CN117965145B - Capsule curing agent for delaying resin curing and preparation method and application thereof - Google Patents
Capsule curing agent for delaying resin curing and preparation method and application thereof Download PDFInfo
- Publication number
- CN117965145B CN117965145B CN202410362380.7A CN202410362380A CN117965145B CN 117965145 B CN117965145 B CN 117965145B CN 202410362380 A CN202410362380 A CN 202410362380A CN 117965145 B CN117965145 B CN 117965145B
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- Prior art keywords
- capsule
- resin
- curing
- curing agent
- plugging
- Prior art date
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- 239000002775 capsule Substances 0.000 title claims abstract description 162
- 229920005989 resin Polymers 0.000 title claims abstract description 118
- 239000011347 resin Substances 0.000 title claims abstract description 118
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 107
- 238000001723 curing Methods 0.000 title claims description 209
- 238000002360 preparation method Methods 0.000 title abstract description 28
- 238000005553 drilling Methods 0.000 claims abstract description 22
- 239000002002 slurry Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000012530 fluid Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 62
- 239000002270 dispersing agent Substances 0.000 claims description 52
- 239000011162 core material Substances 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 41
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 36
- -1 polymethylene urea Polymers 0.000 claims description 34
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 32
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 31
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 31
- 239000003999 initiator Substances 0.000 claims description 29
- 239000003995 emulsifying agent Substances 0.000 claims description 28
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000004793 Polystyrene Substances 0.000 claims description 21
- 229920002223 polystyrene Polymers 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 19
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 229920003987 resole Polymers 0.000 claims description 18
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 16
- WVJKSRJWLIVTGA-UHFFFAOYSA-M 2-hydroxyethyl-dimethyl-octadecylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCCCCCCCCCCCCCCCC[N+](C)(C)CCO WVJKSRJWLIVTGA-UHFFFAOYSA-M 0.000 claims description 16
- 229910019142 PO4 Inorganic materials 0.000 claims description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 16
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 16
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 16
- 239000010452 phosphate Substances 0.000 claims description 16
- 229920000570 polyether Polymers 0.000 claims description 16
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 15
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- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 14
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 12
- 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 12
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 12
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- ZWGSXIDHYSLQGT-UHFFFAOYSA-N 3-hydroxypropyl dimethyl phosphate Chemical compound P(=O)(OCCCO)(OC)OC ZWGSXIDHYSLQGT-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
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- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000007596 consolidation process Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- ZDWQSEWVPQWLFV-UHFFFAOYSA-N C(CC)[Si](OC)(OC)OC.[O] Chemical compound C(CC)[Si](OC)(OC)OC.[O] ZDWQSEWVPQWLFV-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
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- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000003111 delayed effect Effects 0.000 description 16
- 229920000058 polyacrylate Polymers 0.000 description 14
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
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- 235000001014 amino acid Nutrition 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- 239000001099 ammonium carbonate Substances 0.000 description 2
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- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
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- 239000011258 core-shell material Substances 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
The invention relates to a capsule curing agent for delaying resin curing, and a preparation method and application thereof, belonging to the technical field of leakage prevention and stoppage of drilling fluid. The capsule curing agent can delay the curing time of resin under high temperature and high pressure conditions, so that the resin plugging slurry keeps certain fluidity in the drilling process, is favorable for smooth drilling operation, avoids drilling sticking accidents, has good stability, can keep longer activity in the resin plugging slurry, ensures the stability of the resin plugging slurry and forms a high-strength consolidated body after curing.
Description
Technical Field
The invention relates to a capsule curing agent for delaying resin curing, a preparation method and application thereof, in particular to a capsule curing agent suitable for ultra-deep delayed resin curing, a preparation method and application thereof, and belongs to the technical field of leakage prevention and plugging of drilling fluid.
Background
In deep or ultra-deep drilling, stratum rock has high hardness, high abrasiveness and complex ground stress, and is always in a high-temperature and high-pressure state, and all factors bring great challenges to drilling engineering. For example, high temperatures can cause changes in drilling fluid properties and instability of the borehole wall, and high pressures can cause safety issues such as lost circulation, blowout, and the like. Thus, conventional drilling fluid plugging materials tend to be difficult to meet these requirements. The resin is used as a widely applied material, can undergo a crosslinking curing reaction between molecules at a certain temperature to generate a high-strength consolidated body, and is suitable for high-pressure-bearing plugging; meanwhile, the consolidated body has good temperature resistance, and is suitable for plugging high-temperature stratum. Thus, its curing process is critical to the properties of the final material. However, the curing time of the conventional resin is poor in controllability under the high-temperature condition, and particularly, the curing time of the resin under the high-temperature condition is greatly shortened, so that accidents such as sticking of a drill and the like are easily caused.
With the progress of technology, the application field of the capsule curing agent for delaying the curing of resin is expanding continuously, and the application field of the capsule curing agent is potential in extreme environments such as deep sea and underground engineering. In a deep sea environment, the pressure of sea water is huge, the requirement on the performance of the material is extremely high, and the slow curing of resin can be realized in the deep sea environment by using a capsule curing agent for delaying curing, so that the pressure resistance and the corrosion resistance of the material are improved; when engineering construction is carried out in the deep underground, severe environments such as high temperature, high pressure and the like are frequently encountered, and the capsule curing agent for delaying curing can realize slow curing of resin in the deep underground, so that the temperature resistance and the compression resistance of the material are improved; in the preparation of certain specialty materials, it is desirable to achieve delayed curing of the resin to achieve specific properties. For example, in a composite material, good wetting between the fibers and the resin can be achieved by delaying curing, improving the mechanical properties of the composite material.
The core technology of the encapsulated curing agent is how to effectively encapsulate the curing agent and trigger its release when needed. At present, various microencapsulation techniques have been applied in this field, and the encapsulation methods can be broadly classified into three types, chemical methods, physical methods and physicochemical methods, and the chemical methods include interfacial polymerization methods, in-situ polymerization methods, complex coacervation methods, etc., and the main challenges of these techniques are to achieve uniformity, stability and controlled release kinetics of the capsules. To achieve delayed curing under specific conditions, researchers are exploring various chemical reaction mechanisms and physical methods. For example, delayed curing of the resin may be achieved by adjusting the activity of the curing agent, using a retarder, or designing a specific reaction path. In addition, environmental factors such as temperature, pressure, and pH are also used as conditions for triggering curing.
Patent document CN201110214376.9 discloses a preparation method of a latent microcapsule curing agent and an adhesive thereof for initiating thermosetting epoxy resin curing at medium temperature, which uses a high-activity medium-temperature curing agent as a core material, thermoplastic polymer microspheres as wall materials, adopts a solvent volatilization technology to prepare the latent microcapsule curing agent with better curing performance and latency performance, and applies the latent microcapsule curing agent to an epoxy resin system to prepare a single-component medium-temperature curing epoxy resin adhesive. The microcapsule curing agent core material is one or more of boron trifluoride and amine complex thereof, aromatic polyamine, polyamine salt, alicyclic amine, organic acid hydrazide and the like; the wall material is one or more of polyethylene-based microspheres, polystyrene-based microspheres and polyacrylate-based microspheres, the core material and the wall material have poor high-temperature and high-pressure resistance, and the curing agent is easy to release in advance under ultra-deep high-temperature and high-pressure conditions, so that the curing time of the resin of the microcapsule curing agent under high-temperature conditions is greatly shortened, and the effect under high-temperature and high-pressure conditions is greatly reduced.
Patent document CN202110147729.1 discloses a polyimide shell for a microcapsule type curing agent and a preparation method thereof, the polyimide shell reduces the temperature of the polyimide shell when initially melting by introducing aliphatic diamine containing alkyne structure, so that the curing agent in the polyimide shell can be released and contacted with matrix resin, and the polyimide shell can undergo self-crosslinking reaction at 200-300 ℃, thereby improving the heat resistance of the polyimide shell, avoiding the problem of deterioration of the heat resistance of the resin caused by poor heat resistance of the shell, but the controllability of the curing time is poor under the conditions of high temperature and high pressure, and the release rate of the curing agent can not be accurately mastered.
The capsule curing agent commonly used at present is mostly suitable for traditional conditions such as coating, adhesive, composite material manufacturing, 3D printing, biomedicine, microelectronics and the like, and has less application to delay resin curing under high-temperature and high-pressure severe environments such as deep layers or ultra-deep layers.
Therefore, development of a novel capsule curing agent suitable for delayed resin curing under deep or ultra-deep high temperature and high pressure conditions has become an urgent need.
Disclosure of Invention
Aiming at the defects of the prior art, in particular to the problems of poor controllability of curing time and curing strength and the like of the existing curing agent under high-temperature and high-pressure severe environments such as deep ultra-deep layers and the like, the invention provides a capsule curing agent for delaying resin curing, and a preparation method and application thereof.
The capsule curing agent can delay the curing time of the resin under high temperature and high pressure, so that the resin plugging slurry keeps certain fluidity in the drilling process, the smooth drilling operation is facilitated, and the drilling sticking accident is avoided; by delaying the resin curing time, the capsule curing agent can reduce the viscosity of the resin plugging slurry and reduce the resistance in the drilling process, thereby improving the drilling efficiency; the capsule curing agent has good stability, can keep activity for a long time in the resin plugging slurry, ensures the stability of the resin plugging slurry and forms a high-strength consolidated body after curing; meanwhile, the concentration of the capsule curing agent can be adjusted, so that the action time of the capsule curing agent can be adjusted, and a drilling engineer can flexibly control the capsule curing agent according to actual requirements.
The technical scheme of the invention is as follows:
The capsule curing agent for delaying resin curing comprises the following raw materials in percentage by mass: 5-40% of capsule core material, 2-30% of capsule wall material, 0.1-5% of dispersing agent, 0.1-2.5% of emulsifying agent, 0.1-1.5% of initiator and the balance of water, wherein the total content of all components is hundred percent;
The capsule core material is a combination of more than two of aromatic polyamine, resol, dicyandiamide, p-toluenesulfonic acid, hexamethylenetetramine, polyethylene glycol, hydrogen diamine phosphate and ammonium persulfate;
the capsule wall material is a combination of more than two of polyvinyl, polystyrene, polyacrylate, polyvinyl chloride, polyamide, polyoxymethylene, polymethylene urea, polyphenyl ether and polysulfone.
According to a preferred embodiment of the present invention, the aromatic polyamine is one or a combination of two or more of diaminodiphenyl methane, diaminodimethoxy diphenyl methane, diaminodicyclohexyl methane, diaminodichloro diphenyl methane, m-phenylenediamine, and diaminodiphenyl sulfone.
According to the invention, the capsule core material is preferably one of resol, dicyandiamide, p-toluenesulfonic acid, hexamethylenetetramine, polyethylene glycol, hydrogen diamine phosphate and ammonium persulfate.
According to the invention, the capsule core material is a combination of resol, dicyandiamide, p-toluenesulfonic acid and ammonium persulfate, wherein the mass ratio of the resol to the dicyandiamide to the p-toluenesulfonic acid to the ammonium persulfate is (3-6): (1-5): (1-3): (0.5-2).
The capsule core material has the curing effect and is high-temperature-resistant and high-pressure-resistant.
According to the invention, the capsule wall material is preferably a combination of polyvinyl, polystyrene, polyacrylate and polymethylene urea.
According to the present invention, the polyvinyl group is preferably one or a combination of two or more of polyvinyl acetate, polyvinyl alcohol and polyvinyl acetal.
According to a preferred embodiment of the present invention, the polystyrene is one or a combination of two or more of polystyrene, a styrene-acrylonitrile copolymer, a styrene-methyl methacrylate copolymer, and a styrene-divinylbenzene copolymer.
According to the present invention, the polyacrylate is preferably one or a combination of two or more of polymethyl methacrylate, a copolymer of methyl methacrylate and styrene, poly-alpha-methyl chloroacrylate or poly-alpha-methyl cyanoacrylate.
According to a preferred embodiment of the invention, the wall material is a combination of polyvinyl alcohol, polystyrene, polymethyl methacrylate and polymethylene urea.
Further preferably, the mass ratio of polyvinyl alcohol, polystyrene, polymethyl methacrylate to polymethylene urea is (0.5-2): (1-3): (1-5): (1-8).
According to the present invention, the dispersant is preferably an anionic dispersant, a cationic dispersant, a nonionic dispersant, an amphoteric dispersant, or a polymer dispersant, or a combination of two or more thereof;
Further preferably, the dispersant is a combination of an anionic dispersant, a cationic dispersant, an amphoteric dispersant, and a polymeric dispersant.
According to the invention, preferably, the anionic dispersing agent is one or a combination of two or more of fatty acid salts, phosphate salts and sulfonate salts;
Further preferably, the fatty acid salt dispersant is one or a combination of two or more of hexadecanoic acid, octadecanoic acid and dodecanoic acid.
Further preferably, the phosphate salt dispersant is one or a combination of two or more of fatty alcohol polyether phosphate, alkylphenol polyether phosphate and aryl phenol polyether phosphate.
Further preferably, the sulfonate dispersant is one or a combination of two or more of potassium lignin sulfonate, dodecylbenzene sulfonic acid and sodium hydroxyethane sulfonate.
According to the invention, the cationic dispersing agent is one or a combination of two of ammonium salt, quaternary ammonium salt and pyridinium salt.
Further preferably, the ammonium salt is one or a combination of two or more of ammonium chloride, ammonium sulfate, ammonium bisulfate, ammonium nitrate, ammonium carbonate and ammonium bicarbonate;
Further preferably, the quaternary ammonium salt is one or a combination of two or more of benzalkonium chloride, alkyl trimethyl quaternary ammonium salt, dodecyl trimethyl ammonium chloride, alkyl dimethyl benzyl quaternary ammonium salt, alkyl dimethyl hydroxyethyl quaternary ammonium salt, octadecyl dimethyl hydroxyethyl ammonium nitrate and octadecyl dimethyl hydroxyethyl ammonium perchlorate.
According to the invention, the nonionic dispersant is preferably one or a combination of two or more of fatty alcohol polyoxyethylene ether, polyalcohol and polyvinylpyrrolidone.
Further preferably, the polyhydric alcohol is one or a combination of two or more of pentaerythritol, ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane and glycerol.
According to the invention, preferably, the amphoteric dispersant is one or a combination of two of amino acid type and betaine type;
Further preferably, the amino acid type dispersing agent is one or a combination of two or more of N-alkyl amino acid, N-dodecyl glutamic acid and N-dodecyl aspartic acid;
Further preferably, the betaine type dispersing agent is one or a combination of two or more of alkyl dimethyl betaine, alkyl dimethyl sulfoethyl betaine, alkyl dimethyl sulfopropyl betaine, hydroxy sulfopropyl betaine and alkyl dimethyl hydroxypropyl phosphate betaine.
According to the present invention, the polymeric dispersant is preferably one or a combination of two of polyacrylate, polycarboxylic acid, and water-soluble high polymer.
Further preferably, the polyacrylate dispersant is one or a combination of two or more of sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, calcium polyacrylate, magnesium polyacrylate, zinc polyacrylate, aluminum polyacrylate, iron polyacrylate and cobalt polyacrylate.
Further preferably, the water-soluble high molecular polymer dispersant is one or a combination of two of gelatin, methylcellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyacrylate, polymethacrylic acid and maleic anhydride-styrene copolymer.
Most preferably, the dispersant is a combination of alkylphenol polyether phosphate, dodecylbenzene sulfonic acid, octadecyl dimethyl hydroxyethyl ammonium perchlorate, polyvinyl alcohol and alkyl dimethyl hydroxypropyl phosphate betaine, and the mass ratio of alkylphenol polyether phosphate to dodecylbenzene sulfonic acid to octadecyl dimethyl hydroxyethyl ammonium perchlorate to polyvinyl alcohol to alkyl dimethyl hydroxypropyl phosphate betaine is 1:1:3: (1-5): (1-8).
According to the invention, the emulsifier is one or a combination of two or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, tween 60 and span 80.
According to the invention, the initiator is preferably one or a combination of two or more of gamma-aminopropyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, gamma-mercaptopropyl triethoxysilane, benzoyl peroxide and tert-butyl hydroperoxide.
The capsule curing agent obtained from the capsule core material and the capsule wall material of the invention delays the curing time of the resin under the conditions of high temperature and high pressure, and the capsule wall material of the capsule curing agent is urea resin copolymer, so that the capsule has better temperature resistance, and the core-shell structure of the capsule curing agent is not damaged temporarily under the conditions of high temperature and high pressure, the curing agent is wrapped in the core-shell, the release of the curing agent is delayed, and the resin is not cured rapidly, thereby playing the role of delaying the curing of the resin.
The preparation method of the capsule curing agent for delaying resin curing comprises the following steps:
(1) According to the proportion, the dispersing agent is dissolved in deionized water to disperse the solution A;
(2) Adding the core material into the dispersion solution A, and fully and uniformly mixing to obtain a mixture B;
(3) Adding an emulsifier into the mixture B, and uniformly mixing under the protection of inert gas to obtain a mixture C;
(4) Adding an initiator into the mixture C, and uniformly mixing and stirring under the protection of inert gas to obtain a mixture D;
(5) And adding a capsule wall material into the mixture D, mixing and stirring uniformly under the protection of inert gas, and obtaining the product capsule curing agent through centrifugal suction filtration, washing and drying.
The capsule curing agent obtained by the invention is a microcapsule, and the addition sequence of materials ensures that the capsule wall is arranged at the outer layer and the capsule core is arranged at the inner layer.
According to the present invention, preferably, in the step (1), the dissolution is performed under stirring conditions at a stirring temperature of 30 to 60℃at a stirring speed of 100 to 600rpm for 10 to 50 minutes.
Further preferably, in the step (1), the stirring temperature is 40-50 ℃; stirring speed is 300-500 rpm; the stirring time is 20-30 minutes.
Preferably, according to the present invention, in step (2), the mixing is performed under stirring conditions; stirring at 25-75deg.C; the stirring speed is 300-700 rpm; the stirring time is 60-100 minutes.
Further preferably, in the step (2), the stirring temperature is 50-60 ℃; the stirring speed is 400-500 rpm; the stirring time is 75-85 minutes.
Preferably, according to the present invention, in step (3), the mixing is performed under stirring conditions; stirring at 40-70deg.C; the stirring speed is 200-600 rpm; stirring for 80-120 min; the inert gas is nitrogen.
Further preferably, in the step (3), the stirring temperature is 55-65 ℃; the stirring speed is 350-450 rpm; the stirring time is 100-110 minutes.
Preferably, according to the present invention, in step (4), the mixing is performed under stirring conditions; stirring at 60-80deg.C; stirring at 400-800 rpm; the stirring time is 240-300 minutes.
Further preferably, in the step (4), the stirring temperature is 65-70 ℃; the stirring speed is 550-650 rpm; the stirring time is 265-275 minutes.
According to the invention, in the step (5), the pumping filtration device is an SHC-10 type vacuum pump, the pumping filtration temperature is 25 ℃, the centrifugal device is a TG16G table type high-speed centrifugal machine, the centrifugal temperature is 25 ℃, and the washing reagent is deionized water.
According to the invention, in the step (5), the drying is carried out for 10-24 hours under the condition that the vacuum degree is 0.08-0.1MPa and the temperature is 90-99 ℃; preferably, the drying is carried out under the condition that the vacuum degree is 0.08-0.1MPa and the temperature is 93-95 ℃ for 16-20 hours.
The capsule curing agent is applied to plugging of curable resin of deep or ultra-deep drilling fluid and delay of resin curing.
The preferred specific application method according to the invention is as follows:
The capsule curing agent and the curable resin plugging material are dissolved in water on the ground to prepare resin plugging slurry which is directly injected into a plugging layer, the capsule curing agent is excited to release the capsule core material under the formation temperature condition to trigger the resin to generate a crosslinking curing reaction to form a high-strength consolidation slug plugging layer, and the addition amount of the capsule curing agent is 2-5wt% of the curable resin plugging material.
Or the capsule curing agent and the curable resin plugging material are dissolved in water on the ground to prepare resin plugging slurry, and then the resin plugging slurry and the bridging type leakage plugging material are used together to be injected into a plugging layer, and the capsule curing agent is excited to release the capsule core material under the formation temperature condition to trigger the resin to adhere to the bridging type leakage plugging material to be cured to form an integral slug plugging layer, wherein the dosage of the capsule curing agent is 10-20g per liter of resin plugging slurry.
The invention has the technical characteristics and beneficial effects that:
1. the capsule curing agent for delaying the curing of the resin can delay the curing reaction of the resin under the conditions of high temperature and high pressure, and can maintain certain fluidity of the resin plugging slurry in the drilling process by precisely controlling the curing time and degree of the resin, reduce the viscosity of the resin plugging slurry and reduce the resistance in the drilling process, thereby improving the drilling efficiency.
2. The capsule curing agent for delaying the curing of the resin has good stability, can keep activity for a long time in the resin plugging slurry, and can ensure the curing of the resin plugging slurry under the optimal condition and form a high-strength consolidated body after the curing, thereby improving the quality and performance of the resin.
3. The capsule curing agent for delaying resin curing can realize accurate regulation and control of resin curing time and strength by adjusting components and proportion of the capsule curing agent, and is convenient for drilling engineers to flexibly control according to actual field requirements. Meanwhile, compared with the traditional curing agent, the capsule curing agent has lower volatility and toxicity, and has smaller influence on the environment and human health.
4. The capsule curing agent for delaying resin curing can be prepared into resin plugging slurry which is directly injected into a leakage layer by being dissolved with a curable resin plugging material in water on the ground, can be used together with a bridging type leakage-proof plugging material to be injected into the leakage layer, and can trigger the resin to adhere the bridging type leakage-proof plugging material to be cured to form an integral slug plugging layer under the formation temperature condition.
5. The capsule curing agent obtained from the capsule core material and the capsule wall material of the invention delays the curing time of resin under the conditions of high temperature and high pressure, the capsule core material contains resin materials and has the characteristic of high temperature and high pressure resistance, and the capsule wall material has the material of synthetic urea formaldehyde resin such as polyoxymethylene or polymethylene urea and the like, so that the capsule curing agent has higher temperature resistance and pressure resistance, therefore, the capsule curing agent obtained from the capsule core material and the capsule wall material meets the specific requirements of ultra-deep environment, and has important significance for solving the curing time and strength of the curable resin materials in the ultra-deep environment.
Detailed Description
The invention is further illustrated by, but not limited to, the following specific 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.
Example 1
The capsule curing agent for delaying resin curing is prepared from the following raw materials in percentage by mass:
40% of capsule core material, 20% of capsule wall material, 3% of dispersing agent, 2% of emulsifying agent, 1% of initiator and the balance of water, wherein the total content of all components is hundred percent;
the capsule core material is a combination of resol, dicyandiamide, p-toluenesulfonic acid and ammonium persulfate, wherein the mass ratio of the resol to the dicyandiamide to the p-toluenesulfonic acid to the ammonium persulfate is 5:3:2:1.
The capsule wall material is a combination of polyvinyl alcohol, polystyrene, polymethyl methacrylate and polymethylene urea, wherein the mass ratio of the polyvinyl alcohol to the polystyrene to the polymethyl methacrylate to the polymethylene urea is 1:2:4:5.
The dispersing agent is a combination of alkylphenol polyether phosphate, dodecylbenzene sulfonic acid, octadecyl dimethyl hydroxyethyl ammonium perchlorate, polyvinyl alcohol and alkyl dimethyl hydroxypropyl phosphate betaine, wherein the mass ratio of the alkylphenol polyether phosphate to the dodecylbenzene sulfonic acid to the octadecyl dimethyl hydroxyethyl ammonium perchlorate to the polyvinyl alcohol is 1:1:3:5:7.
The emulsifier is a combination of sodium dodecyl benzene sulfonate, tween 60 and Span 80, wherein the mass ratio of the sodium dodecyl benzene sulfonate, the Tween 60 and the Span 80 is 1:2:3.
The initiator is a combination of 3-glycidoxypropyl trimethoxysilane, benzoyl peroxide and tert-butyl hydroperoxide, wherein the mass ratio of the 3-glycidoxypropyl trimethoxysilane to the benzoyl peroxide to the tert-butyl hydroperoxide is 1:2:3.
The preparation method of the capsule curing agent for delaying resin curing comprises the following steps:
(1) Weighing and dissolving a dispersing agent in deionized water according to the proportion, uniformly stirring for 25 minutes at the stirring speed of 400 revolutions per minute under the condition of the temperature of 45 ℃ until the dispersing agent is completely dissolved, and then cooling to 25 ℃ to prepare a dispersing liquid A;
(2) Adding a core material into the dispersion liquid A, heating to 55 ℃, and uniformly stirring at a stirring speed of 450 r/min for 80 min to obtain a mixture B;
(3) Adding an emulsifier into the mixture B, introducing nitrogen at an injection speed of 10 mL/min for nitrogen protection, heating to 60 ℃, and uniformly stirring at a stirring speed of 400 rpm for 105 minutes to obtain a mixture C;
(4) Adding an initiator into the mixture C, heating to 70 ℃, and uniformly stirring at a stirring speed of 600 revolutions per minute for 270 minutes to obtain a mixture D;
(5) Adding a capsule wall material into the mixture D, fully and uniformly stirring, cooling to room temperature of 25 ℃, centrifuging by using a TG16G table type high-speed centrifuge, carrying out suction filtration by using an SHC-10 type vacuum pump, washing by using deionized water after the suction filtration is finished, and drying for 18 hours under the conditions of vacuum degree of 0.1MPa and temperature of 95 ℃ after the washing is finished, so as to obtain solid particles, namely the capsule curing agent for delaying resin curing, and marking as a sample A1.
Example 2
The capsule curing agent for delaying resin curing is prepared from the following raw materials in percentage by mass: 15% of capsule core material, 30% of capsule wall material, 3% of dispersing agent, 2% of emulsifying agent, 1% of initiator and the balance of water, wherein the total content of all components is hundred percent;
the capsule core material is a combination of resol, dicyandiamide, p-toluenesulfonic acid and ammonium persulfate, wherein the mass ratio of the resol to the dicyandiamide to the p-toluenesulfonic acid to the ammonium persulfate is 5:3:2:1.
The capsule wall material is a combination of polyvinyl alcohol, polystyrene, polymethyl methacrylate and polymethylene urea, wherein the mass ratio of the polyvinyl alcohol to the polystyrene to the polymethyl methacrylate to the polymethylene urea is 1:2:4:5.
The dispersing agent is a combination of alkylphenol polyether phosphate, dodecylbenzene sulfonic acid, octadecyl dimethyl hydroxyethyl ammonium perchlorate, polyvinyl alcohol and alkyl dimethyl hydroxypropyl phosphate betaine, wherein the mass ratio of the alkylphenol polyether phosphate to the dodecylbenzene sulfonic acid to the octadecyl dimethyl hydroxyethyl ammonium perchlorate to the polyvinyl alcohol is 1:1:3:5:7.
The emulsifier is a combination of sodium dodecyl benzene sulfonate, tween 60 and Span 80, wherein the mass ratio of the sodium dodecyl benzene sulfonate, the Tween 60 and the Span 80 is 1:2:3.
The initiator is a combination of 3-glycidoxypropyl trimethoxysilane, benzoyl peroxide and tert-butyl hydroperoxide, wherein the mass ratio of the 3-glycidoxypropyl trimethoxysilane to the benzoyl peroxide to the tert-butyl hydroperoxide is 1:2:3.
Preparation of a resin curing delayed capsule curing agent the preparation of the resin curing delayed capsule curing agent was carried out as in example 1 and was designated as sample A2.
Example 3
The capsule curing agent for delaying resin curing is prepared from the following raw materials in percentage by mass: 40% of capsule core material, 20% of capsule wall material, 1% of dispersing agent, 1% of emulsifying agent, 0.5% of initiator and the balance of water, wherein the total content of all components is hundred percent;
the capsule core material is a combination of resol, dicyandiamide, p-toluenesulfonic acid and ammonium persulfate, wherein the mass ratio of the resol to the dicyandiamide to the p-toluenesulfonic acid to the ammonium persulfate is 5:3:2:1.
The capsule wall material is a combination of polyvinyl alcohol, polystyrene, polymethyl methacrylate and polymethylene urea, wherein the mass ratio of the polyvinyl alcohol to the polystyrene to the polymethyl methacrylate to the polymethylene urea is 1:2:4:5.
The dispersing agent is a combination of alkylphenol polyether phosphate, dodecylbenzene sulfonic acid, octadecyl dimethyl hydroxyethyl ammonium perchlorate, polyvinyl alcohol and alkyl dimethyl hydroxypropyl phosphate betaine, wherein the mass ratio of the alkylphenol polyether phosphate to the dodecylbenzene sulfonic acid to the octadecyl dimethyl hydroxyethyl ammonium perchlorate to the polyvinyl alcohol is 1:1:3:5:7.
The emulsifier is a combination of sodium dodecyl benzene sulfonate, tween 60 and Span 80, wherein the mass ratio of the sodium dodecyl benzene sulfonate, the Tween 60 and the Span 80 is 1:2:3.
The initiator is a combination of 3-glycidoxypropyl trimethoxysilane, benzoyl peroxide and tert-butyl hydroperoxide, wherein the mass ratio of the 3-glycidoxypropyl trimethoxysilane to the benzoyl peroxide to the tert-butyl hydroperoxide is 1:2:3.
Preparation of a resin curing delayed capsule curing agent the preparation of the resin curing delayed capsule curing agent was carried out as in example 1 and was designated as sample A3.
Example 4
The capsule curing agent for delaying resin curing is prepared from the following raw materials in percentage by mass: 30% of capsule core material, 20% of capsule wall material, 3% of dispersing agent, 2% of emulsifying agent, 1% of initiator and the balance of water, wherein the total content of all components is hundred percent;
the capsule core material is a combination of resol, dicyandiamide, p-toluenesulfonic acid and ammonium persulfate, wherein the mass ratio of the resol to the dicyandiamide to the p-toluenesulfonic acid to the ammonium persulfate is 4:3:2:1.
The capsule wall material is a combination of polyvinyl alcohol, polystyrene, polymethyl methacrylate and polymethylene urea, wherein the mass ratio of the polyvinyl alcohol to the polystyrene to the polymethyl methacrylate to the polymethylene urea is 1:2:3:4.
The dispersing agent is a combination of alkylphenol polyether phosphate, dodecylbenzene sulfonic acid, octadecyl dimethyl hydroxyethyl ammonium perchlorate, polyvinyl alcohol and alkyl dimethyl hydroxypropyl phosphate betaine, wherein the mass ratio of the alkylphenol polyether phosphate to the dodecylbenzene sulfonic acid to the octadecyl dimethyl hydroxyethyl ammonium perchlorate to the polyvinyl alcohol is 1:1:3:2:1.
The emulsifier is a combination of sodium dodecyl benzene sulfonate, tween 60 and Span 80, wherein the mass ratio of the sodium dodecyl benzene sulfonate, the Tween 60 and the Span 80 is 3:2:1.
The initiator is a combination of 3-glycidoxypropyl trimethoxysilane, benzoyl peroxide and tert-butyl hydroperoxide, wherein the mass ratio of the 3-glycidoxypropyl trimethoxysilane to the benzoyl peroxide to the tert-butyl hydroperoxide is 2:2:3.
Preparation of a resin curing delayed capsule curing agent the preparation of the resin curing delayed capsule curing agent was carried out as in example 1 and was designated as sample A4.
Example 5
The capsule curing agent for delaying resin curing is prepared from the following raw materials in percentage by mass: 35% of capsule core material, 25% of capsule wall material, 5% of dispersing agent, 2.5% of emulsifying agent, 1.5% of initiator and the balance of water, wherein the total content of all components is hundred percent;
the capsule core material is a combination of resol, dicyandiamide, p-toluenesulfonic acid and ammonium persulfate, wherein the mass ratio of the resol to the dicyandiamide to the p-toluenesulfonic acid to the ammonium persulfate is 5:3:2:1.
The capsule wall material is a combination of polyvinyl alcohol, polystyrene, polymethyl methacrylate and polymethylene urea, wherein the mass ratio of the polyvinyl alcohol to the polystyrene to the polymethyl methacrylate to the polymethylene urea is 1:2:3:1.
The dispersing agent is a combination of alkylphenol polyether phosphate, dodecylbenzene sulfonic acid, octadecyl dimethyl hydroxyethyl ammonium perchlorate, polyvinyl alcohol and alkyl dimethyl hydroxypropyl phosphate betaine, wherein the mass ratio of the alkylphenol polyether phosphate to the dodecylbenzene sulfonic acid to the octadecyl dimethyl hydroxyethyl ammonium perchlorate to the polyvinyl alcohol is 1:1:3:5:2.
The emulsifier is a combination of sodium dodecyl benzene sulfonate, tween 60 and Span 80, wherein the mass ratio of the sodium dodecyl benzene sulfonate, the Tween 60 and the Span 80 is 1:2:2.
The initiator is a combination of 3-glycidoxypropyl trimethoxysilane, benzoyl peroxide and tert-butyl hydroperoxide, wherein the mass ratio of the 3-glycidoxypropyl trimethoxysilane to the benzoyl peroxide to the tert-butyl hydroperoxide is 4:2:1.
Preparation of a resin curing delayed capsule curing agent the preparation of a resin curing delayed capsule curing agent was carried out as in example 1 and was designated as sample A5.
Comparative example 1
The capsule curing agent for delaying the curing of the resin described in example 1 is different in that: no wall material is added;
The specific raw materials comprise the following components: 40% of capsule core material, 3% of dispersing agent, 2% of emulsifying agent, 1% of initiator and the balance of water, wherein the sum of the contents of the components is hundred percent.
The preparation was carried out as in example 1, and the product obtained was designated as D1.
Comparative example 2
The capsule curing agent for delaying the curing of the resin described in example 1 is different in that: no dispersant is added;
The specific raw materials comprise the following components: 40% of capsule core material, 20% of capsule wall material, 2% of emulsifier, 1% of initiator and the balance of water, wherein the sum of the contents of all the components is hundred percent. The types of the above components are as described in example 1.
The preparation was carried out as in example 1, and the product obtained was designated as D2.
Comparative example 3
The capsule curing agent for delaying the curing of the resin described in example 1 is different in that: no emulsifying agent is added;
the specific raw materials comprise the following components: 40% of capsule core material, 20% of capsule wall material, 3% of dispersing agent, 1% of initiator and the balance of water, wherein the sum of the contents of all the components is hundred percent. The types of the above components are as described in example 1.
The preparation was carried out as in example 1, and the product obtained was designated as D3.
Comparative example 4
The capsule curing agent for delaying the curing of the resin described in example 1 is different in that: no initiator is added;
the specific raw materials comprise the following components: 40% of capsule core material, 20% of capsule wall material, 3% of dispersing agent, 2% of emulsifying agent, 1% of initiator and the balance of water, wherein the total content of all components is hundred percent. The types of the above components are as described in example 1.
The preparation was carried out as in example 1, and the product obtained was designated as D4.
Comparative example 5
The capsule curing agent for delaying the curing of the resin described in example 1 is different in that: the added core materials are only two types, namely the combination of the resol and the ammonium persulfate, and the mass ratio of the resol to the ammonium persulfate is 2:1;
the specific raw materials comprise the following components: 40% of capsule core material, 20% of capsule wall material, 3% of dispersing agent, 2% of emulsifying agent, 1% of initiator and the balance of water, wherein the total content of all components is hundred percent. The types of the above components are as described in example 1.
The preparation was carried out as in example 1, and the product obtained was designated as D5.
Comparative example 6
The capsule curing agent for delaying the curing of the resin described in example 1 is different in that: the added capsule wall materials are only two types, and are the combination of polystyrene and polymethylene urea, and the mass ratio of the polystyrene to the polymethylene urea is 3:1;
the specific raw materials comprise the following components: 40% of capsule core material, 20% of capsule wall material, 3% of dispersing agent, 2% of emulsifying agent, 1% of initiator and the balance of water, wherein the total content of all components is hundred percent. The types of the above components are as described in example 1.
The preparation was carried out as in example 1, and the product obtained was designated as D6.
Comparative example 7
The capsule curing agent for delaying the curing of the resin described in example 1 is different in that: the added dispersing agent is composed of dodecyl benzene sulfonic acid, octadecyl dimethyl hydroxyethyl ammonium perchlorate and polyvinyl alcohol, and the mass ratio of the dodecyl benzene sulfonic acid to the octadecyl dimethyl hydroxyethyl ammonium perchlorate to the polyvinyl alcohol is 2:1:1;
the specific raw materials comprise the following components: 40% of capsule core material, 20% of capsule wall material, 3% of dispersing agent, 2% of emulsifying agent, 1% of initiator and the balance of water, wherein the total content of all components is hundred percent. The types of the above components are as described in example 1.
The preparation was carried out as in example 1, and the product obtained was designated as D7.
Comparative example 8
The capsule curing agent for delaying the curing of the resin described in example 1 is different in that: the added emulsifier is Span 80;
the specific raw materials comprise the following components: 40% of capsule core material, 20% of capsule wall material, 3% of dispersing agent, 2% of emulsifying agent, 1% of initiator and the balance of water, wherein the total content of all components is hundred percent. The types of the above components are as described in example 1.
The preparation was carried out as in example 1, and the product obtained was designated as D8.
Comparative example 9
The capsule curing agent for delaying the curing of the resin described in example 1 is different in that: the initiator types are only two, namely the combination of 3-glycidoxypropyl trimethoxysilane and tert-butyl hydroperoxide, wherein the mass ratio of the 3-glycidoxypropyl trimethoxysilane to the tert-butyl hydroperoxide is 2:1, a step of;
the specific raw materials comprise the following components: 40% of capsule core material, 20% of capsule wall material, 3% of dispersing agent, 2% of emulsifying agent, 1% of initiator and the balance of water, wherein the total content of all components is hundred percent. The types of the above components are as described in example 1.
The preparation was carried out as in example 1, and the product obtained was designated as D9.
Test examples
The capsule curatives for delayed resin cure prepared in the above examples and comparative examples were subjected to cure time and cure strength tests.
Test 1: capsule curing agent cure time test
Weighing 3g of the prepared capsule curing agent, adding the resin solution into 97g of the resin solution, stirring uniformly (the dosage of the capsule curing agent is 3%), preparing a resin solution plugging system, loading the resin solution plugging system into a temperature-resistant film, placing the film in a high-temperature aging furnace, heating under different temperature conditions, taking out the film at regular intervals, observing the curing condition, and taking the time for curing the standard test sample to form a solidified body by taking out no fluid flowing out after the die is inverted for thirty seconds, namely the curing time of the capsule curing agent.
Test 2: sample compressive strength test after curing of capsule curing agent initiated resin system
And preparing a sample cured by the capsule curing agent initiating resin system into a cylinder with the bottom surface diameter of 20mm and the height of 10mm, adopting an electronic universal testing machine to carry out compression mechanical property test, setting the compression speed to be 3 mm/min, and recording the compression strength of the sample compressed after the capsule curing agent initiating resin system is cured.
The curing times and strengths of the resin-curing-delayed capsule curing agents prepared in the above examples and comparative examples at different temperatures are shown in Table 1.
Table 1 results of cure time and cure strength test of capsule curatives at different temperatures
As can be seen from table 1, the core material, the wall material and the initiator have a larger influence on the curing time and strength of the capsule curing agent, and the dispersing agent and the emulsifying agent have a smaller influence on the curing time and strength of the capsule curing agent. As can be seen from the data in Table 1, the curing time of the capsule curing agent for delaying the curing of the resin prepared in each embodiment of the invention can be controlled to be 380-480min at 140 ℃ and the curing strength is between 12.1-15.6 MPa; the curing time can be controlled to be 270-430min under the condition of 160 ℃, and the curing strength is 11.2-14.3 MPa; the curing time can be controlled to be 210-360min under the condition of 180 ℃ and the curing strength is between 10.1 and 13.4 MPa; the curing time can be controlled to be 170-300min under the condition of 200 ℃ and the curing strength is 9.2-12.7 MPa; the curing time can be controlled to be 120-240min under the condition of 220 ℃ and the curing strength is 7.2-11.9 MPa. Compared with the examples, the comparative examples have obviously shortened curing time, greatly reduced curing strength and obviously deteriorated curing effect of the delayed resin, and further demonstrate the synergy between the raw materials of the invention. Therefore, the capsule curing agent for delaying the curing of the resin prepared in the embodiment of the invention can delay the curing reaction of the resin under ultra-deep high-temperature and high-pressure conditions, ensures the curing of the resin plugging slurry under the optimal conditions and forms a high-strength consolidated body after the curing, thereby improving the quality and the performance of the resin. Meanwhile, the components and the proportion of the capsule curing agent are adjusted, so that the accurate regulation and control of the curing time and the strength of the resin can be realized, and a drilling engineer can flexibly control according to actual requirements.
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 (4)
1. The capsule curing agent for delaying the curing of the resin is characterized by comprising the following raw materials in percentage by mass: 5-40% of capsule core material, 2-30% of capsule wall material, 0.1-5% of dispersing agent, 0.1-2.5% of emulsifying agent, 0.1-1.5% of initiator and the balance of water, wherein the total content of all components is hundred percent;
the capsule core material is a combination of resol, dicyandiamide, p-toluenesulfonic acid and ammonium persulfate;
The capsule wall material is a combination of polyvinyl alcohol, polystyrene, polymethyl methacrylate and polymethylene urea;
The dispersing agent is a combination of alkylphenol polyether phosphate, dodecylbenzene sulfonic acid, octadecyl dimethyl hydroxyethyl ammonium perchlorate, polyvinyl alcohol and alkyl dimethyl hydroxypropyl phosphate betaine;
The emulsifier is a combination of sodium dodecyl benzene sulfonate, tween 60 and Span 80;
The initiator is a combination of 3-glycidol ether oxygen propyl trimethoxy silane, benzoyl peroxide and tert-butyl hydroperoxide;
The method comprises the following steps:
(1) According to the proportion, the dispersing agent is dissolved in deionized water to disperse the solution A;
(2) Adding the core material into the dispersion solution A, and fully and uniformly mixing to obtain a mixture B;
(3) Adding an emulsifier into the mixture B, and uniformly mixing under the protection of inert gas to obtain a mixture C;
(4) Adding an initiator into the mixture C, and uniformly mixing and stirring under the protection of inert gas to obtain a mixture D;
(5) And adding a capsule wall material into the mixture D, mixing and stirring uniformly under the protection of inert gas, and obtaining the product capsule curing agent through centrifugal suction filtration, washing and drying.
2. The capsule curing agent for delaying resin curing according to claim 1, wherein a mass ratio of resole, dicyandiamide, p-toluenesulfonic acid and ammonium persulfate is (3-6): (1-5): (1-3): (0.5-2).
3. The capsule curing agent for delaying resin curing according to claim 1, wherein a mass ratio of polyvinyl alcohol, polystyrene, polymethyl methacrylate to polymethylene urea is (0.5-2): (1-3): (1-5): (1-8).
4. The use of the capsule curing agent of claim 1, wherein the curable resin applied to deep or ultra-deep drilling fluids is lost circulation, delaying the curing of the resin;
the specific application method is as follows:
dissolving a capsule curing agent and a curable resin plugging material in water on the ground to prepare resin plugging slurry, directly injecting the resin plugging slurry into a plugging layer, and exciting the capsule curing agent to release a capsule core material under the formation temperature condition to trigger the resin to undergo a crosslinking curing reaction to form a high-strength consolidation slug plugging layer, wherein the addition amount of the capsule curing agent is 2-5wt% of the curable resin plugging material;
or the capsule curing agent and the curable resin plugging material are dissolved in water on the ground to prepare resin plugging slurry, and then the resin plugging slurry and the bridging type leakage plugging material are used together to be injected into a plugging layer, and the capsule curing agent is excited to release the capsule core material under the formation temperature condition to trigger the resin to adhere to the bridging type leakage plugging material to be cured to form an integral slug plugging layer, wherein the dosage of the capsule curing agent is 10-20g per liter of resin plugging slurry.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202410362380.7A CN117965145B (en) | 2024-03-28 | Capsule curing agent for delaying resin curing and preparation method and application thereof |
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| CN202410362380.7A CN117965145B (en) | 2024-03-28 | Capsule curing agent for delaying resin curing and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167885A (en) * | 2011-03-09 | 2011-08-31 | 东南大学 | High-intensity urea-formaldehyde resin microcapsule and preparation method thereof |
| CN102423673A (en) * | 2011-07-28 | 2012-04-25 | 西北工业大学 | Latent microcapsule curing agent initiating thermosetting epoxy resin curing at medium temperature and preparation method of adhesive thereof |
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167885A (en) * | 2011-03-09 | 2011-08-31 | 东南大学 | High-intensity urea-formaldehyde resin microcapsule and preparation method thereof |
| CN102423673A (en) * | 2011-07-28 | 2012-04-25 | 西北工业大学 | Latent microcapsule curing agent initiating thermosetting epoxy resin curing at medium temperature and preparation method of adhesive thereof |
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