CN104926987B - Hydrophobic associating crosslinked microspheres and preparation method thereof - Google Patents
Hydrophobic associating crosslinked microspheres and preparation method thereof Download PDFInfo
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- CN104926987B CN104926987B CN201410097783.XA CN201410097783A CN104926987B CN 104926987 B CN104926987 B CN 104926987B CN 201410097783 A CN201410097783 A CN 201410097783A CN 104926987 B CN104926987 B CN 104926987B
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- monomer
- salt
- hydrophobic
- hydrophobic association
- crosslinked microsphere
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- 239000004005 microsphere Substances 0.000 title claims abstract description 90
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000004132 cross linking Methods 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims abstract description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 41
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- -1 alkyl Phenol Chemical compound 0.000 claims description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 239000007957 coemulsifier Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
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- 239000012966 redox initiator Substances 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
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- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
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- 230000001590 oxidative effect Effects 0.000 claims description 4
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 claims description 3
- OZFIGURLAJSLIR-UHFFFAOYSA-N 1-ethenyl-2h-pyridine Chemical class C=CN1CC=CC=C1 OZFIGURLAJSLIR-UHFFFAOYSA-N 0.000 claims description 2
- VMSBGXAJJLPWKV-UHFFFAOYSA-N 2-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=C VMSBGXAJJLPWKV-UHFFFAOYSA-N 0.000 claims description 2
- TURITJIWSQEMDB-UHFFFAOYSA-N 2-methyl-n-[(2-methylprop-2-enoylamino)methyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCNC(=O)C(C)=C TURITJIWSQEMDB-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- FXRFEDMPOGKDAA-UHFFFAOYSA-M [NH4+].[Br-].C(C=C)(=O)OCC[P+](CC)(C)C.[Br-] Chemical compound [NH4+].[Br-].C(C=C)(=O)OCC[P+](CC)(C)C.[Br-] FXRFEDMPOGKDAA-UHFFFAOYSA-M 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
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- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([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])C([H])([H])[H] 0.000 claims description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical group OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 125000000913 palmityl group Chemical group [H]C([*])([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
- 229940051841 polyoxyethylene ether Drugs 0.000 claims 1
- 229920000056 polyoxyethylene ether Polymers 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 17
- 238000000605 extraction Methods 0.000 abstract 1
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 6
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
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- 230000001965 increasing effect Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical group CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- PRWXGRGLHYDWPS-UHFFFAOYSA-L sodium malonate Chemical compound [Na+].[Na+].[O-]C(=O)CC([O-])=O PRWXGRGLHYDWPS-UHFFFAOYSA-L 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides hydrophobic associating crosslinked microspheres and a preparation method thereof, and is used for mainly solving the problems in the prior art that conventional oilfield polymer microspheres are extremely easy to hydrate, have uncontrolled expansion and have poor sealing effect on a high-permeability oil layer under high-temperature and high-salt conditions. The problems are better solved by the technical schemes that the hydrophobic associating crosslinked microspheres are prepared by copolymerization of monomers with addition or no addition of a crosslinking agent; the monomers include acrylamide, a water-soluble temperature-resistant salt-resistant monomer and a crosslinking type heat-resistant/hydrophobic monomer represented by the following formula described in the description, wherein R1, R2, R3 and R4 are independently selected from hydrogen atoms, methyl or ethyl, R5 and R6 are independently selected from hydrogen atoms, methyl, ethyl, methoxy or ethoxy. The hydrophobic associating crosslinked microspheres can be used for industrialized production and oilfield tertiary oil extraction water shutoff and profile modification operations.
Description
Technical field
The present invention relates to macromolecule technology of preparing and tertiary oil recovery field, and in particular to a kind of hydrophobic association crosslinked microsphere and
Its preparation method.
Background technology
The seepage flow situation of oil field heterogeneous reservoir how is effectively improved, the sweep efficiency of driven water-replacing is improved and is involved body
Product, so as to improve oil recovery factor, it has also become key subjects urgently to be resolved hurrily during tertiary oil recovery at present.Currently, both at home and abroad
Commonly use chemical reagent to block oilfield high infiltration permeable layers, i.e., so-called water plugging and profile controlling method.Using water plugging profile control agent it is main
Organic/inorganic substance class, polymerization species, foam class etc..But inorganic species water plugging profile control agent causes nearly well because of incompressible or deformation
Area blocks and cannot be deep into earth formation deep；Polymerization species water plugging profile control agent is then due under facile hydrolysiss, high salinity under high temperature
Easily precipitation, sensitive to temperature and salinity, ageing resistace difference and limit its application；Foam class water plugging profile control agent has excellent merchant
Quick effect, but its long-time stability and effectiveness are a big problems.Cross-linked hydrogel microsphere is by acrylamide, acrylic acid, friendship
The hydration properties for joining the inverted emulsion copolymerizations such as agent and being formed, cross-linked polymer microsphere dispersion is that have to receive
The dispersion of meter level or micron-sized cross-linked polymer particle in water, the dispersion is less by ectocine, such as can be direct
With waste water, with heatproof, salt-tolerant trait, and possess low viscosity, the advantages of pollution-free, cost is relatively low.With some strength
Nanometer or micron level hydrogel microsphere, relative to the micron order pore diameter of reservoir rockses, remote well can be realized completely
The purpose of profile control.The selectivity water suction of hydrogel microsphere and super-strong moisture absorbing expansion characteristics are especially suitable for the envelope of current predominant pathway
It is stifled.In addition, after pressure difference of blocking exceedes certain value, microsphere can occur elastic deformation to be continued, toward deep migration, to play by pore throat
Along the effect of journey profile control.
External hydrogel microsphere was applied to improve the research of recovery ratio less than 20 years, but achieved with it is quite plentiful and substantial into
Really.United States Patent (USP) US5465792 report by injection carry submicron hydrogel microsphere hydrocarbon fluid can realize it is hypotonic
The selective shut-off of oil reservoir water stream channel, effectively reduces Produced Liquid moisture content.Document（James P,Frampton H,
Brinkman J,etal.Field application of a new in-depth waterflood conformance
improvement tool.SPE84897,2003）It is good near that the site pilot test of middle report shows that hydrogel microsphere has
Well augmented injection and the performance of deep profile correction, oil increasing effect is obvious.Further, since captivation is the main cause for causing microsphere to be detained；
By adding anion surfactant gravitation can be effectively reduced between microsphere so as to the migration for promoting it in rock core.
It is domestic that the theory and application research that hydrogel microsphere is used to improve oil recovery factor is started late.Chinese patent
CN101029109A is obtained acrylamide and methyl-prop with oxidoreduction/azo composite initiator using via Inverse-Phase Suspension Polymerization
The crosslinking copolymers microsphere of alkene acyloxyethyl trimethyl ammonium chloride, its water suction can gradually expand, and swelling rate and multiplying power are controllable.But
Polymerization used easily forms a large amount of low polymerization degree products, and particle diameter distribution is wider, and total solid content is relatively low（Generally below
15%）.Chinese patent CN101298488A (a kind of preparation method of cationic polyacrylamide reverse microemulsion) is using progressively
Polymerization is prepared for cationic polyacrylamide reverse microemulsion, and product has moderate molecular weight, good emulsion stability, molten
Solution speed is fast, narrow diameter distribution the features such as, but its solid content also only 11.6%.Chinese patent CN1903974A is drawn using low temperature light
Agent is sent out, synthesizes the polymer microgel of nano-scale, its microemulsion is stablized, particle diameter is easy to control, but emulsifier content used
Up to more than 25%, high production cost certainly will be caused.Hydrophobic units are distributed with random or micro-block structure in hydrophobic associated polymer
In macromolecular chain, be conducive to improving the temperature-resistant anti-salt ageing resistace of polymer, and the association between hydrophobic group, it is easy to
Interpolymer Association is built bridge, and is disassociated under shear action, can be replied after shearing, favourable to the retention rate of polymer solution viscosity.Make a general survey of
Domestic and foreign literature and patent, relevant special construction polymer microballoon such as band specific functional groups microsphere, hydrophobic association microsphere are reported
Then shorter mention.
The content of the invention
One of the technical problem to be solved is that conventional oil field polymer microballoon has high temperature height in prior art
Under the conditions of salt easily aquation, expand it is uncontrollable and to the problem of high permeability zonal isolation effect difference, there is provided it is a kind of new to dredge
Water association crosslinked microsphere, for tertiary oil production in oil field field in, with temperature-resistant anti-salt performance, in high temperature, high-salinity brine
Achievable gradual change is swelling, association type occurs between microsphere and builds bridge, and can effectively block stratum macropore, water plugging and profile controlling effect is significant
Feature.
The two of the technical problem to be solved are to provide a kind of hydrophobic association with one of solution technical problem and hand over
The corresponding preparation method of connection microsphere.
The three of the technical problem to be solved are the hydrophobic association crosslinked microspheres described in one of above-mentioned technical problem
Application in tertiary oil production in oil field.
To solve one of above-mentioned technical problem, technical scheme is as follows：Hydrophobic association crosslinked microsphere, it is described hydrophobic
Association crosslinked microsphere is that in the case where adding or being not added with cross-linking agent, copolymerization is obtained by monomer；The monomer include acrylamide,
Water solublity temperature-resistant anti-salt monomer with such as formula（I）Shown cross-linking type is heat-resisting/hydrophobic monomer, wherein, R1~R4Each independently take from hydrogen
Atom, methyl or ethyl, R5、R6Each independently take from hydrogen atom, methyl, ethyl, methoxy or ethoxy.
In above-mentioned technical proposal, the particle diameter of the crosslinked microsphere is preferably 30~1500nm, described such as formula（I）Shown friendship
Connection type is heat-resisting/and the ratio of the amount of the material of hydrophobic monomer, water solublity temperature-resistant anti-salt monomer and acrylamide is（0.01~10）：
（0.01~10）：（80~99.98）.
In above-mentioned technical proposal, the hydrophobic association crosslinked microsphere is preferably in parts by weight, in 5~20 parts of emulsifying agent
Under emulsification, 5~50 parts of monomer is dissolved in 10~70 parts of deionized water and 20~80 parts of oil-based solvent, to aoxidize
Reduction initiator causes, and is obtained by inverse emulsion polymerization.
In above-mentioned technical proposal, the emulsifying agent preferably is selected from span, tween, alkylphenol polyoxyethylene, fatty alcohol polyoxy
It is vinyl Ether, sodium lauryl sulphate, dodecyl sodium sulfate, dodecylbenzene sodium sulfonate, trimethyl quaternary ammonium salt, double
Dodecyl dimethyl quaternary ammonium salt, hexadecanyl trimethyl quaternary ammonium salt, di-cetyl dimethyl quaternary ammonium salt, octadecyl front three
At least one in based quaternary ammonium salt, double octadecyldimethyl quaternary ammonium salts；The quaternary ammonium salt is chlorination ammonium salt or bromination ammonium salt.
In above-mentioned technical proposal, the reversed-phase emulsion preferably includes co-emulsifier.The co-emulsifier preferably is selected from C2~C6's
Monohydric alcohol（For example：Ethanol, propanol, isopropanol, n-butyl alcohol, isobutanol, the tert-butyl alcohol, amylalcohol, hexanol etc.）、C2~C6Dihydroxylic alcohols
（For example：Ethylene glycol, Propylene Glycol, butanediol, pentanediol, hexanediol）、C3~C6Trihydroxylic alcohol（For example：Glycerol, trihydroxy methyl third
Alkane etc.）、C1~C4Carboxylate, C2~C6At least one in dicarboxylate.The C1~C4The preferred ammonium salt of carboxylate or alkali gold
Category salt（For example：Sodium formate, potassium formate, ammonium formate, sodium acetate, potassium acetate, ammonium acetate etc.）；The C2~C6Dicarboxylate is excellent
Select ammonium salt or alkali metal salt（For example：Adipic acid sodium, sodium malonate etc.）.Co-emulsifier consumption is preferably emulsifying agent gross weight
0.01~10%.
In above-mentioned technical proposal, the oil-based solvent preferably is selected from the mixture of hydrocarbon or hydrocarbon.Such as described oil-based solvent can be with
Be thiacyclohexane, hexane, heptane, octane, isobutyltrimethylmethane., benzene, toluene, ethylbenzene, dimethylbenzene, isopropylbenzene, liquid paraffin, white oil, gasoline,
At least one in diesel oil and kerosene.
In above-mentioned technical proposal, the water solublity temperature-resistant anti-salt monomer preferably is selected from non-ionic monomer, anionic monomer or sun
At least one in ion monomer；Wherein described non-ionic monomer preferably is selected from NIPA, N- methylol acryloyls
Amine, N, N- DMAAs, N, in N- acrylamides, N- vinylpyridines or NVP extremely
Few one kind；The anionic monomer preferably be selected from vinyl sulfonic acid and its salt, vinylbenzenesulfonic acid and its salt, allyl sulphonic acid and its
Salt, allyl benzene sulfonic acid and its salt or 2- acrylamide-2-methylpro panesulfonic acids and its at least one in salt, described salt is
Alkali metal salts or ammonium salt；The cationic monomer preferably is selected from dimethyl ethyl allyl ammonium chloride, dimethyl diallyl chlorination
Ammonium, acrylyl oxy-ethyl-trimethyl salmiac, acryloxyethyldimethyl ethyl phosphonium bromide ammonium, methylacryoyloxyethyl front three
At least one in ammonium chloride, 2- acrylamido -2- trimethoxysilyl propyl methacrylate ammonium chlorides.
In above-mentioned technical proposal, oxidant used is selected from inorganic peroxide in the redox initiator；For example
The inorganic peroxide initiator system of ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate or hydrogen peroxide.In the redox initiator
Reducing agent used preferably is selected from alkali metal sulfite, alkali metal bisulfite, alkali metal thiosulfate；The reducing agent
At least one preferably be selected from sodium sulfite, Potassium acid sulfite, sodium sulfite, potassium sulfite, sodium thiosulfate, ferrous chloride
Kind.The mass ratio of the oxidant and the reducing agent is preferably（0.01~10）：1, its total consumption is preferably monomer weight
0.001~5%.
In above-mentioned technical proposal, the cross-linking agent preferably be selected from methylene-bisacrylamide, methylenebismethacrylamide,
Triallylamine, pentaerythritol triacrylate, polyethyleneglycol diacrylate, divinylbenzene or N, N '-penylene span
At least one come in acid imide.The dosage of crosslinking agent accounts for reactant mixture gross weight 10 when preparing hydrophobic association crosslinked microsphere
~10000ppmw.
To solve the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：The hydrophobic association crosslinked microsphere
Preparation method, comprise the following steps：
1）The preparation of water phase：Acrylamide, water solublity temperature-resistant anti-salt monomer, hydrophilic cross-linking agent and reducing agent is molten
In the 90~99.9% of water gross weight water, solution ph is adjusted to 7~12, obtain water phase I with alkali liquor；By oxidant
It is dissolved in the water of surplus and obtains water phase II；
2）The preparation of emulsion：By emulsifying agent and/or co-emulsifier, cross-linking type it is heat-resisting/hydrophobic monomer and lipophilic crosslinking
Agent is dissolved in oil-based solvent and obtains oil phase, by step 1）Water phase I of middle preparation is added in oil phase, is sufficiently stirred for obtaining anti-phase breast
Liquid；
3）Inverse emulsion polymerization：Removing is dissolved in step 2）Reversed-phase emulsion in oxygen, add step 1）Middle preparation
Water phase II, the initiated polymerization at 5~50 DEG C, exothermic peak temperature continues to react 0.5~8 hour after occurring, and obtains hydrophobic
The emulsion system of association crosslinked microsphere.
Heretofore described formula（I）Described cross-linking type is heat-resisting/and hydrophobic monomers can be obtained by commercially available channel, it is also possible to
It is prepared by the following method：Will（Methyl）Acrylonitrile and formula（II）Shown compound be scattered in sulfur trioxide, pyridine and
In the mixed solution of glacial acetic acid, under the conditions of 10~50 DEG C, react 0.5~6 hour, be obtained such as formula（I）Shown cross-linking type is resistance to
Heat/hydrophobic monomer.
Formula（II）Shown cross-linking type is heat-resisting/hydrophobic monomer for example, divinylbenzene can be selected from（It can be ortho position, right
Position, meta divinylbenzene or their mixture）, alkyl replace divinylbenzene or alkoxyl to replace in divinylbenzene
It is at least one.
The three of the technical problem to be solved are any one of the technical scheme of one of above-mentioned technical problem
Application of the hydrophobic association crosslinked microsphere in tertiary oil production in oil field.Its usage, such as breast of described hydrophobic association crosslinked microsphere
Liquid system directly with the dilution of clear water, high-salinity brine or Oil Field recovered water, individually or with other oil field chemicals is compounded
After be applied to make water plugging profile control agent in tertiary oil production in oil field to improve oil recovery factor.The salinity example of the high-salinity brine
Such as can be that total salinity is 50000~250000mg/L.
Emulsion of the present invention includes microemulsion.It is adapted with this concept, emulsion polymerization includes micro-emulsion polymerization, anti-phase
Emulsion includes reverse micro emulsion, and inverse emulsion polymerization is including conversed phase micro emulsion copolymerization etc..
The inventive method it is critical only that using inverse emulsion polymerization method, in conventional acrylamide polymer microsphere
Introducing crosslinked type is heat-resisting/hydrophobic monomer unit, gradual change can occur in 92 DEG C of high temperature, the saline of 170000mg/L high salinities molten
It is swollen, there is association type between microsphere and build bridge, still up to more than 7.6 times of expansion multiplying power after aging 30 days, show under oxygen free condition
Excellent heatproof, salt-resistance and ageing resistace；In addition, can also effective macropore plugging, under oxygen free condition after aging 30 days
Still have 72.2% to the closure efficiency of 1200mD rock cores.According to needs are applied, by the emulsion body of described hydrophobic association crosslinked microsphere
System is directly diluted with clear water, high-salinity brine or Oil Field recovered water, should after compounding individually or with other oil field chemicals
For making water plugging profile control agent in tertiary oil production in oil field to improve oil recovery factor.
Below by embodiment, the invention will be further elaborated.
Specific embodiment
【Embodiment 1】
1st, cross-linking type it is heat-resisting/synthesis of hydrophobic monomer：
Under nitrogen protection, 10g sulfur trioxide, 9mL pyridines are stirred at room temperature, uniform dissolution is in filling 100mL ice
In the glass reaction kettle of acetic acid, then be slowly added dropwise in the mixed solution into 12g methacrylonitriles, after be added dropwise to 28g2,5- bis-
Methyl isophthalic acid, 4- divinylbenzene continuous stirring and is reacted 3.5 hours at 38 DEG C, imports 350mL deionized waters, is stirred
After stand, Jing filter, washing, be dried, obtain cross-linking type it is heat-resisting/hydrophobic monomer 2,5- dimethyl-Isosorbide-5-Nitrae-two（1- methacryls
Amido ethyl）Benzene, yield is 89.6%.
2nd, acrylamide -2,5- dimethyl -1,4- two（1- methacryl amido ethyls）The synthesis of benzene microsphere
75g normal hexane, 27.5g sorbitan monooleates, 12g OPEOs are added in reactor
（10）, 0.6g2,5- dimethyl -1,4- two（1- methacryl amido ethyls）Benzene monomer, stirring is allowed to mix homogeneously, controls
Temperature in the kettle is 35 DEG C, and stir speed (S.S.) is 350 revs/min.50g deionized waters, 95g acrylamides, 0.25g are added in batching kettle
Triallylamine, 0.15g disodiumedetates, the 0.88g tert-butyl alcohols, 1.5g sodium sulfite, stirring is allowed to be uniformly dissolved, and uses
NaOH aqueous solutions adjust pH value to 7.9；In addition, 2g sodium peroxydisulfates are dissolved in 15g deionized waters, it is standby.Above-mentioned water is mutually led
In entering reactor, stirring is allowed to fully emulsified, adds sodium persulfate aqueous solution, and system temperature rise continues to react 3 hours to 71 DEG C,
After terminating reaction, discharging.Resulting polymers microemulsion system is still transparent, not stratified after standing 3 months.
The above-mentioned products of 15g are taken, 7.5g dodecylbenzene sodium sulfonate is added, stirring and dissolving is uniform, sample analysis.Using following
The structure and performance of method or standard testing gained hydrophobic association acrylamide copolymer：By GB/T12005.2-89 polyacrylamides
Amine solid content method determines the solid content of polymer；By Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard
《Polymer microballoon in-depth profile control technical conditions》Assay method tests separated out solid content, the microsphere of microsphere emulsion system
Initial particle and distribution and under 92 DEG C, oxygen free condition, in 170000mg/L salinity saline place 7 days, 15 days, 30 days
The expansion multiplying power of microspherulite diameter afterwards, rock core Seepage Experiment investigates thus obtained microsphere emulsion system under above-mentioned condition after aging 30 days
Closure efficiency.It is as shown in table 1 to the result of above-mentioned analysis.
【Embodiment 2】
Cross-linking type is heat-resisting/synthetic reaction process of the hydrophobic monomer, preparation process of hydrophobic association crosslinked microsphere, together【It is real
Apply example 1】, simply by 2,5- dimethyl-Isosorbide-5-Nitrae-two（1- methacryl amido ethyls）The consumption of benzene monomer increases to 1.05g.
Using following methods or the structure and performance of standard testing gained hydrophobic association crosslinked microsphere：By Q/SH1020 SINOPEC
Shengli Petroleum Administration Bureau's company standard《Polymer microballoon in-depth profile control technical conditions》Assay method tests microsphere emulsion system
Separated out solid content, microsphere initial particle and distribution and under 92 DEG C, oxygen free condition, in 170000mg/L salinities
In saline place 7 days, 15 days, after 30 days microspherulite diameter expansion multiplying power, rock core Seepage Experiment investigate thus obtained microsphere emulsion system
Closure efficiency under above-mentioned condition after aging 30 days.It is as shown in table 1 to the result of above-mentioned analysis.
【Embodiment 3】
Cross-linking type is heat-resisting/synthetic reaction process of the hydrophobic monomer, preparation process of hydrophobic association crosslinked microsphere, together【It is real
Apply example 1】, simply by 2,5- dimethyl-Isosorbide-5-Nitrae-two（1- methacryl amido ethyls）The consumption of benzene monomer increases to 1.61g.
Using following methods or the structure and performance of standard testing gained hydrophobic association crosslinked microsphere：By Q/SH1020 SINOPEC
Shengli Petroleum Administration Bureau's company standard《Polymer microballoon in-depth profile control technical conditions》Assay method tests microsphere emulsion system
Separated out solid content, microsphere initial particle and distribution and under 92 DEG C, oxygen free condition, in 170000mg/L salinities
In saline place 7 days, 15 days, after 30 days microspherulite diameter expansion multiplying power, rock core Seepage Experiment investigate thus obtained microsphere emulsion system
Closure efficiency under above-mentioned condition after aging 30 days.It is as shown in table 1 to the result of above-mentioned analysis.
【Embodiment 4】
1st, cross-linking type it is heat-resisting/synthesis of hydrophobic monomer：
Under nitrogen protection, 9g sulfur trioxide, 8mL pyridines are stirred at room temperature, uniform dissolution is in filling 90mL ice vinegar
In the glass reaction kettle of acid, then be slowly added dropwise in the mixed solution into 10g acrylonitrile, after be added dropwise to 25g p-divinyl benzenes,
Continuous stirring and react 3.5 hours at 38 DEG C, import 350mL deionized waters, stand after stirring, Jing is filtered, washing, dry
It is dry, obtain cross-linking type it is heat-resisting/hydrophobic monomer Isosorbide-5-Nitrae-two（1- acrylamidoethyls）Benzene, yield is 88.7%.
2nd, acrylamide-NVP -1,4- bis-（1- acrylamidoethyls）The conjunction of benzene crosslinked microsphere
Into
72g white oils, 27.5g sorbitan monooleates, 12g OPEOs are added in reactor
（10）, 1.5g1,4- bis-（1- acrylamidoethyls）Benzene monomer, stirring is allowed to mix homogeneously, controls temperature in the kettle for 36 DEG C,
Stir speed (S.S.) is 310rpm.58g water, 82g acrylamides, 20g NVPs, 0.2g is added to gather in batching kettle
Ethylene glycol and acrylate, 0.2g disodiumedetates, 0.25g isopropanols, 2.2g sodium thiosulfate, stirring is allowed to dissolve
Uniformly, with NaOH aqueous solutions pH value is adjusted to 9.8；In addition, 1.2g Ammonium persulfate .s are dissolved in 10g deionized waters, it is standby.Will be upper
State water mutually to import in reactor, stirring be allowed to fully emulsified, add 6g sodium thiosulfate solutions, system temperature rise to 65 DEG C, after
Continuous reaction 2 hours, after terminating reaction, discharging.Resulting polymers microemulsion system is still transparent, not stratified after standing 3 months.
The above-mentioned products of 20g are taken, 9g dodecylbenzene sodium sulfonate is added, stirring and dissolving is uniform, sample analysis.Using following sides
The structure and performance of method or standard testing gained hydrophobic association acrylamide copolymer：Win by Q/SH1020 SINOPEC
Petroleum Authority's company standard《Polymer microballoon in-depth profile control technical conditions》Assay method test microsphere emulsion system can
Solid content, microsphere initial particle and distribution are separated out and under 92 DEG C, oxygen free condition, in 170000mg/L salinity saline
It is middle place 7 days, 15 days, after 30 days microspherulite diameter expansion multiplying power, rock core Seepage Experiment investigate thus obtained microsphere emulsion system in upper
Closure efficiency under the conditions of stating after aging 30 days.It is as shown in table 1 to the result of above-mentioned analysis.
【Embodiment 5】
Cross-linking type is heat-resisting/synthetic reaction process of the hydrophobic monomer, preparation process of hydrophobic association crosslinked microsphere, together【It is real
Apply example 4】, simply by Isosorbide-5-Nitrae-two（1- acrylamidoethyls）The consumption of benzene monomer increases to 1.9g.Using following methods or mark
The structure and performance of quasi- test gained hydrophobic association crosslinked microsphere：Look forward to by Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation
Industry standard《Polymer microballoon in-depth profile control technical conditions》The separated out solid content of assay method test microsphere emulsion system contains
Amount, microsphere initial particle and distribution and under 92 DEG C, oxygen free condition, in 170000mg/L salinity saline place 7 days, 15
My god, after 30 days microspherulite diameter expansion multiplying power, rock core Seepage Experiment investigate thus obtained microsphere emulsion system it is aging under above-mentioned condition
Closure efficiency after 30 days.It is as shown in table 1 to the result of above-mentioned analysis.
【Embodiment 6】
Cross-linking type is heat-resisting/synthetic reaction process of the hydrophobic monomer, preparation process of hydrophobic association crosslinked microsphere, together【It is real
Apply example 4】, simply by Isosorbide-5-Nitrae-two（1- acrylamidoethyls）The consumption of benzene monomer is reduced to 0.9g.Using following methods or mark
The structure and performance of quasi- test gained hydrophobic association crosslinked microsphere：Look forward to by Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation
Industry standard《Polymer microballoon in-depth profile control technical conditions》The separated out solid content of assay method test microsphere emulsion system contains
Amount, microsphere initial particle and distribution and under 92 DEG C, oxygen free condition, in 170000mg/L salinity saline place 7 days, 15
My god, after 30 days microspherulite diameter expansion multiplying power, rock core Seepage Experiment investigate thus obtained microsphere emulsion system it is aging under above-mentioned condition
Closure efficiency after 30 days.It is as shown in table 1 to the result of above-mentioned analysis.
【Comparative example 1】
The preparation process of hydrophobic association crosslinked microsphere, together【Embodiment 1】, simply without 2,5- dimethyl-Isosorbide-5-Nitrae-two
（1- methacryl amido ethyls）Benzene monomer.Using following methods or the structure of standard testing gained hydrophobic association crosslinked microsphere
With performance：By Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard《Polymer microballoon in-depth profile control technology
Condition》Assay method test the separated out solid content of microsphere emulsion system, microsphere initial particle and distribution and 92 DEG C,
Under oxygen free condition, place in the 170000mg/L salinity saline 7 days, 15 days, after 30 days microspherulite diameter expansion multiplying power, rock core
Seepage Experiment investigates closure efficiency of the thus obtained microsphere emulsion system under above-mentioned condition after aging 30 days.Result to above-mentioned analysis
As shown in table 1.
【Comparative example 2】
Cross-linking type is heat-resisting/synthetic reaction process of the hydrophobic monomer, preparation process of hydrophobic association crosslinked microsphere, together【It is real
Apply example 4】, simply without Isosorbide-5-Nitrae-two（1- acrylamidoethyls）Benzene monomer.Dredged using following methods or standard testing gained
The structure and performance of water association crosslinked microsphere：By Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard《Polymerization
Thing microsphere in-depth profile control technical conditions》The separated out solid content of assay method test microsphere emulsion system, microsphere are initial
Particle diameter and distribution and under 92 DEG C, oxygen free condition, place in the 170000mg/L salinity saline 7 days, 15 days, it is micro- after 30 days
The expansion multiplying power in spherolite footpath, rock core Seepage Experiment investigates closure of the thus obtained microsphere emulsion system under above-mentioned condition after aging 30 days
Efficiency.It is as shown in table 1 to the result of above-mentioned analysis.
Table 1
Claims (10)
1. hydrophobic association crosslinked microsphere, the hydrophobic association crosslinked microsphere be by monomer in the case where adding or being not added with cross-linking agent
Copolymerization is obtained；The monomer include acrylamide, water solublity temperature-resistant anti-salt monomer it is heat-resisting with cross-linking type as shown in formula (I)/dredge
Aqueous monomer, wherein, R1~R4Each independently take from hydrogen atom, methyl or ethyl, R5、R6Each independently take from hydrogen atom, methyl,
Ethyl, methoxy or ethoxy：
2. the hydrophobic association crosslinked microsphere described in claim 1, it is characterised in that the particle diameter of the crosslinked microsphere is 30~
1500nm, the cross-linking type as shown in formula (I) is heat-resisting/thing of hydrophobic monomer, water solublity temperature-resistant anti-salt monomer and acrylamide
The ratio of the amount of matter is (0.01~10)：(0.01~10)：(80~99.98).
3. the hydrophobic association crosslinked microsphere described in claim 1, it is characterised in that the hydrophobic association crosslinked microsphere is with weight
Part meter, 5~20 parts emulsifiers effect under, by 5~50 parts of monomer be dissolved in 10~70 parts deionized water and 20~
In 80 parts of oil-based solvent, with redox initiator initiation, it is obtained by inverse emulsion polymerization.
4. the hydrophobic association crosslinked microsphere described in claim 3, it is characterised in that the emulsifying agent is selected from span, tween, alkyl
Phenol polyethenoxy ether, fatty alcohol-polyoxyethylene ether, sodium lauryl sulphate, dodecyl sodium sulfate, dodecylbenzene sodium sulfonate,
Trimethyl quaternary ammonium salt, double dodecyl dimethyl quaternary ammonium salts, hexadecanyl trimethyl quaternary ammonium salt, double hexadecyl two
At least one in methyl quaternary ammonium, octadecyl trimethyl quaternary ammonium salt, double octadecyldimethyl quaternary ammonium salts；The quaternary ammonium salt
For chlorination ammonium salt or bromination ammonium salt.
5. the hydrophobic association crosslinked microsphere described in claim 3, it is characterised in that mixing of the oil-based solvent selected from hydrocarbon or hydrocarbon
Thing.
6. the hydrophobic association crosslinked microsphere described in claim 1, it is characterised in that the water solublity temperature-resistant anti-salt monomer is selected from non-
At least one in ion monomer, anionic monomer or cationic monomer；Wherein described non-ionic monomer is selected from N- isopropyls third
Acrylamide, N hydroxymethyl acrylamide, N-N- DMAAs, N-N- acrylamides, N- vinylpyridines or
At least one in NVP；The anionic monomer is selected from vinyl sulfonic acid and its salt, vinylbenzenesulfonic acid
And its in salt, allyl sulphonic acid and its salt, allyl benzene sulfonic acid and its salt or 2- acrylamide-2-methylpro panesulfonic acids and its salt
At least one, described salt is alkali metal salts or ammonium salt；The cationic monomer selected from dimethyl ethyl allyl ammonium chloride,
Dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, acryloxyethyldimethyl ethyl phosphonium bromide ammonium, first
At least one in base acrylyl oxy-ethyl-trimethyl salmiac, 2- acrylamido -2- trimethoxysilyl propyl methacrylate ammonium chlorides.
7. the hydrophobic association crosslinked microsphere described in claim 3, it is characterised in that oxygen used in the redox initiator
Agent is selected from inorganic peroxide；Reducing agent used is selected from alkali metal sulfite, alkali gold in the redox initiator
Category bisulfites, alkali metal thiosulfate.
8. the hydrophobic association crosslinked microsphere described in claim 1, it is characterised in that the cross-linking agent is selected from methylene bisacrylamide acyl
Amine, methylenebismethacrylamide, triallylamine, pentaerythritol triacrylate, polyethyleneglycol diacrylate, diethyl
Alkenyl benzene or N, N ' at least one in-penylene a BMI.
9. the preparation method of hydrophobic association crosslinked microsphere any one of claim 1~8, comprises the following steps：
1) preparation of water phase：Acrylamide, water solublity temperature-resistant anti-salt monomer, hydrophilic cross-linking agent and reducing agent are dissolved in into institute
In stating 90~99.9% water of water gross weight, solution ph is adjusted to 7~12, obtain water phase I with alkali liquor；Oxidant is dissolved in
Water phase II is obtained in the water of surplus；
2) preparation of emulsion：By emulsifying agent and/or co-emulsifier, cross-linking type it is heat-resisting/hydrophobic monomer and lipophilic cross-linking agent it is molten
Oil phase is obtained in oil-based solvent, by step 1) in prepare water phase I be added in oil phase, be sufficiently stirred for obtaining reversed-phase emulsion；
3) inverse emulsion polymerization：Removing be dissolved in step 2) reversed-phase emulsion in oxygen, add step 1) in prepare water phase
II, the initiated polymerization at 5~50 DEG C, exothermic peak temperature continues to react 0.5~8 hour after occurring, and obtains hydrophobic association
The emulsion system of crosslinked microsphere.
10. application of the hydrophobic association crosslinked microsphere any one of claim 1~8 in tertiary oil production in oil field.
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