CN107722958A - Water-soluble diverter dissolved at 60-90 ℃ and preparation method thereof - Google Patents
Water-soluble diverter dissolved at 60-90 ℃ and preparation method thereof Download PDFInfo
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- CN107722958A CN107722958A CN201710735424.6A CN201710735424A CN107722958A CN 107722958 A CN107722958 A CN 107722958A CN 201710735424 A CN201710735424 A CN 201710735424A CN 107722958 A CN107722958 A CN 107722958A
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- water
- soluble
- antioxidant
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- polyethylene glycol
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 28
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 28
- 229920000954 Polyglycolide Polymers 0.000 claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 12
- 239000004970 Chain extender Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 239000004014 plasticizer Substances 0.000 claims abstract description 8
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 8
- 238000012216 screening Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 55
- 239000003795 chemical substances by application Substances 0.000 claims description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 25
- -1 poly- aminoalkyl ester Chemical class 0.000 claims description 25
- 235000010409 propane-1,2-diol alginate Nutrition 0.000 claims description 17
- 238000001125 extrusion Methods 0.000 claims description 15
- 239000012948 isocyanate Substances 0.000 claims description 14
- 238000012986 modification Methods 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 230000004224 protection Effects 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 8
- 238000006073 displacement reaction Methods 0.000 claims description 7
- RZYKUPXRYIOEME-UHFFFAOYSA-N CCCCCCCCCCCC[S] Chemical compound CCCCCCCCCCCC[S] RZYKUPXRYIOEME-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000005453 pelletization Methods 0.000 claims description 5
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000004200 microcrystalline wax Substances 0.000 claims description 4
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 4
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- GXVUZYLYWKWJIM-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanamine Chemical compound NCCOCCN GXVUZYLYWKWJIM-UHFFFAOYSA-N 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 125000004103 aminoalkyl group Chemical group 0.000 claims 1
- 235000013339 cereals Nutrition 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 125000003696 stearoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 2
- 125000005907 alkyl ester group Chemical group 0.000 abstract 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 8
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 5
- DGYMCGCIUWHSNH-UHFFFAOYSA-N C(CCC)[Sn]CCCC.C(CCCCCCCCCCC)[S] Chemical compound C(CCC)[Sn]CCCC.C(CCCCCCCCCCC)[S] DGYMCGCIUWHSNH-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229920000426 Microplastic Polymers 0.000 description 4
- 229920006022 Poly(L-lactide-co-glycolide)-b-poly(ethylene glycol) Polymers 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- GTDHYNXLIKNVTJ-UHFFFAOYSA-N n-(1-hydroxy-2-methylpropan-2-yl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NC(C)(C)CO GTDHYNXLIKNVTJ-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229960003511 macrogol Drugs 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000009466 transformation Effects 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/428—Lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5086—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention relates to a water-soluble diverter dissolved at 60-90 ℃ and a preparation method thereof, wherein the preparation method comprises the following steps: copolymerizing polyglycolide, polyethylene glycol and polylactide in different proportions to obtain a block prepolymer, and then carrying out chain extension reaction on the mixture of the prepolymer and a certain amount of polyethylene glycol by using a chain extender to obtain a modified polyamino alkyl ester material which can be completely and rapidly degraded; and then uniformly mixing the modified polyamino alkyl ester material, the plasticizer, the nano reinforcing agent, the antioxidant and the lubricant in a banbury mixer according to a proportion, extruding and granulating in a double-screw extruder, extruding and bracing the mixture by the extruder, cooling the mixture by water, drying the mixture by air, granulating and crushing the mixture, and screening the mixture to prepare the water-soluble diverter with different particle sizes. The modified polyamino alkyl ester material comprises, by weight, 50-100 parts of a modified polyamino alkyl ester material, 10-20 parts of a plasticizer, 5-10 parts of a nano reinforcing agent, 0.1-0.3 part of an antioxidant and 0.5-1 part of a lubricant. The water-soluble diverter can be dissolved in water at the temperature of 60-90 ℃ and degraded in the water; has higher bearing strength and can bear more than 30 MPa.
Description
Technical field
The invention belongs to the fracturing yield increasing technical field during gas-field exploitation, and in particular to a kind of 60~90 DEG C of dissolvings
Water-soluble diversion agent and preparation method thereof.
Background technology
Pressure break diversion agent is a kind of auxiliary additive in Oil/gas Well transformation process, is called pressure break diverting agent, and it is to turn to
Important part in fracturing technique.In pressing crack construction, act on temporarily stifled old seam using the bridge blinding of diversion agent or added sand
Seam, winding shaft bottom net pressure, makes fluid turn in the earth formation, forms the new crack for being different from old fractuer direction or makes pressure
Split sand to be uniformly distributed in crack, so as to open new fluid flowing passage in reservoir, more broadly link up old crack not
The oil-gas Layer employed, increase oil and gas production.The diversion agent used at present mainly has：Silicic acid salt grain, haydite, polyacrylamide etc.,
It is big density to be present in silicic acid salt grain, haydite, and pumping is extremely difficult, and efficiency is low, insoluble；It is low closure pressure to be present in polyacrylamide
The defects of.
The content of the invention
The purpose of the present invention be overcome existing diversion agent to exist density is big, pumping is extremely difficult low with closure pressure etc. lacks
Fall into.
Therefore, the invention provides the water-soluble diversion agents of a kind of 60~90 DEG C dissolvings, prepared by following parts by weight of component and
：
The poly- aminoalkyl ester material of modification is to be expanded by PGA, polyethylene glycol and polylactide by three block
Chain agent co-polymeric forms, and the reaction equation of co-polymeric reaction is：
The poly- aminoalkyl ester material of modification is prepared by following methods：
Step 1：By proportioning, by 20~30 parts of PGAs, 40~60 polyethylene glycol, 20~30 parts of polylactides with
0.2~0.5 part of catalyst A adds reactor under nitrogen protective condition, keeps vacuumizing in kettle and repeatedly nitrogen displacement ensures
Dried in kettle, then to material, molten be warming up to again under 175 DEG C of molten conditions reacts 14 hours systems entirely within 2 hours for 100 DEG C of mixings
Obtain poly (glycolide-lactide)-polyethylene glycol；
Step 2：5~20 parts of three block chain extenders and 0.5 are added into poly (glycolide-lactide)-polyethylene glycol under nitrogen protection
~1 part of catalyst B simultaneously continues 5 hours obtained modified poly- aminoalkyl ester materials of reaction in the case where 175 DEG C of nitrogen are protected.
The three block chain extender is toluene di-isocyanate(TDI)-ethylene glycol-toluene di-isocyanate(TDI)；
The catalyst A be two (dodecyl sulphur) dibutyl tins, two mercaptan tin alkyls, one kind in dioctyl tin or
Several mixing；
The catalyst B is two (dodecyl sulphur) dibutyl tins, two mercaptan tin alkyls, pentamethyl-diethylenetriamine, double
One or more of mixing in dimethylaminoethyl ether.
The molecular weight of the PGA is 60,000~300,000, and the molecular weight of polyethylene glycol is 200~10000, and poly- third hands over
Ester is Study of Meso-Lactide, and molecular weight is 120,000~400,000.
The plasticiser is the one or more in poly-hydroxy fatty acid, polyethylene glycol, PTMC.
The nanometer reinforcing agent is the one or more in nano-calcium carbonate, Nano carbon white, nanoscale talcum powder.
The antioxidant is one in antioxidant 1010, antioxidant 1076, antioxidant 164, antioxidant 264, antioxidant CA
Kind is several.
The lubricant is one kind or several in stearmide, tristerin, microcrystalline wax, Tissuemat E, silicone oil
Kind.
A kind of preparation method of the water-soluble diversion agent of 60~90 DEG C of dissolvings, it is characterised in that comprise the following steps that：
(1) proportioning is pressed by the poly- aminoalkyl ester material of modification, plasticiser, nanometer reinforcing agent, antioxidant, lubricant close
It is kneaded uniform in mill, banbury temperature control control is at 90~120 DEG C or so, mixing time 8~10 minutes；
(2) and then by double screw extruder extruding pelletization, extrusion temperature is 90~100 DEG C of an area, area of 2nd area~tetra-
110~125 DEG C, 5th area~105~120 DEG C of tenth area, 11 110 DEG C of areas, through extruding tie rod, water cooling, wind after extruded machine extrusion
It is dry, it is granulated and crushes, obtains water-soluble diversion agent after screening.
Beneficial effects of the present invention：
1. there is higher bearing strength, can more than pressure-bearing 30MPa；
2. being dissolved at 60~90 DEG C, by adjusting poly (glycolide-lactide) ratio and molecular size range in polymer, make dissolving
Speed is controllable, and dissolution time can adjust；
3. dissolving is thorough, without insoluble resin particle；
4. diversion agent grain diameter can be controlled by broken milling process, different pressure break scale requirements can be met.
Embodiment
Invention provides a kind of water-soluble diversion agent of 60~90 DEG C of dissolvings, is prepared by following parts by weight of component：
The poly- aminoalkyl ester material of modification is to be expanded by PGA, polyethylene glycol and polylactide by three block
Chain agent co-polymeric forms, and the reaction equation of co-polymeric reaction is：
The poly- aminoalkyl ester material of modification is prepared by following methods：
Step 1：By proportioning, by 20~30 parts of PGAs, 40~60 polyethylene glycol, 20~30 parts of polylactides with
0.2~0.5 part of catalyst A adds reactor under nitrogen protective condition, keeps vacuumizing in kettle and repeatedly nitrogen displacement ensures
Dried in kettle, then to material, molten be warming up to again under 175 DEG C of molten conditions reacts 14 hours systems entirely within 2 hours for 100 DEG C of mixings
Obtain poly (glycolide-lactide)-polyethylene glycol；
Step 2：5~20 parts of three block chain extenders and 0.5 are added into poly (glycolide-lactide)-polyethylene glycol under nitrogen protection
~1 part of catalyst B simultaneously continues 5 hours obtained modified poly- aminoalkyl ester materials of reaction in the case where 175 DEG C of nitrogen are protected.
The three block chain extender is toluene di-isocyanate(TDI)-ethylene glycol-toluene di-isocyanate(TDI)；
The catalyst A be two (dodecyl sulphur) dibutyl tins, two mercaptan tin alkyls, one kind in dioctyl tin or
Several mixing；
The catalyst B is two (dodecyl sulphur) dibutyl tins, two mercaptan tin alkyls, pentamethyl-diethylenetriamine, double
One or more of mixing in dimethylaminoethyl ether.
The molecular weight of the PGA is 60,000~300,000, and the molecular weight of polyethylene glycol is 200~10000, and poly- third hands over
Ester is Study of Meso-Lactide, and molecular weight is 120,000~400,000.
The plasticiser is the one or more in poly-hydroxy fatty acid, polyethylene glycol, PTMC.
The nanometer reinforcing agent is the one or more in nano-calcium carbonate, Nano carbon white, nanoscale talcum powder.
The antioxidant is one in antioxidant 1010, antioxidant 1076, antioxidant 164, antioxidant 264, antioxidant CA
Kind is several.
The lubricant is one kind or several in stearmide, tristerin, microcrystalline wax, Tissuemat E, silicone oil
Kind.
A kind of preparation method of the water-soluble diversion agent of 60~90 DEG C of dissolvings, it is characterised in that comprise the following steps that：
(1) proportioning is pressed by the poly- aminoalkyl ester material of modification, plasticiser, nanometer reinforcing agent, antioxidant, lubricant close
It is kneaded uniform in mill, banbury temperature control control is at 90~120 DEG C or so, mixing time 8~10 minutes；
(2) and then by double screw extruder extruding pelletization, extrusion temperature is 90~100 DEG C of an area, area of 2nd area~tetra-
110~125 DEG C, 5th area~105~120 DEG C of tenth area, 11 110 DEG C of areas, through extruding tie rod, water cooling, wind after extruded machine extrusion
It is dry, it is granulated and crushes, obtains water-soluble diversion agent after screening.
Embodiment 1：
Step 1：The synthesis of PGA, polyethylene glycol, polylactide ternary polymerization performed polymer
50g polyethylene glycol 400s and PGA 25g, poly- M- lactides 25g are sequentially added in 250mL reactors, taken out
Vacuum and with nitrogen displacement three times, add two (dodecyl sulphur) dibutyl tin 0.3g, and repeat before the nitrogen that vacuumizes put
Operation is changed, until being dried in reactor；Then lower 100 DEG C of nitrogen atmosphere is mixed 2 hours and is warming up to again to material is entirely molten
14 hours obtained PLGA-PEG performed polymers are reacted under 175 DEG C of molten conditions；
Step 2：Poly- aminoalkyl ester block polymer synthesis
Three block chain extender TDI-PEG-TDI (toluene di-isocyanate(TDI)s-second are added into this performed polymer under nitrogen protection
Glycol-toluene di-isocyanate(TDI)) 15g and double dimethylaminoethyl ether 0.5g and continue reaction 12 in the case where 175 DEG C of nitrogen are protected
Hour, obtained target was modified poly- aminoalkyl ester material 115g；
Step 3：The preparation of Water soluble diversion agent
By 75.2 parts of the poly- aminoalkyl ester material of modification, 11 parts of polyethylene glycol, 13 parts of nano-calcium carbonate, 0.2 part of antioxidant
1010,0.1 parts of antioxidant 264s, 0.5 part of stearmide are put into banbury, banburying 8 minutes at 110 DEG C；Then double spiral shells are passed through
Extruding pelletization in bar extruder, extrusion temperature are 100 DEG C of an area, 2nd area~120 DEG C of 4th area, 5th area~110 DEG C of tenth area, 11
110 DEG C of area's temperature, through extruding tie rod after extruded machine extrusion, water cooling, air-dry, be granulated, obtaining well mixed plastic pellet is
Water soluble diversion agent.
Embodiment 2：
Step 1：The synthesis of PGA, polyethylene glycol, polylactide ternary polymerization performed polymer
50g Macrogol 600s and PGA 20g, poly- M- lactides 30g are sequentially added in 250mL reactors, taken out
Vacuum and with nitrogen displacement three times, add two mercaptan tin alkyl 0.5g, and repeat before vacuumized nitrogen operation, directly
Dried in reactor；Then heating is started the lower 100 DEG C of mixings of stirring nitrogen atmosphere and heated up again to material is entirely molten for 2 hours
18 hours obtained PLGA-PEG performed polymers are extremely reacted under 175 DEG C of molten conditions；
Step 2：Poly- aminoalkyl ester block polymer synthesis
Three block chain extender TDI-PEG-TDI (toluene di-isocyanate(TDI)s-second are added into this performed polymer under nitrogen protection
Glycol-toluene di-isocyanate(TDI)) 13g and two (dodecyl sulphur) dibutyl tin 0.2g and continue in the case where 175 DEG C of nitrogen are protected
12 hours obtained targets of reaction are modified poly- aminoalkyl ester material 115g；
Step 3：The preparation of Water soluble diversion agent
By 75 parts of the poly- aminoalkyl ester material of modification, 14 parts of PHA esters, 10 parts of Nano carbon white, 0.2 part of antioxidant 1010,
0.1 part of antioxidant 164,0.7 part of Tissuemat E are put into banbury, and banburying 8 minutes, then pass through twin-screw extrusion at 120 DEG C
Extruding pelletization in machine, extrusion temperature are 90 DEG C of an area, 2nd area~115 DEG C of 4th area, 5th area~115 DEG C of tenth area, 11 area's temperature
110 DEG C, through extruding tie rod after extruded machine extrusion, water cooling, air-dry, be granulated, obtain well mixed plastic pellet.
Embodiment 3：
Step 1：The synthesis of PGA, polyethylene glycol, polylactide ternary polymerization performed polymer
150g polyethylene glycol 400s and PGA 90g, poly- M- lactides 60g are sequentially added in 500mL reactors, taken out
Vacuum and with nitrogen displacement three times, add two (dodecyl sulphur) dibutyl tin 1g, and repeat before vacuumized nitrogen
Operation, until being dried in reactor；Then heating start stirring nitrogen atmosphere it is lower 100 DEG C mix 3 hours it is entirely molten to material
It is warming up to again under 175 DEG C of molten conditions and reacts 14 hours obtained PLGA-PEG performed polymers；
Step 2：Poly- aminoalkyl ester block polymer synthesis
Three block chain extender TDI-PEG-TDI (toluene di-isocyanate(TDI)s-second are added into this performed polymer under nitrogen protection
Glycol-toluene di-isocyanate(TDI)) 42g and double dimethylaminoethyl ether 0.5g, two (dodecyl sulphur) dibutyl tin 1g and
Continue 18 hours obtained targets of reaction under 175 DEG C of nitrogen protections and be modified poly- aminoalkyl ester material 345g；
Step 3：The preparation of Water soluble diversion agent
By 63 parts of the poly- aminoalkyl ester material of modification, 20 parts of polyethylene glycol 400s, 16 parts of nanomete talc powder, 0.3 part of antioxygen
Agent CA, 0.7 part of microcrystalline wax are put into banbury, banburying 8 minutes at 100 DEG C；Then made by being extruded in double screw extruder
Grain, extrusion temperature be 100 DEG C of an area, 2nd area~110 DEG C of 4th area, 5th area~120 DEG C of tenth area, 11 110 DEG C of area's temperature, through crowded
Go out after machine extrusion through extruding tie rod, water cooling, air-dry, be granulated, obtain well mixed plastic pellet, be Water soluble diversion agent.
Embodiment 4：
Step 1：The synthesis of PGA, polyethylene glycol, polylactide ternary polymerization performed polymer
500g polyethylene glycol 500 and PGA 250g, poly- M- lactides 250g are sequentially added into 3000mL reactors
In, vacuumize and with nitrogen displacement three times, add two (dodecyl sulphur) dibutyl tin 5g, and repeat before vacuumize nitrogen
Gas replacement operator, until being dried in reactor；Then heating starts lower 100 DEG C of stirring nitrogen atmosphere and mixes 5 hours to thing
Complete molten be warming up to again under 175 DEG C of molten conditions of material reacts 20 hours obtained PLGA-PEG performed polymers；
Step 2：Poly- aminoalkyl ester block polymer synthesis
Three block chain extender TDI-PEG-TDI (toluene di-isocyanate(TDI)s-second are added into this performed polymer under nitrogen protection
Glycol-toluene di-isocyanate(TDI)) 150g and double dimethylaminoethyl ether 5g and to continue reaction 18 in the case where 175 DEG C of nitrogen are protected small
When target be made be modified poly- aminoalkyl ester material 1150g；
Step 3：The preparation of Water soluble diversion agent
By 85 parts, 8 parts of PTMC PTMC of the poly- aminoalkyl ester material of modification, 6 parts, 3 parts of nano-corundum
Antioxidant CA 0,0.7 part of silicone oil are put into banbury, banburying 8 minutes at 110 DEG C；Then by being extruded in double screw extruder
It is granulated, extrusion temperature is 100 DEG C of an area, 2nd area~110 DEG C of 4th area, 5th area~115 DEG C of tenth area, 11 110 DEG C of area's temperature, is passed through
Through extruding tie rod after extruder extrusion, water cooling, air-dry, be granulated, obtain well mixed plastic pellet, be Water soluble diversion agent.
In order to examine the actual performance of 60~90 DEG C of water-soluble diversion agents of the invention, it is also necessary to granular water-soluble steering
Agent is put into a diameter of 8cm cylindrical shapes punching block, and punching block has water filling port and delivery port up and down, carries out soluble test and pressure-bearing energy
Power is tested：
Rock core is put into punching block first, water is injected, sealing frock, is warming up to test temperature, is gradually forced into delivery port
Outflow water, record water flow；
Then water-soluble diversion agent obtained by embodiment is put into punching block on rock core again, pavement thickness 2cm, be compacted, injection
Water, sealing frock are warming up to test temperature, are gradually forced into delivery port outflow water, record breakthrough pressure, and go out after breaking through
Mouth of a river water flow；Temporarily stifled rate is calculated by below equation.
(water flow after rock core water flow-breakthrough)/rock core water flow × 100%=temporarily blocks up rate
In the case where keeping pressure and solution temperature constant, when temporary stifled rate is reduced to 0, show that diversion agent is completely molten
Solution, record are completely dissolved the time.
The water-soluble diversion agent pressure of table 1, dissolving statistical form
As shown in Table 1, compared to the water-soluble diversion agent of other domestic polyacrylamides, aqueous solvent pressure-bearing provided by the invention
Up to more than 30MPa, other significantly larger than domestic water-soluble diversion agents of producer's polyacrylamide, water is dissolved at 60~90 DEG C,
And degraded in water, and temporarily stifled rate is high.The aqueous solvent of the present invention has been added into for temporarily stifled old seam or sand seam, can be with winding shaft bottom
Net pressure, fluid is turned in the earth formation, form the new crack for being different from old fractuer direction or make fracturing sand in crack
It is uniformly distributed, so as to open new fluid flowing passage in reservoir, more broadly links up the oil gas that old crack is not employed
Layer, increase oil and gas production.
It is exemplified as above be only to the present invention for example, do not form the limitation to protection scope of the present invention, it is all
It is to be belonged to the same or analogous design of the present invention within protection scope of the present invention.What the present embodiment did not describe in detail
The well-known components and common structure or conventional means of part and the structure category industry, are not described one by one here.
Claims (9)
1. a kind of water-soluble diversion agent of 60~90 DEG C of dissolvings, it is characterised in that be prepared by following parts by weight of component：
The poly- aminoalkyl ester material of modification is to be total to by PGA, polyethylene glycol and polylactide by three block chain extender
It is polymerized, the reaction equation of co-polymeric reaction is：
2. the water-soluble diversion agent of 60~90 DEG C of dissolvings as claimed in claim 1, it is characterised in that the poly- aminoalkyl of modification
Ester material is prepared by following methods：
Step 1：By proportioning, by 20~30 parts of PGAs, 40~60 polyethylene glycol, 20~30 parts of polylactides and 0.2~
0.5 part of catalyst A adds reactor under nitrogen protective condition, keeps vacuumizing in kettle and repeatedly nitrogen displacement ensures to do in kettle
Dry, then to material, molten be warming up to again under 175 DEG C of molten conditions reacts 14 hours obtained poly- second entirely within 2 hours for 100 DEG C of mixings
Lactide-polyethylene glycol；
Step 2：5~20 parts of three block chain extenders and 0.5~1 part are added into poly (glycolide-lactide)-polyethylene glycol under nitrogen protection
Catalyst B simultaneously continues 5 hours obtained modified poly- aminoalkyl ester materials of reaction in the case where 175 DEG C of nitrogen are protected.
3. the water-soluble diversion agent of 60~90 DEG C of dissolvings as claimed in claim 1 or 2, it is characterised in that the three block chain extension
Agent is toluene di-isocyanate(TDI)-ethylene glycol-toluene di-isocyanate(TDI)；
The catalyst A is one or more of in two (dodecyl sulphur) dibutyl tins, two mercaptan tin alkyls, dioctyl tin
Mixing；
The catalyst B is two (dodecyl sulphur) dibutyl tins, two mercaptan tin alkyls, pentamethyl-diethylenetriamine, double diformazans
One or more of mixing in amino-ethyl ether.
4. the water-soluble diversion agent of 60~90 DEG C of dissolvings as claimed in claim 1 or 2, it is characterised in that the PGA
Molecular weight is 60,000~300,000, and the molecular weight of polyethylene glycol is 200~10000, and polylactide is Study of Meso-Lactide, molecular weight
For 120,000~400,000.
5. the water-soluble diversion agent of 60~90 DEG C of dissolvings as claimed in claim 1, it is characterised in that the plasticiser is poly- hydroxyl
One or more in aliphatic acid, polyethylene glycol, PTMC.
6. the water-soluble diversion agent of 60~90 DEG C of dissolvings as claimed in claim 1, it is characterised in that the nanometer reinforcing agent is to receive
One or more in rice calcium carbonate, Nano carbon white, nanoscale talcum powder.
7. the water-soluble diversion agent of 60~90 DEG C of dissolvings as claimed in claim 1, it is characterised in that the antioxidant is antioxidant
1010th, the one or more in antioxidant 1076, antioxidant 164, antioxidant 264, antioxidant CA.
8. the water-soluble diversion agent of 60~90 DEG C of dissolvings as claimed in claim 1, it is characterised in that the lubricant is stearoyl
One or more in amine, tristerin, microcrystalline wax, Tissuemat E, silicone oil.
9. a kind of preparation method of the water-soluble diversion agent of 60~90 DEG C of dissolvings as described in any one of claim 1~8, its
It is characterised by, comprises the following steps that：
(1) press and match the poly- aminoalkyl ester material of modification, plasticiser, nanometer reinforcing agent, antioxidant, lubricant in banbury
It is kneaded uniform, banbury temperature control control is at 90~120 DEG C or so, mixing time 8~10 minutes；
(2) and then by double screw extruder extruding pelletization, extrusion temperature is 90~100 DEG C of an area, area of 2nd area~tetra- 110~
125 DEG C, 5th area~105~120 DEG C of tenth area, 11 110 DEG C of areas, through extruding tie rod after extruded machine extrusion, water cooling, air-dry, make
Grain simultaneously crushes, and obtains water-soluble diversion agent after screening.
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