CN118271513A - High-stability water-in-water emulsion and polymerization method and application thereof - Google Patents
High-stability water-in-water emulsion and polymerization method and application thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000000839 emulsion Substances 0.000 title claims abstract description 66
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000003756 stirring Methods 0.000 claims abstract description 101
- 239000000178 monomer Substances 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000003999 initiator Substances 0.000 claims abstract description 31
- 239000003381 stabilizer Substances 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 230000009194 climbing Effects 0.000 claims abstract description 12
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 36
- 230000008569 process Effects 0.000 claims description 29
- 239000012530 fluid Substances 0.000 claims description 28
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 15
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 11
- 230000000977 initiatory effect Effects 0.000 claims description 11
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- 238000005553 drilling Methods 0.000 claims description 9
- 125000000129 anionic group Chemical group 0.000 claims description 8
- 125000002091 cationic group Chemical group 0.000 claims description 7
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 7
- 239000012986 chain transfer agent Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 230000033116 oxidation-reduction process Effects 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 3
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000003926 acrylamides Chemical class 0.000 claims description 2
- 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 description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- -1 phosphonic acid isopropenyl phosphoric acid Chemical compound 0.000 claims description 2
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims description 2
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 2
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 claims description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012966 redox initiator Substances 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 23
- 229920003169 water-soluble polymer Polymers 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 39
- 239000007864 aqueous solution Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 24
- 239000012071 phase Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 239000002002 slurry Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 230000002829 reductive effect Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 230000009471 action Effects 0.000 description 11
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 10
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 10
- 238000012546 transfer Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 8
- 235000011130 ammonium sulphate Nutrition 0.000 description 8
- 238000010008 shearing Methods 0.000 description 8
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920002401 polyacrylamide Polymers 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000004908 Emulsion polymer Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000005185 salting out Methods 0.000 description 4
- 239000012267 brine Substances 0.000 description 3
- 238000004581 coalescence Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 3
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- RQAFMLCWWGDNLI-UHFFFAOYSA-N 2-[4-[bis(2-chloroethyl)amino]phenyl]acetic acid Chemical compound OC(=O)CC1=CC=C(N(CCCl)CCCl)C=C1 RQAFMLCWWGDNLI-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- 229920000867 polyelectrolyte Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- 101100084595 Caenorhabditis elegans pam-1 gene Proteins 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000281 calcium bentonite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000002493 climbing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 239000012895 dilution Substances 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
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- 230000001804 emulsifying effect Effects 0.000 description 1
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- 238000009775 high-speed stirring Methods 0.000 description 1
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- 230000000670 limiting effect Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 239000000575 pesticide Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
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Abstract
The invention relates to the technical field of water-soluble polymers, in particular to a high-stability water-in-water emulsion, a polymerization method and application thereof. Specifically provided are. The method comprises the following steps: (1) Mixing an ionic monomer, a nonionic monomer, a dispersing agent and water; (2) Mixing the mixed system obtained in the step (1) with a stabilizer, stirring, and setting the stirring speed to 300-800 rpm; (3) Mixing the mixed system obtained in the step (2) with an initiator for reaction, and setting the stirring speed to be 50-300 rpm; (4) Setting the stirring speed to 800-2000 rpm after the pole climbing phenomenon or liquid level wrinkling occurs in the polymerization system; (5) After emulsion droplets are formed in the polymerization system, the stirring speed is set to 300-800 rpm, and after the reaction is finished, the water-in-water emulsion is obtained. The method has the advantages of simple operation, low product viscosity, high production efficiency, high product dissolution speed and safe pollution.
Description
Technical Field
The invention relates to the technical field of water-soluble polymers, in particular to a high-stability water-in-water emulsion, a polymerization method and application thereof.
Background
The water-soluble polymer has multiple functions of viscosity increasing, flocculation, viscosity reducing, defoaming, collapse preventing, plugging, lubricating, emulsifying and the like, and has wide and large-scale application in industries such as oil fields, water treatment, papermaking, paint and the like. With the great progress of China in the aspects of development, development and application of water-soluble polymers, the development direction is more clearly focused on novel, efficient, low-pollution and low-cost green processes and products. The water-in-water (w/w) emulsion polymerization is a dispersion polymerization reaction in aqueous solution, when the primary polymer generated in the polymerization process reaches a critical chain length, the primary polymer is separated out (such as salting-out effect) due to the rejection of the system, and phase-rich particles of the polymer and hydration water thereof are formed as a dispersed phase (internal phase) under the action of a stabilizer, and are dispersed in a continuous phase aqueous solution (external phase) in the form of emulsion to continue the polymerization reaction, so that the aqueous dispersion system similar to the emulsion in appearance is finally obtained, and the water-based emulsion polymerization catalyst has the characteristics of short dissolution time and convenience in use. Because the internal phase and the external phase of the product are both water phases, the process is called water-in-water emulsion polymerization, and is a safe, environment-friendly and low-cost process for producing the water phase of the polymer emulsion. (Feng Yujun: water-in-Polyacrylamide emulsion: an environmentally friendly new class of water-soluble polymer materials [ J ], fine and specialty chemicals, 2009,17 (06): 11-15).
Water-in-water emulsion polymerization is limited by a specific polymerization mechanism of "self-polymerization nucleation" and has two major drawbacks of high viscosity and relative stability (controlled free radical polymerization in CN104395352a aqueous dispersion in water). The high viscosity is due to the primary polymer produced in the early stage of polymerization, and a part causes an increase in the viscosity of the medium in solution in a similar manner to the solution polymerization, and problems encountered in the solution polymerization remain, limiting the polymer size and concentration. The relative stability is the tendency of the polymer particles to agglomerate during polymerization, and this may then cause solidification during polymerization and/or sedimentation during transportation or storage of the dispersion. Thus, there are limitations in terms of polymer size and/or concentration. In view of these drawbacks, the polymer content in the dispersions obtained rarely exceeds 20% by weight.
Disclosure of Invention
In view of the above, the invention aims to provide a high-stability water-in-water emulsion, a polymerization method and application thereof, and the method has the advantages of simple operation, low product viscosity, high production efficiency, high product dissolution speed and safe pollution.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a high stability water-in-water emulsion polymerization process comprising:
(1) Mixing an ionic monomer, a nonionic monomer, a dispersing agent and water;
(2) Mixing the mixed system obtained in the step (1) with a stabilizer, stirring, and setting the stirring speed to 300-800 rpm;
(3) Mixing the mixed system obtained in the step (2) with an initiator for reaction, and setting the stirring speed to be 50-300 rpm;
(4) Setting the stirring speed to 800-2000 rpm after the pole climbing phenomenon or liquid level wrinkling occurs in the polymerization system;
(5) After emulsion droplets are formed in the polymerization system, the stirring speed is set to 300-800 rpm, and after the reaction is finished, the water-in-water emulsion is obtained.
Stirring is strong material flow to raise heat and mass transfer speed, and has the functions of strengthening mixing, stirring, heat transfer, mass transfer, shearing, dispersing, suspending, etc. Wherein, the suspension is to uniformly suspend small particles in the liquid so as to achieve the purposes of accelerating dissolution, strengthening leaching, promoting liquid-solid phase reaction, preventing sedimentation and the like; the dispersing is to make the gas and liquid fully disperse into fine bubbles or liquid drops in the liquid, increase the phase contact surface to promote mass transfer or chemical reaction and meet the requirement of polymer on granularity. The water-in-water emulsion polymerization process of the present invention, step (1): mixing an ionic monomer, a nonionic monomer, a dispersing agent and water; preferably stirring the mixed system, and setting the stirring speed to be 500-800 rpm; the method of step (1) preferably comprises:
Adding the ionic monomer, the nonionic monomer and the dispersing agent into quantitative water, fully stirring and dissolving, and controlling the stirring speed to be 500-800 rpm. The mixed system obtained in the step (1) is a non-viscosity liquid, and stirring is used for quick dissolution. The polarity of the aqueous solution can be changed by introducing the dispersing agent, the salting-out effect is exerted, the solubility of the nascent polymer is reduced, and the nascent polymer is separated out in the polymerization process; the dispersing agent has certain dissolution assisting effect because the dispersing agent can shield electrostatic action among polymer chains in the using link of the product, especially in dilution.
In the invention, the ionic monomer and the nonionic monomer are 5-20wt% of the total mass of the reaction system;
The mass ratio of the ionic monomer to the nonionic monomer is (0.1-1.5): 1.
In the invention, the nonionic monomer is one or more of acrylamide, an acrylamide derivative and a hydrophobic monomer;
the ionic monomer is an anionic monomer and/or a cationic monomer;
The anionic monomer is one or more of acrylic acid, methacrylic acid, itaconic acid, vinyl sulfonic acid, p-styrene sulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, phosphonic acid isopropenyl phosphoric acid and 2-acrylamide-2-methylpropanephosphonic acid;
The cationic monomer is one or more of methacryloxyethyl trimethyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride, methacrylamidopropyl trimethyl ammonium chloride and dimethyl diallyl ammonium chloride.
In the present invention, the dispersant is one or more of neutral inorganic salt, weak acidic inorganic salt, or weak basic inorganic salt.
The dispersing agent is selected to meet the salting-out effect requirement of the target polymer of the water-in-water emulsion polymerization, and the subsequent application range is also required to be considered. The peak viscosity in the polymerization process is derived from the dissolution of the precipitated polymer and the stabilizer in the continuous phase, the concentration of the precipitated polymer and the average molecular weight have a large influence, and increasing the concentration of the dispersant can reduce the peak viscosity, which necessarily requires that the dispersant have higher solubility and have lower interference on the solubility of the monomer.
In the invention, the dispersant accounts for 15 to 20 weight percent of the total mass of the reaction system, and is preferably 16 to 18 weight percent.
The water-in-water emulsion polymerization process of the present invention, step (2): mixing the mixed system obtained in the step (1) with a stabilizer, stirring, and setting the stirring speed to 300-800 rpm;
the stabilizer is a homopolymer or a copolymer of an ionic monomer;
the ionic monomer is a cationic monomer and/or an anionic monomer;
the anionic monomer is selected from one or more of carboxylate, phosphonate and sulfonate;
the carboxylate is Polyacrylate (PAAM);
The phosphonate is poly (2-acrylamide-2-methylpropionate) (PAMPPM);
The sulfonate is poly-2-acrylamide-2-methylpropanesulfonic acid (PAMPS);
the anionic monomer is preferably PAAM and/or PAMPSM;
The cationic monomer is preferably polyacryl oxyethyl trimethyl ammonium chloride (PDAC); the stabilizer can be a homopolymer of a single monomer, a mixture of the same type of electropolymerization, or a copolymer of multiple monomers; the selection is based on the electrical property of the target polymer, and the stabilizer needs to be adsorbed on the surface of the emulsion drop to provide a protective effect, wherein the synthesis of anionic water-in-water emulsion is preferred, and the synthesis of cationic water-in-water emulsion is preferred to PDAC based on the price of raw materials and the stabilization effect;
the stabilizer is 3-7wt%, preferably 4wt% -6wt% of the total mass of the reaction system;
the method of step (2) preferably comprises:
Adding a stabilizer into the mixed system obtained in the step (1), fully dissolving under stirring, controlling the stirring speed to be 300-800 rpm, and stirring to push liquid to flow and uniformly mixing materials.
The stabilizer is polyelectrolyte, can greatly improve the solution viscosity after being dissolved in the solution, and has two defects of low stirring speed: (1) slow dissolution and dispersion; (2) The monomer is adsorbed on the surface of polyelectrolyte, and template polymerization exists to induce irregular polymerization of the monomer, so that the consumption of the monomer leads to unstable composition and performance of the product. The stirring speed is too high, and the stabilizer ensures that the solution has certain viscosity (50-200 mPa.s), so that the gas is wrapped at high stirring speed to form bubbles, the air is difficult to replace, the material is unevenly distributed, and the product quality is fluctuated. The stabilizer can be adsorbed on the surface of emulsion droplets to exert space and static double stabilization effects by hair particles and inhibit coalescence among emulsion droplets.
The water-in-water emulsion polymerization process of the present invention, step (3):
And (3) mixing the mixed system obtained in the step (2) with an initiator for reaction, and setting the stirring speed to be 50-300 rpm.
The polymerization place occurs in the continuous phase in the initial stage of polymerization reaction, is homogeneous aqueous solution polymerization, and the stirring speed is too fast, so that the material contact speed is accelerated, the termination probability of active double radicals is increased, the average molecular weight of the polymer is easy to be lower, the monomer conversion rate is low, and the product quality cannot be ensured.
In the invention, the initiator is one or more of a thermal initiator, persulfate, azo initiator or oxidation-reduction initiation system;
In the oxidation-reduction initiation system, the oxidant is one or more of ammonium persulfate, sodium persulfate and potassium persulfate, and the reducing agent is one or more of sodium bisulfite, ferrous sulfate, sodium sulfite or sodium metabisulfite, wherein the weight ratio of the oxidant to the reducing agent in the oxidation-reduction initiator is 1 (0.5-2).
The initiator is 0.05 to 0.5 weight percent of the total mass of the monomers;
step (3) is preferably carried out in the presence of an inert gas; the inert gas is used for replacing air in the reaction liquid, so that the polymerization inhibition effect of oxygen at low temperature can be eliminated;
The reaction temperature of the step (3) is 30-60 ℃;
The method of step (3) preferably comprises:
Heating to the temperature of the mixed system obtained in the step (2) to be constant at 30-60 ℃, adding an initiator to initiate polymerization reaction, and controlling the stirring speed to be 50-300 rpm.
The water-in-water emulsion polymerization process of the present invention, step (4): after the pole climbing phenomenon or liquid level wrinkling occurs in the polymerization system, the stirring speed is set to 800-2000 rpm, and the stirring function is to generate shearing force to improve the heat transfer rate, increase the turbulence of liquid, increase the material transfer efficiency, accelerate the dispersion and combination of materials, promote the material exchange efficiency and update the surface of the high-viscosity system;
the purpose of improving the stirring speed is to improve the contact opportunity between the stabilizer and the generated primary polymer, promote the adsorption of the stabilizer in the primary polymer micro-area, fully form uniform and fine emulsion drops under the shearing action, enable the primary polymer and the stabilizer to exist in the emulsion drops in a large amount, reduce the amount of the polymer in the disperse phase and realize the control of continuous phase adhesion. And at this time, the double-radical termination caused by the high stirring speed is suppressed due to the large viscosity of the solution.
The emulsion has smaller and more uniform particle size due to the large shearing force generated under the action of high stirring speed, can fully adsorb/wrap the stabilizer and the nascent polymer, reduces the distribution in a continuous phase, and plays a role in reducing viscosity.
The method of step (4) preferably comprises:
After the polymerization reaction is carried out for a period of time, turbidity appears about 3-5 min, obvious pole climbing phenomenon appears 10-15 min or liquid surface wrinkles appear on the liquid surface caused by stirring difference, and the stirring speed is increased by 800-2000 rpm.
The water-in-water emulsion polymerization process of the present invention, step (5): after emulsion drops are formed in the polymerization system, the stirring speed is set to be 300-800 rpm, and the stirring function is to suspend and disperse materials, so that the material exchange efficiency is improved, and the heat transfer rate is improved.
After the emulsion droplets are formed, as the active free radicals are wrapped in the emulsion droplets, the polymerization reaction is transferred into the emulsion droplets for proceeding, and the stirring function is to promote the diffusion of the monomers into the emulsion droplets.
The method of step (5) preferably comprises:
under the action of high shearing, along with the formation and stabilization of emulsion drops, the polymerization reaction gradually transits from aqueous solution polymerization to emulsion polymerization, the stirring speed is reduced to 300-800 rpm, and the reaction is continued for 10-30 min.
The water-in-water emulsion polymerization process of the present invention further comprises step (6): adding an initiator into a polymerization system to continue the reaction, setting the stirring speed to be 200-500 rpm, and obtaining water-in-water emulsion after the reaction is finished;
The method of step (6) preferably comprises:
when the temperature of the polymerization reaction system is reduced to the ambient temperature, adding an initiator to continue the reaction for 15-30min, raising the temperature to 60-90 ℃, preserving the heat for 1-2 h, and reducing the stirring speed to 200-500 rpm.
Step (6) may convert all of the monomers that have not been fully reacted into a polymer. The initiator is added and/or the temperature is increased, the heat preservation is continued for a period of time, in order to fully convert the residual monomers and eliminate the initiator, especially the thermal decomposition oxidation type initiator such as persulfates, which can be a thermal initiator, persulfates, azo type initiator or oxidation-reduction initiation system, wherein the oxidant is one or a mixture of a plurality of ammonium persulfate, sodium persulfate, potassium persulfate and the like, the reducing agent is one or a mixture of a plurality of sodium bisulfite, ferrous sulfate, sodium sulfite or sodium metabisulfite and the like, the amount of the initiator is 0.05-0.3 wt% of the monomers (m initiator/m monomer), the temperature is increased to 60-90 ℃, the temperature is preferably increased to 60-80 ℃, and the initiator is preferably a redox type initiator.
In the present invention, in the step (1), the reaction raw material further includes a chain transfer agent;
The chain transfer agent is one or more of formate, lower alcohol or mercaptan;
The chain transfer agent accounts for 0.05wt% -1wt% of the total mass of the monomers.
The invention also provides the high-stability water-in-water emulsion prepared by the polymerization method.
The invention also provides application of the high-stability water-in-water emulsion in preparing drilling fluid.
The invention develops a stirring process meeting the requirements of water-in-water emulsion polymerization in different periods:
(1) Dissolving materials: adding materials such as monomer, stabilizer and dispersant into water for dissolution, wherein the stabilizer is polymer with a certain chain length, so that the viscosity of reaction liquid is increased (50-300 mPa.s), partial monomer such as Acrylamide (AM) and inorganic salt such as ammonium sulfate ((NH 4)2SO4) are dissolved and absorbed, the dissolution heat in pure water is respectively 32.5 kcal.kg -1 and 71 kcal.kg -1, and the stirring is required to have a certain speed and strength, so that the dissolution is accelerated;
(2) Aqueous solution polymerization pre-stage: the polymer micro-region is formed by initiation and chain growth of a monomer chain, polymer is separated out, the polymerization early stage is a special aqueous solution polymerization, the stirring has great influence on the initiation efficiency of an initiator and the chain growth reaction of active free radicals, the stirring speed is too high, double-radical termination is easy to occur, the monomer conversion rate is reduced, and the stirring is required to be limited;
(3) Post-polymerization of aqueous solution: along with the gel acceleration effect, the viscosity of the solution reaches a peak value, and a certain stirring speed is needed to promote heat dissipation;
(4) Separating out and separating phases: after the polymerization reaction is carried out for a period of time, the new polymer is separated out under the salting-out action of the dispersing agent to form polymer microdomains, the stabilizer is adsorbed under the shearing action to form emulsion drops, the shearing action is required to have certain strength, the shearing action is carried out on liquid microdomains in or around the polymer microdomains, the polymer is torn into micro drops, the stabilizer is rapidly adsorbed, emulsion drop coalescence is inhibited, and emulsion drops with certain stability are formed;
(5) Late stage of polymerization: emulsion-like polymerization, the action of microscopic flow requiring shear formation promotes localized mixing and heterogeneous surface renewal, promoting heat transfer, mass transfer, and dispersion of suspended emulsion droplets.
The invention has the beneficial effects that:
The invention develops a multistage water-in-water emulsion polymerization process by selecting different stirring combinations based on different actions of stirring in the water-in-water emulsion polymerization process, and has the following advantages:
(1) The problem of controlling the viscosity peak value in the water-in-water emulsion polymerization is solved, so that the polymerization process is smoothly transited from the aqueous solution polymerization to the emulsion-like polymerization;
(2) The particle size of the prepared water-in-water emulsion is 1-5 mu m, so that the storage stability and the dissolution speed of the emulsion are improved;
(3) The viscosity of the prepared water-in-water emulsion is 500-1000 mPa.s (Brookfield viscometer RV3T, the test condition is 30 ℃, the rotation speed is 30rpm/min, the end condition is 1min, and single-point acquisition) and the transfer and dissolution performance of the emulsion are improved;
(4) The prepared water-in-water emulsion is used as a drilling fluid filtrate reducer, can effectively control the drilling fluid filtrate loss, and has good application prospect.
Drawings
FIG. 1 is an external view of the water-in-water emulsion polymerization process in example 1: (a) and (b) are aqueous solution polymerization process diagrams; (c) is a pole climbing phenomenon of the polymerization system; (d) an emulsification process; (e) and (f) are emulsion-like polymerization process diagrams;
Fig. 2: (a) (b) and (e) are appearance charts of the polymerization process in comparative example 2 (at 700 rpm); (c) And (d) is an appearance of the polymerization process in comparative example 3 (at 800 rpm);
FIG. 3 is an optical micrograph of emulsion droplets in the emulsion product of example 1;
FIG. 4 is a graph of the dissolution properties of the emulsion product of example 1.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to further illustrate the present invention, the following examples are provided. The raw materials used in the following examples of the present invention are all commercially available.
1. Examples and comparative examples
Example 1: water-in-water emulsion polymerization of AM and AMPS binary copolymers
AMPS (15 g,72.4 mmol) was dissolved in 97.5g of water, the pH was adjusted to 7-8 with NaOH (2.91 g,72.9 mmol), acrylamide (60 g,84.4 mmol) and ammonium sulfate (67.5 g,510.8 mmol) were added and dissolved under stirring at 800 rpm; then PAMPSNa aqueous solution (125 g, 18.75g of polymer, 106.25g of water) was added, dissolved under stirring at 500rpm, nitrogen was introduced and the temperature was raised to 30 ℃; stirring at 100rpm, adding ammonium persulfate ((NH 4)2S2O8, 0.075g,0.263 mmol) water solution (0.0118 wt%) and sodium bisulphite (NaHSO 3, 0.075g,0.576 mmol) water solution (0.0118 wt%) 5g in sequence, monomer concentration of 20wt% of the whole system, and initiating polymerization reaction; obvious pole climbing phenomenon or liquid level wrinkling caused by stirring difference appears on the liquid level, and stirring is carried out at 1000 rpm; the polymerization reaction gradually transits from aqueous solution polymerization to emulsion polymerization, the viscosity is reduced, the stirring speed is reduced to 400rpm, the reaction is continued for 30min, when the temperature of the reaction solution is reduced to the ambient temperature, the stirring speed is reduced to 300rpm, the initiator ammonium persulfate ((NH 4)2S2O8, 0.075g,0.263 mmol) and sodium bisulphite (NaHSO 3, 0.075g,0.576 mmol) are added, the reaction is continued for 30min, the temperature is increased to 80 ℃, the temperature is kept for 1.5h after the polymerization reaction is finished, the emulsion droplet size of 1-5 mu m can be obtained, the solution viscosity of 600 mPas (a test instrument Brookfield viscometer RV3T, the test condition is 30 ℃ and rotor-06, the rotation speed is 30rpm/min, the finishing condition is 1min, and single point acquisition) PAM/AMPS water emulsion (see figure 1, wherein (a) and (b) are water solution polymerization process diagrams, (c) are climbing rod phenomena of a polymerization system, (d) are emulsification processes, (e) and (f) are emulsion droplet dissolution process diagrams) are optical droplet size diagrams in the product of the emulsion polymerization system, the embodiment, the solution droplet size of the product has a relatively high dissolution speed of about 1 mu m, the viscosity is shown in the image of 2 mu m, the solution viscosity is shown in the image of the embodiment, the solution droplet size is reached, the solution viscosity is relatively high, the dissolution speed is shown in the image of 2 mu m, the image is shown in the image, the image is 2, has the advantage of fast utility.
Comparative example 1:
AMPS (15 g,72.4 mmol) was dissolved in 97.5g of water under nitrogen atmosphere, the pH was adjusted to 7-8 with NaOH (2.91 g,72.9 mmol), acrylamide (60 g,84.4 mmol) and ammonium sulfate (67.5 g,510.8 mmol) were added and dissolved under stirring at 800 rpm; then PAMPSNa aqueous solution (125 g, 18.75g of polymer, 106.25g of water) was added and dissolved under stirring at 200rpm, the dissolution process always occurring as self-polymerization due to the template effect of PAMPSNa, at low stirring speed, polymerization of the monomers was induced.
Comparative example 2:
AMPS (15 g,72.4 mmol) was dissolved in 97.5g of water under nitrogen atmosphere, the pH was adjusted to 7-8 with NaOH (2.91 g,72.9 mmol), acrylamide (60 g,84.4 mmol) and ammonium sulfate (67.5 g,510.8 mmol) were added and dissolved under stirring at 800 rpm; then PAMPSNa aqueous solution (125 g, 18.75g of polymer, 106.25g of water) was added, dissolved under stirring at 500rpm, nitrogen was introduced and the temperature was raised to 30 ℃; the mixture was stirred at 100rpm, ammonium persulfate ((NH 4)2S2O8, 0.075g,0.263 mmol) and sodium bisulphite (NaHSO 3, 0.075g,0.576 mmol) were added in this order (0.0118 wt%) and 5g of sodium bisulphite (0.0118 wt%) were added, the monomer concentration was 20wt% of the whole system mass, polymerization was initiated, a significant pole climbing phenomenon occurred or liquid surface wrinkles caused by the difference in stirring occurred, the stirring was increased to 800rpm respectively, the appearance of the polymerization process was as shown in FIGS. 2 (a) and (b), wrinkles were formed on the emulsion surface, and gel particles were found in the product when dissolved, see FIG. 2 (e).
Comparative example 3:
AMPS (15 g,72.4 mmol) was dissolved in 97.5g of water under nitrogen atmosphere, the pH was adjusted to 7-8 with NaOH (2.91 g,72.9 mmol), acrylamide (60 g,84.4 mmol) and ammonium sulfate (67.5 g,510.8 mmol) were added and dissolved under stirring at 800 rpm; then PAMPSNa aqueous solution (125 g, 18.75g of polymer, 106.25g of water) was added, dissolved under stirring at 500rpm, nitrogen was introduced and the temperature was raised to 30 ℃; reducing to 100rpm for stirring, sequentially adding ammonium persulfate ((NH 4)2S2O8, 0.075g,0.263 mmol) aqueous solution (0.0118 wt%) and sodium bisulphite (NaHSO 3, 0.075g,0.576 mmol) aqueous solution (0.0118 wt%) 5g, monomer concentration of 20wt% of the whole system, initiating polymerization reaction, and raising to 700rpm for stirring respectively, wherein the appearance of the polymerization process is shown in figures 2 (c) and (d), and the surface of the emulsion is wrinkled at 700rpm, so that the climbing effect is too strong and stable emulsion cannot be obtained.
Example 2: water-in-water emulsion polymerization of AM and AMPS binary copolymers
AMPS (45 g,217.3 mmol) was dissolved in 130g of water, the pH was adjusted to 7-8 with NaOH (8.74 g,218.6 mmol), acrylamide (30 g,422.1 mmol) and ammonium sulfate (60 g,454.1 mmol) were added and dissolved with stirring at 800 rpm; then PAMPSNa aqueous solution (100 g, polymer 15g, water 85 g) was added, dissolved under stirring at 600rpm, nitrogen was introduced and the temperature was raised to 30 ℃; reducing to 200rpm for stirring, sequentially adding ammonium persulfate ((NH 4)2S2O8, 0.075g,0.263 mmol) aqueous solution (0.0118 wt%) and sodium bisulfate (NaHSO 3, 0.075g, 0.578 mmol) aqueous solution (0.0118 wt%) 5g, monomer concentration of 20wt% of the whole system, initiating polymerization reaction, obvious pole climbing phenomenon or obvious liquid surface fold caused by stirring difference and stirring to 2000rpm, gradually over-polymerizing the polymerization reaction from aqueous solution to emulsion polymerization, reducing the stirring speed to 500rpm for continuous reaction for 30min, reducing the stirring speed to 200rpm when the temperature of the reaction solution is reduced to the ambient temperature, supplementing an initiator ((NH 4)2S2O8, 0.075g,0.263 mmol) and sodium bisulphite (NaHSO 3, 0.075g,0.576 mmol) for continuous reaction for 30min, raising the temperature to 80 ℃, and keeping the temperature for 1.5h after the polymerization reaction is finished, obtaining emulsion droplet size of 1-5 mu m, solution viscosity of the solution of 1-800 mPa.mPas (Brookfield, a 3 Md, a water-phase meter, a PAM 1/fluid viscosity of a fluid is collected under the condition of a single-point of a liquid phase meter, and a viscosity of a liquid phase meter of a liquid phase, and a temperature of a PAM is 1/a liquid of a liquid meter, and a temperature of a liquid phase is measured at 1/a temperature of one or a liquid, and a temperature of one).
Example 3: water-in-water emulsion polymerization of AM, AA and AMPS terpolymers
AMPS (30 g,144.8 mmol) and AA (6 g,83.3 mmol) were dissolved in 130g water, the pH was adjusted to 7-8 with NaOH (9.11 g,227.8 mmol), acrylamide (39 g,548.7 mmol) and ammonium sulfate (67.5 g,510.8 mmol) were added and dissolved under stirring at 700 rpm; then PAMPSNa aqueous solution (125 g, 18.75g of polymer, 106.25g of water) was added, dissolved under stirring at 600rpm, nitrogen was introduced and the temperature was raised to 30 ℃; reducing to 200rpm for stirring, sequentially adding ammonium persulfate ((NH 4)2S2O8, 0.075g,0.263 mmol) aqueous solution (0.0118 wt%) and sodium bisulfate (NaHSO 3, 0.075g, 0.578 mmol) aqueous solution (0.0118 wt%) 5g, monomer concentration of 20wt% of the whole system, initiating polymerization reaction, obvious pole climbing phenomenon or obvious liquid surface fold caused by stirring difference and stirring to 1000rpm, gradually over-polymerizing the polymerization reaction from aqueous solution to emulsion polymerization, reducing the stirring speed to 500rpm for continuous reaction for 30min, reducing the stirring speed to 200rpm when the temperature of the reaction solution is reduced to the ambient temperature, adding an initiator ((NH 4)2S2O8, 0.075g,0.263 mmol) and sodium bisulphite (NaHSO 3,0.075g,0.576 mmol) for continuous reaction for 30min, raising the temperature to 80 ℃, and keeping the temperature for 1.5h, obtaining emulsion drop size of 1-5 mu m, viscosity of the solution after the polymerization reaction is finished, viscosity of the solution is subjected to Brompas (test instrument, PAM is 1-06 McS, and the viscosity of a fluid is subjected to a test condition of one-1/80 rpm, and a fluid viscosity is subjected to a test condition of a fluid (RV) of a fluid is 1/a fluid, a fluid is subjected to a temperature of a test, and a fluid is subjected to a fluid, and a temperature is subjected to a fluid condition, and a temperature is subjected to a fluid, and a temperature is a temperature, and a temperature is further test, and a temperature is reduced.
Example 4: water-in-water emulsion polymerization of AM and DAC binary copolymers
DAC (15 g,154.9 mmol) and AM (60 g,844.1 mmol) were dissolved in 130g water, ammonium sulphate (67.5 g,510.8 mmol) was added and dissolved with stirring at 600 rpm; then PDAC aqueous solution (125 g, polymer 18.75g, water 106.25 g) was added, dissolved under stirring at 600rpm, nitrogen was introduced and the temperature was raised to 30 ℃; reducing to 200rpm for stirring, sequentially adding ammonium persulfate ((NH 4)2S2O8, 0.075g,0.263 mmol) aqueous solution (0.0118 wt%) and sodium bisulfate (NaHSO 3, 0.075g, 0.578 mmol) aqueous solution (0.0118 wt%) 5g, monomer concentration of 20wt% of the whole system, initiating polymerization reaction, obvious pole climbing phenomenon or obvious liquid surface fold caused by stirring difference and stirring to 1500rpm, gradually over-polymerizing the polymerization reaction from aqueous solution to emulsion polymerization, reducing the stirring speed to 600rpm for continuous reaction for 30min, reducing the stirring speed to 200rpm when the temperature of the reaction solution is reduced to ambient temperature, supplementing an initiator ((NH 4)2S2O8, 0.075g,0.263 mmol) and sodium bisulphite (NaHSO 3, 0.075g,0.576 mmol), raising the temperature to 80 ℃ for 1.5h, obtaining emulsion droplet size of 1-5 mu m after the polymerization reaction is finished, solution viscosity of 600 mPas (Bro.s, PAM is measured at 3 m/RV for 1-30 min, and a single-point water-phase viscosity of a fluid (PAM) is measured at a temperature of a rotor, a temperature of 1-3 min, a temperature of a fluid is collected by a fluid, and a fluid viscosity meter is measured at a temperature of a fluid of a temperature of a fluid, and a temperature of a single-phase, and a temperature of a fluid is equal to 1.80 rpm).
2. Test example stability test
The reason for the instability of the emulsion, including coalescence, flocculation, and floating and sinking of the emulsion droplets to make the active substances unevenly distributed, refer to GB/T1603-2001 (pesticide emulsion stability determination method), transfer the samples of examples 1-4 into a test vessel respectively, perform the test treatment of static stability, medium speed (4000 rpm) centrifugal stability and thawing stability, dilute the upper emulsion after the corresponding treatment into 1wt% aqueous solution, determine the viscosity with a six-speed rotational viscometer (Qingdao Heng Tadada), the viscosity of the solution is related to the polymer content, and measure the emulsion stability by the change of the viscosity. From Table 1, it can be seen that the emulsion prepared by the present invention is a high stability emulsion.
Table 1 emulsion stability test results table
The product of the embodiment of the invention is subjected to performance evaluation in composite brine slurry and saturated brine slurry, and the performance evaluation is specifically as follows:
(1) Preparation of composite salt water slurry
Measuring 350mL of distilled water, placing the distilled water in a cup, adding 16.0g of sodium chloride, 2.6g of anhydrous calcium chloride and 6.9g of magnesium chloride, adding 52.5g of slurry bentonite for drilling fluid (calcium bentonite meets GB/T20973-2007 standard) and 3.15g of anhydrous sodium carbonate after the materials are dissolved, stirring at a high speed for 20min, stopping at least twice during the stirring to scrape clay adhered to the wall of the container, and hermetically curing for 24h at 24+/-3 ℃ to obtain composite salt slurry.
Adding 10% (effective addition amount of 2%) of water-in-water emulsion into the obtained base slurry, stirring at high speed for 20min, rolling and aging at 150deg.C in a high-temperature roller furnace for 16h, taking out, cooling to room temperature, stirring at high speed for 5min, measuring the room temperature medium pressure filtrate loss and apparent viscosity of drilling fluid according to the specification of GB/T16783.1-20067.2, and testing the temperature at 24deg.C+ -3deg.C and the pressure at 690kPa. The test results are shown in Table 2.
(2) Preparation of saturated brine slurry
Measuring 350mL of distilled water, placing the distilled water into a high-speed stirring cup, adding 0.49g of sodium carbonate, adding 14g of slurry bentonite for drilling fluid after the sodium carbonate is dissolved, stirring the mixture for 20min, sealing and placing the mixture for 24h to obtain 4% fresh water base slurry, adding 126g of NaCl under the stirring state, and performing airtight maintenance for 24h at the temperature of 24+/-3 ℃ to obtain saturated brine base slurry.
Adding 10% (effective addition amount of 2%) of water-in-water emulsion into the saturated brine-based slurry, stirring for 20min, rolling and aging at 180 ℃ for 16h in a high-temperature roller furnace, taking out, cooling to room temperature, stirring at high speed for 5min, measuring the room temperature medium pressure filtration loss and apparent viscosity of the drilling fluid according to the specification of GB/T16783.1-20067.2, and measuring the temperature of 24+/-3 ℃ and the pressure of 690kPa. The test results are shown in Table 3.
(3) Dissolution time
400ML of deionized water was added to a 500mL beaker and stirred with a magnetic rotor (rotation speed 50-300 r/min)
Slowly adding 4g of water-in-water emulsion polymer under the state, and observing the time for completely dissolving the water-in-water emulsion to obtain the dissolving time. The test results are shown in Table 4.
Table 2 evaluation of product performance in composite brine-based slurries
Table 3 evaluation of product Performance in saturated brine-based slurries
Table 4 dissolution time of the product of the example
| Examples | Dissolution time/s |
| Example 1 | 120 |
| Example 2 | 140 |
| Example 3 | 125 |
| Example 4 | 145 |
As can be seen from the measurement results in tables 1-4, after 10 percent (effective addition amount of 2 percent) of the water-in-water emulsion polymer is added into the composite brine slurry and the saturated brine slurry, the filtration loss is respectively 8.4 ml-10.6 ml and 7.6 ml-10.2 ml after the water-in-water emulsion polymer is aged for 16 hours at high temperature, and the filtration loss of drilling fluid is greatly reduced, which indicates that the water-in-water emulsion polymer has better temperature resistance, salt resistance and filtration loss reduction capability. Meanwhile, the dissolution time of the product is less than 150s, which indicates that the dissolution performance is good.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A high stability water-in-water emulsion polymerization process comprising:
(1) Mixing an ionic monomer, a nonionic monomer, a dispersing agent and water;
(2) Mixing the mixed system obtained in the step (1) with a stabilizer, stirring, and setting the stirring speed to 300-800 rpm;
(3) Mixing the mixed system obtained in the step (2) with an initiator for reaction, and setting the stirring speed to be 50-300 rpm;
(4) Setting the stirring speed to 800-2000 rpm after the pole climbing phenomenon or liquid level wrinkling occurs in the polymerization system;
(5) After emulsion droplets are formed in the polymerization system, the stirring speed is set to 300-800 rpm, and after the reaction is finished, the water-in-water emulsion is obtained.
2. The high stability water-in-water emulsion polymerization process of claim 1, wherein the ionic monomer and the nonionic monomer are 5wt% to 20wt% of the total mass of the reaction system;
The mass ratio of the ionic monomer to the nonionic monomer is (0.1-1.5): 1.
3. The high stability water-in-water emulsion polymerization process according to claim 1 or 2, wherein the nonionic monomer is one or more of acrylamide, an acrylamide derivative, a hydrophobic monomer;
the ionic monomer is an anionic monomer and/or a cationic monomer;
The anionic monomer is one or more of acrylic acid, methacrylic acid, itaconic acid, vinyl sulfonic acid, p-styrene sulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, phosphonic acid isopropenyl phosphoric acid and 2-acrylamide-2-methylpropanephosphonic acid;
The cationic monomer is one or more of methacryloxyethyl trimethyl ammonium chloride, acryloxyethyl trimethyl ammonium chloride, methacrylamidopropyl trimethyl ammonium chloride and dimethyl diallyl ammonium chloride.
4. The high stability water-in-water emulsion polymerization process of claim 1 wherein the dispersant is one or more of a neutral inorganic salt, a weakly acidic inorganic salt, or a weakly basic inorganic salt;
the dispersant accounts for 15-20wt% of the total mass of the reaction system.
5. The high stability water-in-water emulsion polymerization process of claim 1 wherein the stabilizer is a homopolymer or copolymer of an ionic monomer;
The stabilizer accounts for 3-7wt% of the total mass of the reaction system.
6. The high stability water-in-water emulsion polymerization process of claim 1 wherein the initiator is one or more of a thermal initiator, persulfate, azo-based initiator, or a redox initiation system;
In the oxidation-reduction initiation system, the oxidant is one or more of ammonium persulfate, sodium persulfate and potassium persulfate, the reducing agent is one or more of sodium bisulfite, ferrous sulfate, sodium sulfite or sodium metabisulfite, and the mass ratio of the oxidant to the reducing agent in the oxidation-reduction initiator is 1 (0.5-2).
7. The high stability water-in-water emulsion polymerization process according to claim 1, wherein the initiator is 0.05 to 0.5wt% of the total mass of the monomers.
8. The high stability water-in-water emulsion polymerization process of claim 1 wherein in step (1), the reaction feed further comprises a chain transfer agent;
The chain transfer agent is one or more of formate, lower alcohol or mercaptan;
The chain transfer agent accounts for 0.05wt% -1wt% of the total mass of the monomers.
9. A high stability water-in-water emulsion prepared by the high stability water-in-water emulsion polymerization process of any one of claims 1-8.
10. Use of a high stability water-in-water emulsion according to claim 9 for the preparation of a drilling fluid.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118271513A true CN118271513A (en) | 2024-07-02 |
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