a mixed solution; and (3) placing the mixed solution into a vacuum drying oven, drying at 60 ℃ for 24 hours, and grinding the dried solid to form granular powder to obtain the compression-resistant composite resin plugging agent I 1.
Example 2
The compression-resistant composite resin plugging agent comprises the following raw materials in percentage by mass: 20% of epoxy resin, 5% of unsaturated polyester resin, 5% of phenolic resin, 0.1% of isocyanate-terminated polyurethane prepolymer, 0.2% of PPAM, 0.2% of styrene, 0.1% of trimethylolpropane and the balance of water.
The preparation method of the compression-resistant composite resin plugging agent is as described in example 1, and compression-resistant composite resin plugging agent I 2 is obtained.
Example 3
The compression-resistant composite resin plugging agent comprises the following raw materials in percentage by mass: 25% of epoxy resin, 5% of unsaturated polyester resin, 5% of phenolic resin, 0.3% of isocyanate-terminated polyurethane prepolymer, 0.3% of PPAM, 0.3% of styrene, 0.2% of trimethylolpropane and the balance of water.
The preparation method of the compression-resistant composite resin plugging agent is as described in example 1, and compression-resistant composite resin plugging agent I 3 is obtained.
Example 4
The compression-resistant composite resin plugging agent comprises the following raw materials in percentage by mass: 20% of epoxy resin, 10% of unsaturated polyester resin, 10% of phenolic resin, 0.4% of isocyanate-terminated polyurethane prepolymer, 0.3% of PPAM, 0.4% of styrene, 0.2% of trimethylolpropane and the balance of water.
The preparation method of the compression-resistant composite resin plugging agent is as described in example 1, and compression-resistant composite resin plugging agent I 4 is obtained.
Example 5
The compression-resistant composite resin plugging agent comprises the following raw materials in percentage by mass: 20% of epoxy resin, 5% of unsaturated polyester resin, 5% of phenolic resin, 0.3% of isocyanate-terminated polyurethane prepolymer, 0.2% of PPAM, 0.5% of styrene, 0.3% of trimethylolpropane and the balance of water.
The preparation method of the compression-resistant composite resin plugging agent is as described in example 1, and compression-resistant composite resin plugging agent I 5 is obtained.
Comparative example 1
A resin plugging agent was as described in example 1, except that unsaturated polyester resin was not added.
The preparation method of the resin plugging agent is as described in example 1, and the resin plugging agent II 1 is obtained.
Comparative example 2
A resin plugging agent was as described in example 1, except that no phenolic resin was added.
The preparation method of the resin plugging agent is as described in example 1, and the resin plugging agent II 2 is obtained.
Comparative example 3
A resin plugging agent was as described in example 1, except that unsaturated polyester resin and phenolic resin were not added.
The preparation method of the resin plugging agent is as described in example 1, and the resin plugging agent II 3 is obtained.
Comparative example 4
A resin plugging agent was as described in example 1, except that the isocyanate-terminated polyurethane prepolymer was not added.
The preparation method of the resin plugging agent is as described in example 1, and the resin plugging agent II 4 is obtained.
Comparative example 5
A resin plugging agent was as described in example 1, except that PPAM was not added.
The preparation method of the resin plugging agent is as described in example 1, and the resin plugging agent II 5 is obtained.
Comparative example 6
A resin plugging agent was as described in example 1, except that no styrene was added.
The preparation method of the resin plugging agent is as described in example 1, and the resin plugging agent II 6 is obtained.
Comparative example 7
A resin plugging agent was as described in example 1, except that trimethylolpropane was not added.
The preparation method of the resin plugging agent is as described in example 1, and the resin plugging agent II 7 is obtained.
Comparative example 8
A resin plugging agent was as described in example 1, except that styrene and trimethylolpropane were not added.
The preparation method of the resin plugging agent is as described in example 1, and the resin plugging agent II 8 is obtained.
Test examples
The compressive strength and the plugging effect of the cured product of the compressive composite resin plugging agent are tested.
1. The compressive strength test method of the cured product of the composite resin plugging agent comprises the following steps:
(1) Sample preparation
160G of the composite resin plugging agents prepared in examples 1-5 and comparative examples 1-8 are respectively added into 240ml of water, uniformly stirred at a rotating speed of 300r/min, then 12g of trimethyl hexamethylene diamine curing agent is added, uniformly stirred at a rotating speed of 400r/min, 4 heat-resistant molds with 100ml capacity are filled, and the heat-resistant molds are put into a roller heating furnace to be thermally roll-cured for 5h, 4h, 2h and 1h at a temperature of 100 ℃, 120 ℃, 140 ℃ and 160 ℃ respectively, so that composite resin cured products at different temperatures are obtained. Cooling for 5h at normal temperature after aging, taking out the sample from the tank, and airing until the sample can be subjected to compressive strength test.
(2) Test procedure
The compressive strength of the test sample is tested by using a digital display type hydraulic universal testing machine (model is NGY-WE-100) manufactured by Chongqing Nagra technology Co-Ltd, and the test sample is placed in a compression and bending test space between a lower cross beam and a workbench below the testing machine. The test space is adjusted by the movement of the lower beam, and a load is applied to the surface of the sample. For samples with a strength of more than 10MPa, the loading rate should be 65.7 kN/min.+ -. 3.5kN/min, and the control section of the machine should not be adjusted from the beginning of the deformation of the sample to before the fracture.
2. The method for testing the plugging effect of the composite resin plugging agent comprises the following steps:
(1) Sample preparation
Adding 12g of the composite resin plugging agent prepared in examples 1-5 and comparative examples 1-8 into 18ml of water, uniformly stirring at a rotating speed of 300r/min, adding 0.9g of trimethyl hexamethylenediamine curing agent, uniformly stirring at a rotating speed of 400r/min, filling 4 steel crack models with the length of 10cm and the crack width of 3.0mm, sealing the models, and curing for 5h, 4h, 2h and 1h in a high-temperature ageing furnace at the temperature of 100 ℃, 120 ℃, 140 ℃ and 160 ℃ respectively.
(2) Test method
And testing the plugging effect of the composite resin plugging agent on the cracks by adopting a high-temperature high-pressure plugging testing device, taking out the composite resin plugging agent from an aging furnace after the composite resin plugging agent in the steel crack model is solidified, naturally cooling, injecting well slurry by using a large-displacement horizontal pump for pressurizing, and recording the pressure at the inlet end of the crack model in real time, wherein the highest pressure when the well slurry leaks from the outlet end of the crack model is used as the highest plugging pressure of the composite resin plugging agent on the cracks.
The compression strength and the plugging effect of the cured product of the compression-resistant composite resin plugging agent are tested by adopting the two methods, and the test results are shown in tables 1 and 2.
Table 1, compressive Strength test data after curing resin plugging agent
As can be seen from Table 1, the maximum compressive strength of the cured composite resin plugging agent prepared in examples 1-5 of the present invention is 56MPa, 35MPa, 45MPa, 43MPa and 40MPa respectively at 100 ℃, which exceed 35MPa, which indicates that the cured composite resin plugging agent of the present invention has excellent compressive properties and high strength; however, the compressive strength is reduced with the rise of the temperature, and the compressive strength of the composite resin plugging agent cured at 160 ℃ is the lowest, but still has a certain compressive strength.
In contrast to the composite resin plugging agent prepared in example 1, which is not added with unsaturated polyester resin, the compressive strength of the composite resin plugging agent is reduced after curing, which indicates that the unsaturated polyester resin can improve the strength of the resin plugging agent; in comparative example 2, phenolic resin is not added, and the compressive strength of the composite resin plugging agent is greatly reduced along with the rise of temperature, so that the temperature resistance of the composite resin plugging agent is obviously deteriorated, and the addition of the phenolic resin can effectively improve the temperature resistance of the resin plugging agent; compared with the comparative example 3 and the example 1, the unsaturated polyester resin and the phenolic resin are not added, namely, only the epoxy resin is used for preparing the single resin plugging agent, and from the compressive strength test data, the single resin plugging agent (comparative example 1) has very low strength, which indicates that the composite resin plugging agent can achieve very high compressive property under the combined action of the epoxy resin, the unsaturated polyester resin and the phenolic resin; in comparative example 4, the compressive strength of the cured composite resin plugging agent becomes low without adding the modifier-terminated isocyanate-based polyurethane prepolymer, which just illustrates that the modifier-terminated isocyanate-based polyurethane prepolymer can remarkably improve the mechanical properties of the resin; the comparative example 5, in which the tackifying polymer PPAM was not added, the adhesion between the composite resins was reduced, the compressive strength after curing was reduced, the comparative example 6, in which no styrene was added, and the comparative example 7, in which no trimethylolpropane was added, demonstrated that the crosslinking agents styrene and trimethylolpropane had an effect on the strength of the composite resin plugging agent after curing, and the compressive strength data showed that the effect of the absence of styrene on the composite resin plugging agent strength was greater.
Table 2 test data of crack plugging effect after curing of composite resin plugging agent
As can be seen from Table 2, the composite resin plugging agent prepared in examples 1-5 of the present invention has a good plugging effect on cracks after curing, the highest plugging pressure is generally higher than 10MPa at the medium and low temperature conditions of 100-120 ℃, wherein the highest plugging pressure reaches 21.53MPa, and the highest plugging pressure on cracks after curing is also about 10MPa, so that the composite resin plugging agent of the present invention has excellent pressure-bearing plugging performance.
In comparative example 1, unsaturated polyester resin is not added, and the plugging effect of the obtained composite resin plugging agent is weakened after curing; the comparative example 2 is not added with phenolic resin, and the plugging pressure-bearing performance of the comparative example 2 at 140 ℃ and 160 ℃ is far lower than that of the example 1, so that the temperature resistance of the composite resin plugging agent is obviously reduced, and the addition of the phenolic resin is beneficial to improving the temperature resistance of the resin plugging agent; in the comparative example 3, the unsaturated polyester resin and the phenolic resin are not added, and the plugging effect of a single epoxy resin plugging agent is poor from the view of the plugging effect test data, which indicates that the combination of the unsaturated polyester resin, the phenolic resin and the epoxy resin can lead the composite resin plugging agent to exert good plugging and bearing effects; in comparative example 4, the blocking capacity of the composite resin plugging agent is deteriorated after curing without adding the modifier-terminated isocyanate-based polyurethane prepolymer, which proves that the existence of the modifier-terminated isocyanate-based polyurethane prepolymer is greatly helpful for improving the blocking effect of the resin; the blocking effect of the composite resin plugging agent after curing is weakened by not adding the tackifying polymer PPAM in the comparative example 5; in comparative example 6, no styrene was added, in comparative example 7, no trimethylolpropane was added, and the highest blocking pressure data of both were compared with that of comparative example 8, in which no styrene and no trimethylolpropane were added, to show that the effect of the crosslinking agent styrene on blocking the composite resin blocking agent was greater than that of trimethylolpropane.
As can be seen from the data, the composite resin plugging agent prepared by the embodiment of the invention has excellent compression resistance and plugging performance, which shows that the composite resin plugging agent has the advantage of high strength, and the composite resin plugging agent also has certain temperature resistance due to the addition of phenolic resin, so that the plugging agent can be used for solving the lost circulation problem of a high Wen Shenceng fractured lost stratum.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (6)
1. The compression-resistant composite resin plugging agent is characterized by comprising the following raw materials in percentage by mass: 20-50% of a composite resin matrix, 0.05-1.0% of a modifier, 0.1-0.5% of a tackifying polymer, 0.1-1.2% of a crosslinking agent and the balance of water;
The composite resin matrix is composed of epoxy resin, unsaturated polyester resin and phenolic resin; in the composite resin matrix, the mass ratio of the epoxy resin, the unsaturated polyester resin and the phenolic resin is (4-5): (1-2): (1-2);
The modifier is isocyanate-terminated polyurethane prepolymer;
the tackifying polymer is a copolymer PPAM, and the preparation method comprises the following steps:
1) Adding an acrylamide monomer, an acrylic acid monomer, a methacrylamide monomer and a 2-acrylamide-2-methylpropanesulfonic acid monomer into deionized water for full dissolution, and adjusting the pH value to 7-8 by using an alkaline regulator to obtain a mixed solution;
wherein the mass concentration of the acrylamide monomer in the mixed solution is 15%, the mass concentration of the acrylic acid monomer is 20%, the mass concentration of the methacrylamide monomer is 10%, and the mass concentration of the 2-acrylamide-2-methylpropanesulfonic acid monomer is 30%; the alkaline regulator is sodium hydroxide or sodium bicarbonate;
2) Introducing nitrogen into the obtained mixed solution to remove oxygen, heating the mixed solution to 75-85 ℃ under the protection of nitrogen, adding an initiator, reacting for 5-7 hours, and washing, crushing and drying to obtain a copolymer PPAM;
the initiator is ammonium persulfate, and the use amount of the initiator, namely the use amount of the ammonium persulfate, is 1% of the total mass of an acrylamide monomer, an acrylic acid monomer, a methacrylamide monomer and a 2-acrylamide-2-methylpropanesulfonic acid monomer; the washing is carried out for 4-6 times by using absolute ethyl alcohol or acetone; the drying condition is that the drying is carried out for 4 hours at 60 ℃;
the cross-linking agent is a combination of styrene and trimethylolpropane; the mass ratio of the styrene to the trimethylolpropane is (1-2) 1;
the preparation method of the compression-resistant composite resin plugging agent is characterized by comprising the following steps of:
(a) Heating the resin monomer to 95-105 ℃, vacuumizing for 20-40 min, cooling to 45-55 ℃, pumping in a modifier, heating to 75-85 ℃, and reacting for 1-3 h at constant temperature to obtain a modified resin monomer; finally, mixing the modified resin monomer and the unmodified resin monomer to obtain a composite resin matrix;
wherein the modified resin monomer is epoxy resin, and the unmodified resin monomer is unsaturated polyester resin and phenolic resin;
(b) Adding the composite resin matrix into water, sequentially adding the cross-linking agent and the tackifying polymer, stirring at 100-400 rpm until the cross-linking agent and the tackifying polymer are completely dissolved, drying and crushing the obtained mixed solution, and thus obtaining the compression-resistant composite resin plugging agent.
2. The pressure-resistant composite resin plugging agent according to claim 1, wherein the pressure-resistant composite resin plugging agent comprises the following raw materials in percentage by mass: 30-45% of composite resin matrix, 0.1-0.5% of modifier, 0.2-0.4% of tackifying polymer, 0.3-0.9% of cross-linking agent and the balance of water.
3. The pressure-resistant composite resin plugging agent according to claim 1, wherein the modifier is an isocyanate-terminated polyurethane prepolymer with high-activity isocyanate-terminated groups on the surface, and the preparation method comprises the following steps:
(1) Adding hydroxyl-terminated polybutadiene into a three-neck flask, then adding tetrahydrofuran, stirring to fully dissolve the hydroxyl-terminated polybutadiene, then heating to 90-120 ℃, and carrying out vacuum degassing reaction for 20-40 min at constant temperature;
The molecular weight of the hydroxyl-terminated polybutadiene is 3000-3500, and the mass ratio of the hydroxyl-terminated polybutadiene to the tetrahydrofuran is 1:5, a step of;
(2) Cooling the reaction system to 10-20 ℃, sequentially adding a complexing agent and a catalyst, slowly heating to 90-120 ℃, performing vacuum degassing reaction at constant temperature for 15-25 min, stopping the reaction, and vacuumizing to obtain an isocyanate-terminated polyurethane prepolymer;
Wherein the complexing agent is toluene diisocyanate, and the dosage of the complexing agent toluene diisocyanate is such that the molar ratio of isocyanate groups in toluene diisocyanate to hydroxyl groups in hydroxyl-terminated polybutadiene is 1.3:1;
The catalyst is dibutyl tin dilaurate or dimethyl cyclohexylamine, and the addition amount of the catalyst is 2% of the mass of the hydroxyl-terminated polybutadiene.
4. The pressure-resistant composite resin plugging agent according to claim 1, wherein in step (a), said heating is performed to 100 ℃, said evacuation time is 0.5h, said cooling is performed to 50 ℃, said heating is performed to 80 ℃, and said constant temperature reaction time is 2h.
5. The pressure-resistant composite resin plugging agent according to claim 1, wherein the stirring rate in the step (b) is 200 to 300 rpm; the drying condition is that the drying is carried out for 12 hours at 60 ℃.
6. The use of the pressure-resistant composite resin plugging agent according to claim 1, wherein the agent is applied to plugging while drilling or plugging by slugging.
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