CN104558403A - Cross-linked gradient swelling polymeric microsphere and preparation method thereof - Google Patents
Cross-linked gradient swelling polymeric microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention provides a cross-linked gradient swelling polymeric microsphere and a preparation method thereof and mainly solves the problems in the prior art that a conventional oil field polymer microsphere has extremely high probability of hydration under high-temperature and high-salinity conditions, is uncontrollable in swelling and is poor in plugging effect on high-permeability oil reservoir. The cross-linked gradient swelling polymeric microsphere is formed by radical polymerization of a monomer in presence of a cross-linking agent, wherein the monomer comprises acrylamide and/or other water-soluble monomers and a heat-proof/hydrophobic monomer shown in formula I; R1 and R2 are respectively independently selected from hydrogen atom, methyl or ethyl; and R3 is alkoxy of C1-C16 or alkyl except for alkenyl. Through the adoption of the technical scheme, the problems are better solved and the cross-linked gradient swelling polymeric microsphere can be used in tertiary oil recovery operation of an oil field.
Description
Technical field
The present invention relates to crosslinked gradual change swellable polymer microballoon and preparation method thereof, and the application of described crosslinked gradual change swellable polymer microballoon in tertiary oil production in oil field.
Background technology
How effectively to improve the seepage flow situation of oil field heterogeneous reservoir, improve sweep efficiency and the swept volume of driven water-replacing, thus improve oil recovery factor, become key subjects urgently to be resolved hurrily in current tertiary oil recovery process.Current, generally use chemical reagent to carry out shutoff oilfield high infiltration permeable layers, i.e. so-called water plugging and profile controlling method both at home and abroad.The water plugging profile control agent of application mainly contains inorganics class, polymer class, foam class etc.But inorganics class water plugging profile control agent is because of incompressible or distortion, immediate vicinity of wellbore is caused to block and earth formation deep cannot be deep into; Polymer class water plugging profile control agent is then owing to easily precipitating under facile hydrolysis, high salinity under high temperature, and to temperature and salinity sensitivity, ageing resistance is poor and limit its application; Foam class water plugging profile control agent has excellent Jamin effect, but its permanent stability and validity are large problems.Cross-linked hydrogel microballoon is the hydration properties formed through reversed-phase emulsion or Inverse mi-croemulsion copolymerization by acrylamide, vinylformic acid, linking agent etc., cross-linked polymer microsphere dispersion system has nano level or the dispersion of micron-sized cross-linked polymer particle in water, this dispersion is less by ectocine, as directly waste water can be used, there is heatproof, salt-tolerant trait, and possess the advantages such as low viscosity, pollution-free, cost is lower.There is the nanometer of some strength or the hydrogel microsphere of micron level, relative to the micron order pore diameter of reservoir rocks, the object of well profile control far away can be realized completely.The selectivity water suction of hydrogel microsphere and super-strong moisture absorbing expansion characteristics are especially applicable to the shutoff of current predominant pathway.In addition, after pressure difference of blocking exceedes certain value, elastic deformation can occur microballoon continues, toward deep migration, to play the effect along journey profile control by pore throat.
External hydrogel microsphere is applied to the not enough Two decades years of the research improving recovery ratio, but has achieved suitable great successes.US Patent No. 5465792 reports the selectively blocking off that can realize LOW PERMEABILITY RESERVOIR water stream channel by injecting the hydrocarbon fluid carrying submicron hydrogel microsphere, effectively reduces Produced Liquid water ratio.Document (James P, Frampton H, Brinkman J, etal. Field application of a new in-depth waterflood conformance improvement tool. SPE84897,2003) in, the site pilot test of report shows that hydrogel microsphere has good nearly well augmented injection and the performance of deep profile correction, and oil increasing effect is obvious.In addition, because magnetism is the major cause causing microballoon to be detained; Gravitation between microballoon can be effectively reduced thus the migration promoting it in rock core by adding anion surfactant.
Domestic hydrogel microsphere to be started late for the theory and application research improving oil recovery factor.Chinese patent CN101029109A is with redox/azo composite initiator, via Inverse-Phase Suspension Polymerization is adopted to obtain the crosslinking copolymers microballoon of acrylamide and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, its water suction can be expanded gradually, swelling rate and multiplying power controlled.But polymerization process used easily forms a large amount of low polymerization degree product, and size distribution is wider, total solid content relatively low (generally lower than 15%).Chinese patent CN101298488 adopts progressively polymerization process to prepare cationic polyacrylamide reverse microemulsion, the features such as product has that molecular weight is moderate, good emulsion stability, dissolution rate are fast, narrow diameter distribution, but its solid content also only 11.6%.Chinese patent CN 1903974A adopts low temperature light trigger, synthesizes the polymer microgel of nano-scale, and its microemulsion is stablized, and particle diameter is convenient to control, but emulsifier content used is up to more than 25%, certainly will cause high production cost.In hydrophobic associated polymer, hydrophobic units is distributed in macromolecular chain with random or micro-block structure, be conducive to the temperature resistant antisalt ageing resistance improving polymkeric substance, and the association between hydrophobic grouping, be easy to Interpolymer Association build bridge, under shearing action, solution is formed, can reply after shearing, favourable to the retention rate of polymer solution viscosity.Make a general survey of domestic and foreign literature and patent, then shorter mention reported by relevant special construction polymer microballoon such as band specific functional groups microballoon, hydrophobic association microballoon etc.
Summary of the invention
One of technical problem to be solved by this invention be in prior art conventional oil field polymer microballoon to exist under high temperature and high salt condition very easily aquation, expand uncontrollable and to high permeability zonal isolation weak effect problem, there is provided a kind of novel crosslinked gradual change swellable polymer microballoon, it has good heatproof, salt resistance and ageing resistance and the high feature of shutoff efficiency.
Two of technical problem to be solved by this invention is to provide a kind of preparation method corresponding with the crosslinked gradual change swellable polymer microballoon of one of technical solution problem.
Three of technical problem to be solved by this invention be the described crosslinked gradual change swellable polymer microballoon of one of above-mentioned technical problem in tertiary oil production in oil field in application.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: crosslinked gradual change swellable polymer microballoon, and it is the polymer microballoon formed through radical polymerization under linking agent exists by monomer; Described monomer comprise acrylamide and/or other water-soluble monomer with as shown in the formula (I) heat-resisting/hydrophobic monomers;
formula (I);
Wherein, R
1and R
2independently take from hydrogen atom, methyl or ethyl separately; R
3for C
1~ C
16alkoxyl group or thiazolinyl beyond alkyl.
In technique scheme, the particle diameter of described polymer microballoon is preferably 30 ~ 1500nm, described as shown in the formula (I) heat-resisting/ratio of the amount of substance of hydrophobic monomers and acrylamide and/or other water-soluble monomer is preferably (0.01 ~ 20): (80 ~ 99.99).
In technique scheme, described polymer microballoon is preferably with parts by weight, under the emulsifier effect of 5 ~ 20 parts, the monomer of 5 ~ 50 parts is dissolved in the oil-based solvent of the deionized water of 10 ~ 70 parts and 20 ~ 80 parts, cause with redox initiator, obtained by reversed-phase emulsion or conversed phase micro emulsion copolymerization.
In technique scheme, at least one of described emulsifying agent preferably in sapn, tween, alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, trimethyl quaternary ammonium salt, two dodecyl dimethyl quaternary ammonium salt, hexadecanyl trimethyl quaternary ammonium salt, di-cetyl dimethyl quaternary ammonium salt, octadecyl trimethyl quaternary ammonium salt, two octadecyldimethyl quaternary ammonium salt.
In technique scheme, described reversed-phase emulsion or reverse micro emulsion preferably also comprise assistant for emulsifying agent; Described assistant for emulsifying agent is preferably from C
2~ C
6monohydroxy-alcohol (such as: ethanol, propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, amylalcohol, hexanol etc.), C
2~ C
6dibasic alcohol (such as: ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol), C
3~ C
6trivalent alcohol (such as: glycerine, TriMethylolPropane(TMP) etc.), C
1~ C
4carboxylate salt, C
2~ C
6at least one in dicarboxylate.Described C
1~ C
4the preferred ammonium salt of carboxylate salt or an alkali metal salt (such as: sodium formiate, potassium formiate, ammonium formiate, sodium acetate, potassium acetate, ammonium acetate etc.); Described C
2~ C
6the preferred ammonium salt of dicarboxylate or an alkali metal salt (such as: adipic acid sodium, sodium malonate etc.); Assistant for emulsifying agent consumption is preferably 0.01 ~ 10% of emulsifying agent gross weight.
In technique scheme, described oil-based solvent is selected from the mixture of hydrocarbon or hydrocarbon.Such as described oil-based solvent can be at least one in cyclohexane, hexane, heptane, octane, octane-iso, benzene, toluene, ethylbenzene, dimethylbenzene, isopropyl benzene, whiteruss, white oil, gasoline, diesel oil and kerosene.
In technique scheme, at least one of other water-soluble monomer described preferably in non-ionic monomer, anionic monomer or cationic monomer; At least one of wherein said non-ionic monomer preferably in NIPA, N hydroxymethyl acrylamide, N-N-DMAA, N-N-acrylamide, N-vinyl pyridine or NVP; Described anionic monomer is selected from least one in vinyl carboxylic acid and salt, vinyl sulfonic acid and salt thereof, vinylbenzenesulfonic acid and salt, allyl sulphonic acid and salt thereof, allyl benzene sulfonic acid and salt thereof or 2-acrylamide-2-methylpro panesulfonic acid and salt thereof, and described salt is preferably alkali metal salts or ammonium salt; At least one of described cationic monomer preferably in dimethyl ethyl allyl ammonium chloride, dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, acryloxyethyldimethyl ethyl phosphonium bromide ammonium, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, 2-acrylamido-2-trimethoxysilyl propyl methacrylate ammonium chloride.
In technique scheme, oxygenant used in described redox initiator is preferably from inorganic peroxide; At least one in the preferred persulphate of described inorganic peroxide or hydrogen peroxide; The preferred ammonium salt of described persulphate or an alkali metal salt (such as: at least one in ammonium persulphate, Potassium Persulphate and Sodium Persulfate); Reductive agent used in the described redox initiator at least one preferably in alkali metal sulfite, alkali metal bisulfite and alkali metal thiosulfate.The example of described reductive agent has at least one in sodium bisulfite, Potassium hydrogen sulfite, S-WAT, potassium sulfite, Sulfothiorine, iron protochloride or ferrous sulfate etc.The mass ratio of described oxygenant and described reductive agent is preferably (0.01 ~ 10): 1, and described oxygenant and the total consumption of described reductive agent are 0.001 ~ 5% of monomer weight.
In technique scheme, described linking agent is selected from Vinylstyrene, methylene-bisacrylamide, methylenebismethacrylamide, triallylamine, pentaerythritol triacrylate, N, N ' at least one in-penylene a bismaleimides.Described dosage of crosslinking agent accounts for reaction mixture gross weight 10 ~ 10000ppmw when preparing crosslinked gradual change swellable polymer microballoon.
For solve the problems of the technologies described above two, technical scheme of the present invention is as follows: the preparation method of the crosslinked gradual change swellable polymer microballoon described in any one of the described technical scheme of one of above-mentioned technical problem, comprises the following steps:
1) preparation of aqueous phase: acrylamide and/or other water-soluble monomer, water-soluble cross-linker, reductive agent are dissolved in the water of 90 ~ 99.9% of described water gross weight, with alkali lye regulator solution pH value to 7 ~ 12, obtain aqueous phase I; Oxygenant is dissolved in separately in the water of surplus and obtains aqueous phase II;
2) preparation of reversed-phase emulsion or reverse micro emulsion: emulsifying agent or emulsifying agent and assistant for emulsifying agent, heat-resisting/hydrophobic monomers and oil-soluble crosslinking agent are dissolved in oil-based solvent and obtain oil phase, the aqueous phase I prepared in step 1) is joined in oil phase, fully stirs and obtain reversed-phase emulsion or reverse micro emulsion;
3) reversed-phase emulsion or conversed phase micro emulsion copolymerization: remove and be dissolved in step 2) reversed-phase emulsion or reverse micro emulsion in oxygen, add the aqueous phase II prepared in step 1), initiated polymerization at 5 ~ 50 DEG C, continue reaction 0.5 ~ 8 hour after exothermic peak temperature occurs, obtain the emulsion system of crosslinked gradual change swellable polymer microballoon.
Described in formula described in the present invention (I) heat-resisting/hydrophobic monomers obtains by commercially available channel, also can be prepared by following method: the compound shown in (methyl) vinyl cyanide and formula (II) is scattered in the mixing solutions of sulphur trioxide, pyridine and Glacial acetic acid, under 10 ~ 50 DEG C of conditions, react 0.5 ~ 6 hour, obtained as shown in the formula (I) heat-resisting/hydrophobic monomers.
formula (II)
For solve the problems of the technologies described above three, technical scheme of the present invention is as follows: the application of crosslinked gradual change swellable polymer microballoon in tertiary oil production in oil field according to any one of the technical scheme of one of above-mentioned technical problem.Its usage, such as the emulsion system of described crosslinked gradual change swellable polymer microballoon is directly with the dilution of clear water, high-salinity brine or Oil Field recovered water, is applied in tertiary oil production in oil field and makes water plugging profile control agent to improve oil recovery factor after independent or composite with other oil field chemical.The salinity of described high-salinity brine can be such as total mineralization is 50000 ~ 250000mg/L.
The present invention is cross-linked gradual change swellable polymer microballoon, and in the salt solution of 93 DEG C of high temperature, 160000mg/L high salinity, gradual change can to occur swelling, there is association type between microballoon to build bridge, under oxygen free condition, after aging 45 days, expansion multiplying power, still up to more than 4.5 times, shows excellent heatproof, salt resistance and ageing resistance; In addition, also can effective macropore plugging, under oxygen free condition, after aging 1 month, 69.8% is still had to the shutoff efficiency of 800mD rock core, achieve good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
1, the synthesis of heat-resisting/hydrophobic monomers
Under nitrogen protection; by 8.5g sulphur trioxide, 7mL pyridine in stirred at ambient temperature, be dissolved in and fill in the glass reaction still of 85mL Glacial acetic acid; 9g vinyl cyanide is slowly added dropwise to again in this mixing solutions; after be added dropwise to 24g to n-butylstyrene, continuously stirring at 33 DEG C also reacts 4 hours, imports 350mL deionized water; leave standstill after stirring; after filtration, washing, dry, obtain heat-resisting/hydrophobic monomers N-(1-to n-butylphenyl ethyl) acrylamide, productive rate is 90.1%.
2, vinylformic acid-acrylamide-N-(1-is to n-butylphenyl ethyl) synthesis of acrylamide microballoon
75g normal heptane, 27.5g Brij 35 (3), 7.5g polyoxyethylene octylphenol ether (4), 0.49g N-(1-is added to n-butylphenyl ethyl in reactor) acrylamide monomer, stirring makes it to mix, controlling temperature in the kettle is 25 DEG C, and stir speed (S.S.) is 255 revs/min.42g deionized water, 4g sodium hydroxide, 7.2g vinylformic acid, 52.8g acrylamide, 0.11g methylenebismethacrylamide, 0.15g disodium ethylene diamine tetraacetate, the 0.88g trimethyl carbinol, 1.5g S-WAT is added in batching kettle, stirring makes it to be uniformly dissolved, by NaOH aqueous solution adjust ph to 7.9; In addition, 2g Sodium Persulfate is dissolved in 15g deionized water, for subsequent use.Above-mentioned aqueous phase is imported in reactor, stir and make it fully emulsified, add sodium persulfate aqueous solution, system temperature rise to 71 DEG C, continue reaction 3 hours, after termination reaction, discharging.Resulting polymers microballoon emulsion system leaves standstill still transparent, not stratified after 3 months.
Get the above-mentioned product of 20g, add 9g Sodium dodecylbenzene sulfonate, stirring and dissolving is even, sampling analysis.Following method or standard testing gained is adopted to be cross-linked the Structure and Properties of gradual change swellable polymer microballoon: by the solid content separated out of Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard " polymer microballoon in-depth profile control technical qualification " measuring method test microballoon emulsion system, microballoon initial particle and distribution and at 93 DEG C, under oxygen free condition, place 7 days in 160000mg/L salinity salt solution, 15 days, 30 days, the expansion multiplying power of microspherulite diameter after 45 days, rock core Seepage Experiment investigates the shutoff efficiency of thus obtained microsphere emulsion system under above-mentioned condition after aging 1 month.As shown in table 1 to the result of above-mentioned analysis.
[embodiment 2]
The preparation process of the synthetic reaction process of heat-resisting/hydrophobic monomers, crosslinked gradual change swellable polymer microballoon, all with [embodiment 1], is to n-butylphenyl ethyl by N-(1-) consumption of acrylamide monomer is increased to 0.97g.Following method or standard testing gained is adopted to be cross-linked the Structure and Properties of gradual change swellable polymer microballoon: by the solid content separated out of Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard " polymer microballoon in-depth profile control technical qualification " measuring method test microballoon emulsion system, microballoon initial particle and distribution and at 93 DEG C, under oxygen free condition, place 7 days in 160000mg/L salinity salt solution, 15 days, 30 days, the expansion multiplying power of microspherulite diameter after 45 days, rock core Seepage Experiment investigates the shutoff efficiency of thus obtained microsphere emulsion system under above-mentioned condition after aging 1 month.As shown in table 1 to the result of above-mentioned analysis.
[embodiment 3]
The preparation process of the synthetic reaction process of heat-resisting/hydrophobic monomers, crosslinked gradual change swellable polymer microballoon, all with [embodiment 1], is to n-butylphenyl ethyl by N-(1-) consumption of acrylamide monomer is increased to 1.22g.Following method or standard testing gained is adopted to be cross-linked the Structure and Properties of gradual change swellable polymer microballoon: by the solid content separated out of Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard " polymer microballoon in-depth profile control technical qualification " measuring method test microballoon emulsion system, microballoon initial particle and distribution and at 93 DEG C, under oxygen free condition, place 7 days in 160000mg/L salinity salt solution, 15 days, 30 days, the expansion multiplying power of microspherulite diameter after 45 days, rock core Seepage Experiment investigates the shutoff efficiency of thus obtained microsphere emulsion system under above-mentioned condition after aging 1 month.As shown in table 1 to the result of above-mentioned analysis.
[embodiment 4]
The preparation process of the synthetic reaction process of heat-resisting/hydrophobic monomers, crosslinked gradual change swellable polymer microballoon, all with [embodiment 1], is to n-butylphenyl ethyl by N-(1-) consumption of acrylamide monomer is increased to 1.91g.Following method or standard testing gained is adopted to be cross-linked the Structure and Properties of gradual change swellable polymer microballoon: the solid content measuring polymkeric substance by GB/T12005.2-89 polyacrylamide solid content method; By the solid content separated out of Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard " polymer microballoon in-depth profile control technical qualification " measuring method test microballoon emulsion system, microballoon initial particle and distribution and 93 DEG C, under oxygen free condition, in 160000mg/L salinity salt solution, place the expansion multiplying power of microspherulite diameter after 7 days, 15 days, 30 days, 45 days, rock core Seepage Experiment investigates the shutoff efficiency of thus obtained microsphere emulsion system under above-mentioned condition after aging 1 month.As shown in table 1 to the result of above-mentioned analysis.
[embodiment 5]
1, the synthesis of heat-resisting/hydrophobic monomers:
Under nitrogen protection; by 9g sulphur trioxide, 8mL pyridine in stirred at ambient temperature, be dissolved in and fill in the glass reaction still of 90mL Glacial acetic acid; 11g methacrylonitrile is slowly added dropwise to again in this mixing solutions; after be added dropwise to 25g to t-butoxystyrene, continuously stirring at 38 DEG C also reacts 4 hours, imports 340mL deionized water; leave standstill after stirring; after filtration, washing, dry, obtain heat-resisting/hydrophobic monomers N-(1-to tert .-butoxyphenyl ethyl) acrylamide, productive rate is 88.7%.
2, acrylamide-N-(1-is to tert .-butoxyphenyl ethyl) synthesis of acrylamide microballoon
72g white oil, 27.5g sorbitan monooleate, 12g polyoxyethylene octylphenol ether (10), 1g N-(1-is added to tert .-butoxyphenyl ethyl in reactor) acrylamide monomer, stirring makes it to mix, controlling temperature in the kettle is 36 DEG C, and stir speed (S.S.) is 310 revs/min.In batching kettle, add 58g water, 102g acrylamide, 0.15g methylene-bisacrylamide, 0.2g disodium ethylene diamine tetraacetate, 0.25g Virahol, 2.2g Sulfothiorine, stir and make it to be uniformly dissolved, by NaOH aqueous solution adjust ph to 9.8; In addition, 1.2g ammonium persulphate is dissolved in 10g deionized water, for subsequent use.Above-mentioned aqueous phase is imported in reactor, stir and make it fully emulsified, add ammonium persulfate aqueous solution, system temperature rise to 65 DEG C, continue reaction 2 hours, after termination reaction, discharging.Resulting polymers microemulsion system leaves standstill still transparent, not stratified after 3 months.
Get the above-mentioned product of 20g, add 9g Sodium dodecylbenzene sulfonate, stirring and dissolving is even, sampling analysis.Following method or standard testing gained is adopted to be cross-linked the Structure and Properties of gradual change swellable polymer microballoon: by the solid content separated out of Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard " polymer microballoon in-depth profile control technical qualification " measuring method test microballoon emulsion system, microballoon initial particle and distribution and at 93 DEG C, under oxygen free condition, place 7 days in 160000mg/L salinity salt solution, 15 days, 30 days, the expansion multiplying power of microspherulite diameter after 45 days, rock core Seepage Experiment investigates the shutoff efficiency of thus obtained microsphere emulsion system under above-mentioned condition after aging 1 month.As shown in table 1 to the result of above-mentioned analysis.
[embodiment 6]
The preparation process of the synthetic reaction process of heat-resisting/hydrophobic monomers, crosslinked gradual change swellable polymer microballoon, all with [embodiment 5], is to tert .-butoxyphenyl ethyl by N-(1-) consumption of acrylamide monomer is down to 0.72g.Following method or standard testing gained is adopted to be cross-linked the Structure and Properties of gradual change swellable polymer microballoon: by the solid content separated out of Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard " polymer microballoon in-depth profile control technical qualification " measuring method test microballoon emulsion system, microballoon initial particle and distribution and at 93 DEG C, under oxygen free condition, place 7 days in 160000mg/L salinity salt solution, 15 days, 30 days, the expansion multiplying power of microspherulite diameter after 45 days, rock core Seepage Experiment investigates the shutoff efficiency of thus obtained microsphere emulsion system under above-mentioned condition after aging 1 month.As shown in table 1 to the result of above-mentioned analysis.
[embodiment 7]
The preparation process of the synthetic reaction process of heat-resisting/hydrophobic monomers, crosslinked gradual change swellable polymer microballoon, all with [embodiment 5], is to tert .-butoxyphenyl ethyl by N-(1-) consumption of acrylamide monomer is increased to 1.45g.Following method or standard testing gained is adopted to be cross-linked the Structure and Properties of gradual change swellable polymer microballoon: by the solid content separated out of Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard " polymer microballoon in-depth profile control technical qualification " measuring method test microballoon emulsion system, microballoon initial particle and distribution and at 93 DEG C, under oxygen free condition, place 7 days in 160000mg/L salinity salt solution, 15 days, 30 days, the expansion multiplying power of microspherulite diameter after 45 days, rock core Seepage Experiment investigates the shutoff efficiency of thus obtained microsphere emulsion system under above-mentioned condition after aging 1 month.As shown in table 1 to the result of above-mentioned analysis.
[comparative example 1]
The preparation process of cross-linked polymer microsphere, all with [embodiment 1], does not just add N-(1-to n-butylphenyl ethyl) acrylamide monomer.Following method or standard testing gained is adopted to be cross-linked the Structure and Properties of gradual change swellable polymer microballoon: by the solid content separated out of Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard " polymer microballoon in-depth profile control technical qualification " measuring method test microballoon emulsion system, microballoon initial particle and distribution and at 93 DEG C, under oxygen free condition, place 7 days in 160000mg/L salinity salt solution, 15 days, 30 days, the expansion multiplying power of microspherulite diameter after 45 days, rock core Seepage Experiment investigates the shutoff efficiency of thus obtained microsphere emulsion system under above-mentioned condition after aging 1 month.As shown in table 1 to the result of above-mentioned analysis.
[comparative example 2]
The preparation process of cross-linked polymer microsphere, all with [embodiment 5], does not just add N-(1-to tert .-butoxyphenyl ethyl) acrylamide monomer.Following method or standard testing gained is adopted to be cross-linked the Structure and Properties of gradual change swellable polymer microballoon: by the solid content separated out of Q/SH1020 Shengli Oilfiedld Subsidiary Company Of China Petrochemical Corporation company standard " polymer microballoon in-depth profile control technical qualification " measuring method test microballoon emulsion system, microballoon initial particle and distribution and at 93 DEG C, under oxygen free condition, place 7 days in 160000mg/L salinity salt solution, 15 days, 30 days, the expansion multiplying power of microspherulite diameter after 45 days, rock core Seepage Experiment investigates the shutoff efficiency of thus obtained microsphere emulsion system under above-mentioned condition after aging 1 month.As shown in table 1 to the result of above-mentioned analysis.
Table 1
Claims (10)
1. crosslinked gradual change swellable polymer microballoon, described polymer microballoon is the polymer microballoon formed through radical polymerization under linking agent exists by monomer; Described monomer comprise acrylamide and/or other water-soluble monomer with as shown in the formula (I) heat-resisting/hydrophobic monomers;
formula (I);
Wherein, R
1and R
2independently take from hydrogen atom, methyl or ethyl separately; R
3for C
1~ C
16alkoxyl group or thiazolinyl beyond alkyl.
2. crosslinked gradual change swellable polymer microballoon according to claim 1, it is characterized in that the particle diameter of described polymer microballoon is 30 ~ 1500nm, described as shown in the formula (I) heat-resisting/ratio of the amount of substance of hydrophobic monomers and acrylamide and/or other water-soluble monomer is (0.01 ~ 20): (80 ~ 99.99).
3. crosslinked gradual change swellable polymer microballoon according to claim 1, it is characterized in that it is with parts by weight, under the emulsifier effect of 5 ~ 20 parts, the monomer of 5 ~ 50 parts is dissolved in the oil-based solvent of the deionized water of 10 ~ 70 parts and 20 ~ 80 parts, cause with redox initiator, obtained by reversed-phase emulsion or conversed phase micro emulsion copolymerization.
4. crosslinked gradual change swellable polymer microballoon according to claim 3, is characterized in that described emulsifying agent is selected from least one in sapn, tween, alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, trimethyl quaternary ammonium salt, two dodecyl dimethyl quaternary ammonium salt, hexadecanyl trimethyl quaternary ammonium salt, di-cetyl dimethyl quaternary ammonium salt, octadecyl trimethyl quaternary ammonium salt, two octadecyldimethyl quaternary ammonium salt.
5. crosslinked gradual change swellable polymer microballoon according to claim 3, is characterized in that described oil-based solvent is selected from the mixture of hydrocarbon or hydrocarbon.
6. crosslinked gradual change swellable polymer microballoon according to claim 3, is characterized in that other water-soluble monomer described is selected from least one in non-ionic monomer, anionic monomer or cationic monomer; Wherein said non-ionic monomer is selected from least one in NIPA, N hydroxymethyl acrylamide, N-N-DMAA, N-N-acrylamide, N-vinyl pyridine or NVP; Described anionic monomer is selected from least one in vinyl carboxylic acid and salt, vinyl sulfonic acid and salt thereof, vinylbenzenesulfonic acid and salt, allyl sulphonic acid and salt thereof, allyl benzene sulfonic acid and salt thereof or 2-acrylamide-2-methylpro panesulfonic acid and salt thereof, and described salt is alkali metal salts or ammonium salt; Described cationic monomer is selected from least one in dimethyl ethyl allyl ammonium chloride, dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, acryloxyethyldimethyl ethyl phosphonium bromide ammonium, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, 2-acrylamido-2-trimethoxysilyl propyl methacrylate ammonium chloride.
7. crosslinked gradual change swellable polymer microballoon according to claim 3, is characterized in that oxygenant used in described redox initiator is selected from inorganic peroxide; Reductive agent used in described redox initiator is selected from alkali metal sulfite, alkali metal bisulfite, alkali metal thiosulfate.
8. crosslinked gradual change swellable polymer microballoon according to claim 1, it is characterized in that described linking agent is selected from Vinylstyrene, methylene-bisacrylamide, methylenebismethacrylamide, triallylamine, pentaerythritol triacrylate, N, N ' at least one in-penylene a bismaleimides.
9. the preparation method of the crosslinked gradual change swellable polymer microballoon described in any one of claim 1 ~ 8, is characterized in that comprising the following steps:
1) preparation of aqueous phase: acrylamide and/or other water-soluble monomer, water-soluble cross-linker, reductive agent are dissolved in the water of 90 ~ 99.9% of described water gross weight, with alkali lye regulator solution pH value to 7 ~ 12, obtain aqueous phase I; Oxygenant is dissolved in separately in the water of surplus and obtains aqueous phase II;
2) preparation of reversed-phase emulsion or reverse micro emulsion: emulsifying agent or emulsifying agent and assistant for emulsifying agent, heat-resisting/hydrophobic monomers and oil-soluble crosslinking agent are dissolved in oil-based solvent and obtain oil phase, the aqueous phase I prepared in step 1) is joined in oil phase, fully stirs and obtain reversed-phase emulsion or reverse micro emulsion;
3) reversed-phase emulsion or conversed phase micro emulsion copolymerization: remove and be dissolved in step 2) reversed-phase emulsion or reverse micro emulsion in oxygen, add the aqueous phase II prepared in step 1), initiated polymerization at 5 ~ 50 DEG C, continue reaction 0.5 ~ 8 hour after exothermic peak temperature occurs, obtain the emulsion system of crosslinked gradual change swellable polymer microballoon.
10. the application of crosslinked gradual change swellable polymer microballoon in tertiary oil production in oil field described in claim 1 ~ 8.
Priority Applications (1)
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| CN106349114A (en) * | 2015-07-16 | 2017-01-25 | 中国石油化工股份有限公司 | Hydrophobic monomer and tackifier for non-solid-phase drilling liquid based on monomer |
| CN106349115A (en) * | 2015-07-16 | 2017-01-25 | 中国石油化工股份有限公司 | Bis-phenyl hydrophobic monomer and plugging gel based on monomer |
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| CN106589229A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Microemulsion system and preparation method |
| CN106589232A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Hydrophobic association acrylamide copolymer and preparing method |
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| CN107402286A (en) * | 2017-08-01 | 2017-11-28 | 东北石油大学 | Delay swollen performance test experimental method in a kind of polymer microballoon rock core |
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