CN102807503B - Polymerizable monomer with surface activity and tackifying copolymer with surface activity as well as preparation methods and application thereof - Google Patents
Polymerizable monomer with surface activity and tackifying copolymer with surface activity as well as preparation methods and application thereof Download PDFInfo
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- 239000000178 monomer Substances 0.000 title claims abstract description 104
- 229920001577 copolymer Polymers 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title abstract description 37
- 230000000694 effects Effects 0.000 title abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 46
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 239000003999 initiator Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 5
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 abstract description 29
- 238000006073 displacement reaction Methods 0.000 abstract description 12
- 150000003839 salts Chemical class 0.000 abstract description 11
- 239000010779 crude oil Substances 0.000 abstract description 8
- 230000008719 thickening Effects 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000037048 polymerization activity Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 229920000642 polymer Polymers 0.000 description 28
- -1 halogenated alkyl sulfonic acid alkali metal salt Chemical class 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulphite Substances [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910052783 alkali metal Inorganic materials 0.000 description 12
- 229920002401 polyacrylamide Polymers 0.000 description 11
- 239000007787 solid Substances 0.000 description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 230000033558 biomineral tissue development Effects 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000005587 bubbling Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 235000010265 sodium sulphite Nutrition 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 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 description 2
- JNDVNJWCRZQGFQ-UHFFFAOYSA-N 2-methyl-N,N-bis(methylamino)hex-2-enamide Chemical compound CCCC=C(C)C(=O)N(NC)NC JNDVNJWCRZQGFQ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 229910001410 inorganic ion Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 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 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052740 iodine Chemical group 0.000 description 1
- 239000011630 iodine Chemical group 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000012703 microemulsion polymerization Methods 0.000 description 1
- DCBBWYIVFRLKCD-UHFFFAOYSA-N n-[2-(dimethylamino)ethyl]-2-methylprop-2-enamide Chemical compound CN(C)CCNC(=O)C(C)=C DCBBWYIVFRLKCD-UHFFFAOYSA-N 0.000 description 1
- WDQKICIMIPUDBL-UHFFFAOYSA-N n-[2-(dimethylamino)ethyl]prop-2-enamide Chemical compound CN(C)CCNC(=O)C=C WDQKICIMIPUDBL-UHFFFAOYSA-N 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a kind of surface-active polymerisable monomers, surface-active thickening copolymer and its preparation method and application, wherein surface-active polymerisable monomer has structure shown in formula (1), which has high surface-active and high polymerization activity; The surface-active polymerisable monomer and other monomers are copolymerized available surface-active and viscosify copolymer. The heat and salt resistance and apparent viscosity of surface-active thickening copolymer solution are good, and surface-active thickening copolymer is when being used as oil displacement agent, the effects of solubilising, dispersion effectively can also being played to crude oil, so as to carry, pull the irreducible oil of difficult drive, improve its oil displacement efficiency.
Formula (1)
Description
Technical Field
The invention relates to a surface active polymerizable monomer, a surface active tackifying copolymer and a preparation method thereof, in particular to a surface active polymerizable monomer and a preparation method thereof, a surface active tackifying copolymer and a preparation method thereof, and application of the surface active tackifying copolymer in an oil displacement agent.
Background
At present, large oil fields in Daqing, Shengli, China, North China, big harbor and the like all enter the middle and later periods of exploitation, the water content of the produced oil is up to more than 90 percent, the temperature and the mineralization are greatly improved, and the primary and secondary oil extraction technologies can not meet the increasing crude oil requirements any more, so that the improvement of the recovery ratio by adopting the tertiary oil extraction technology becomes an important strategic measure of the petroleum industry in China.
Polymer flooding is one of the most effective methods in tertiary oil recovery technology. The method requires that the polymer must have excellent viscosifying properties under reservoir conditions and have high viscosity retention under the action of temperature, pressure and salt. Polyacrylamide (PAM) and partially Hydrolyzed Polyacrylamide (HPAM) are generally adopted in China, and the oil displacement mechanism is that the polymer aqueous solution has high viscosity under very low concentration so as to reduce the permeability of a water phase, control the fluidity of water, improve the sweep efficiency and finally achieve the aim of improving the recovery ratio of crude oil. However, the polymer has the defects of shear thinning, pyrolysis and salt-encountering viscosity reduction, and in the tertiary oil recovery stage, an oil layer is deep, the temperature in an oil well is high, the use temperature of PAM cannot exceed 75 ℃, and phase separation is easy to occur in the oil layer with high mineralization, so that the solution viscosity is reduced violently.
In addition, in addition to displacement of reservoir oil by using hydrophilic polymers such as PAM and HPAM, surface active polymers having affinity to both aqueous phase and oil phase are commonly used as oil displacement agents to displace reservoir oil, and such surface active polymers include two major classes, amphiphilic block water-soluble polymers and hydrophobically associating water-soluble polymers. In order to overcome the above disadvantages of polyacrylamide, researchers at home and abroad have made a lot of research works, for example, US4814096 discloses a method of emulsion polymerization for preparing a copolymer of acrylamide, acrylic acid and lauryl methacrylate, and the hydrophobic association of the copolymer makes the polymer have better temperature resistance, salt resistance and shear resistance. Zhaoyong (the research on the synthesis and performance of hydrophobic association polyacrylamide in reverse microemulsion, 2000, (5): 550-553) synthesizes hydrophobic modified polyacrylamide by reverse microemulsion polymerization, and the water solution of the copolymer has excellent tackifying property. However, the preparation of the above-mentioned hydrophobically associating water-soluble polymer uses water-insoluble hydrophobic monomer, so that a large amount of surfactant is consumed, which results in huge industrial cost, and the surfactant is not easy to remove at the later stage to destroy the environment.
In order to solve various defects existing when a large amount of surfactant is used, a method for preparing the surfactant is providedThe copolymer with ionic surfactant side chain obtained by copolymerizing polymerizable surfactant monomer and acrylamide and other monomers is used as the oil displacement agent, and the copolymer obtains good salt resistance through the aggregation of the salt-induced surfactant side chain, and can be used as the oil displacement agent under the conditions of high temperature and high mineralization. Rong Yupeng (AM/AA/AMPS/AMC)14Preparation and characterization of S copolymer, proceedings of university of celadon science and technology, 2006, 27 (1): 1-4) preparation of polymerizable surface-active monomer AMC14S, the quadripolymer with higher molecular weight is prepared by utilizing a micelle polymerization method, the copolymer aqueous solution shows better viscosity increasing property under low temperature and low mineralization degree, but the quadripolymer has poor viscosity increasing property under high temperature and high salt and poor solubility, and the application of the quadripolymer in oil fields is greatly limited.
Disclosure of Invention
The invention aims to overcome the defect that the copolymer obtained by copolymerizing the existing surface active monomer and monomers such as acrylamide has poor tackifying performance under high temperature and high salt, and provides a surface active polymerizable monomer with good surface activity, a surface active copolymer with strong tackifying performance under high temperature and high salt and good solubility and a preparation method thereof.
The invention provides a surface active polymerizable monomer, wherein the surface active polymerizable monomer has a structure shown in a formula (1),
formula (1)
Wherein R is H or CH3N1 is 2 or 3, and n2 is an integer of 4 to 18.
The invention also provides a preparation method of the surface active polymerizable monomer, wherein the preparation method comprises the following steps: under the condition of alkylation reaction, under the alkaline condition, the acrylamide shown in the formula (2) and the halogenated alkyl sulfonic acid alkali metal salt shown in the formula (3) are contacted in an organic solvent,
formula (2)
X-(CH2)n2-SO3 -Y+Formula (3)
Wherein, in the formula (2), R is H or CH3N1 is 2 or 3; in the formula (3), n2 is an integer of 4 to 18, X is halogen, and Y is an alkali metal.
The invention also provides a surface active tackifying copolymer, wherein the copolymer contains a structural unit A shown in a formula (4) and a structural unit B shown in a formula (5), the content of the structural unit B is 0.1-20 wt% based on the copolymer, the molar ratio of the structural unit A to the structural unit B is 30-1000: 1, the intrinsic viscosity [ eta ] of the copolymer is 1200-2600mL/g,
formula (4)
Formula (5)
Wherein, in the formula (4), R1’、R2' and R3' are each independently hydrogen or alkyl of 1 to 3 carbon atoms, R4' is selected from-CONH2-COOH and-CONHC (CH)3)2CH2SO3Any one of H; in the formula (5), R is H or CH3N1 is 2 or 3, and n2 is an integer of 4 to 18.
The invention also provides a preparation method of the surface active tackifying copolymer, wherein the method comprises the following steps: polymerizing a monomer mixture in water in the presence of an initiator under polymerization conditions, the monomer mixture containing the monomer represented by the formula (6) and the above surface-active polymerizable monomer according to the present invention, and the surface-active polymerizable monomer being used in an amount of 0.1 to 20% by weight based on the monomer mixture, the molar ratio of the monomer represented by the formula (6) to the surface-active polymerizable monomer being 30 to 1000: 1, the polymerization conditions being such that the intrinsic viscosity [. eta. ] of the resulting copolymer is 1200 to 2600mL/g,
formula (6)
Wherein, in the formula (6), R1’、R2' and R3' are each independently hydrogen or alkyl of 1 to 3 carbon atoms, R4' is selected from-CONH2-COOH and-CONHC (CH)3)2CH2SO3Any one of H.
The surface active polymerizable monomer has a hydrophilic group and a hydrophobic group on a molecular structure, so that the surface active polymerizable monomer has good surface activity, has a self-solubilization effect when used for preparing a polymer, can obtain a copolymer with a surface active micro-block structure and good solubility performance without adding a surfactant, belongs to a derivative of acrylamide, is easy to copolymerize with an acrylamide monomer, and enhances the hydrolysis resistance of the surface active polymerizable monomer and the copolymer by using a substituted large group on amide N, so that the stability of the copolymer at high temperature is improved.
The surface active tackifying copolymer is prepared by carrying out homogeneous polymerization on the surface active polymerizable monomer and acrylic acid and/or acrylamide monomers in an aqueous solution, the preparation process is simple, a large amount of surfactant is not required to be added, and the production cost is greatly reduced. In addition, the copolymer solution has good temperature resistance, salt resistance and apparent viscosity, which is probably because the hydrodynamic radius of macromolecules is increased by the charge repulsion and association between molecules of the sulfonic acid group type strong anion hydrophilic group and the introduction of the fat or aryl hydrophobic side chain. When the surface active tackifying copolymer is used as an oil displacement agent, the surface active tackifying copolymer can also effectively play roles of solubilization, dispersion and the like on crude oil, so that residual crude oil difficult to displace can be carried and pulled, and the oil displacement efficiency of the residual crude oil is improved. The surface active tackifying copolymer can be used as a polymer oil displacement agent, is suitable for high-temperature high-salt oil reservoirs and polymer post-displacement oil reservoirs, and further improves the crude oil recovery rate in tertiary oil recovery.
Drawings
FIG. 1 is a graph showing the relationship between the apparent viscosities of a thickening copolymer of the present invention and a conventional thickening copolymer at different concentrations;
FIG. 2 is a graph showing the relationship between the apparent viscosities of a thickening copolymer of the present invention and a conventional thickening copolymer at different temperatures.
Detailed Description
The invention provides a surface active polymerizable monomer, wherein the surface active polymerizable monomer has a structure shown in a formula (1),
formula (1)
Wherein R is H or CH3N1 is 2 or 3, and n2 is an integer of 6 to 18.
Preferably, R is H, n1 is 2, n2 is an integer from 6 to 12; or R is CH3N1 is 2, n2 is an integer from 6 to 12; or R is H, n1 is 3, n2 is an integer from 6 to 12; or R is CH3N1 is 3, and n2 is an integer of 6 to 12.
The invention also provides a preparation method of the surface active polymerizable monomer, wherein the preparation method comprises the following steps: under the condition of alkylation reaction, under the alkaline condition, the acrylamide shown in the formula (2) and the halogenated alkyl sulfonic acid alkali metal salt shown in the formula (3) are contacted in an organic solvent,
formula (2)
X-(CH2)n2-SO3 -Y+Formula (3)
Wherein, in the formula (2), R is H or CH3N1 is 2 or 3; in the formula (3), n2 is an integer of 6 to 18, X is halogen, and Y is an alkali metal.
Preferably, in formula (3), n2 is an integer of 6 to 12;
in the formula (3), X is preferably chlorine, bromine or iodine; more preferably chlorine or bromine.
In the formula (3), Y is an alkali metal element, preferably sodium element.
The amounts of the acrylamide represented by the formula (2) and the alkali metal salt of a haloalkylsulfonic acid represented by the formula (3) may be widely varied depending on the method for preparing the surface-active polymerizable monomer. Preferably, the acrylamide represented by the formula (2) and the alkali metal salt of a haloalkylsulfonic acid represented by the formula (3) are used in a molar ratio of 0.7 to 2.5: 1, preferably 0.75 to 1.5: 1, more preferably 0.8 to 1.3: 1, and further preferably 1.0 to 1.2: 1. When the amounts of the acrylamide represented by the formula (2) and the alkali metal salt of a halogenated alkylsulfonic acid represented by the formula (3) are within the above ranges, the resulting surface-active polymerizable monomer has better solubility and higher surface activity.
The acrylamide represented by the formula (2) may be one or more of N, N-dimethylaminopropyl acrylamide, N-dimethylaminopropyl methacrylamide, N-dimethylaminoethyl acrylamide and N, N-dimethylaminoethyl methacrylamide according to a preparation method of a surface active polymerizable monomer.
According to the method for preparing the surface active polymerizable monomer of the present invention, preferably, the alkaline condition means a pH value of 9 to 11. The alkaline condition can be achieved, for example, by adding an alkaline compound (e.g., NaOH, KOH, etc.) to the mixture, so long as the desired pH range is achieved.
According to the method for producing a surface-active polymerizable monomer of the present invention, in a preferable case, the molar ratio of the organic solvent to the total amount of the acrylamide represented by the formula (2) and the alkali metal salt of a haloalkylsulfonic acid represented by the formula (3) may be 1 to 50: 1, more preferably 1.5 to 20: 1, and further preferably 2 to 10: 1.
The organic solvent may be any of various solvents known in the art. Preferably, it is selected from one or more of ethanol, isopropanol, tetrahydrofuran, diethyl ether, chloroform, ethyl acetate, dimethylformamide, benzene and toluene.
According to the preparation method of the surface active polymerizable monomer, the conditions for contacting the acrylamide shown in the formula (2) and the halogenated alkyl sulfonic acid alkali metal salt shown in the formula (3) comprise the contact temperature and the contact time, and the contact temperature can be selected in a wide temperature range. Preferably the contact temperature is from 10 to 50 deg.C, more preferably from 30 to 45 deg.C; the increase in the reaction yield is facilitated by the increase in the contact time, but the increase in the yield is not significant by the excessively long contact time, and therefore, it is generally preferred that the contact time is 10 to 20 hours, more preferably 10 to 14 hours.
According to the preparation method of the surface active polymerizable monomer, the method also comprises the steps of cooling the contacted product at room temperature, carrying out solid-liquid separation, and carrying out vacuum drying to obtain the surface active polymerizable monomer. In order to further increase the purity of the obtained surface-active polymerizable monomer, it is preferable that the solid obtained by the solid-liquid separation is crystallized and then dried.
The filtration, vacuum drying and recrystallization can adopt the methods or methods which are commonly used in the field, and the invention has no special requirements. For example, the solvent for recrystallization may be one or more of ethanol, acetone, isopropanol, ethyl acetate.
Since the surface-active polymerizable monomer is prepared by dehydrohalogenation reaction between halogenated hydrocarbon and organic amine, which is a reaction which is very conventional and well-studied in the field of organic chemistry, the solid product obtained after contacting the acrylamide represented by the formula (2) and the alkali metal salt of halogenated alkylsulfonic acid represented by the formula (3) can be proved to have the structure represented by the formula (1) without special structural characterization, but can also be characterized, for example, by nuclear magnetic resonance and infrared spectroscopy.
The invention also provides a surface active tackifying copolymer, wherein the copolymer contains a structural unit A shown in a formula (4) and a structural unit B shown in a formula (5), the content of the structural unit B is 0.1-20 wt% based on the copolymer, the molar ratio of the structural unit A to the structural unit B is 30-1000: 1, the intrinsic viscosity [ eta ] of the copolymer is 1200-2600mL/g,
formula (4)
Formula (5)
Wherein, in the formula (4), R1’、R2' and R3' are each independently hydrogen or alkyl of 1 to 3 carbon atoms, R4' is selected from-CONH2-COOH and-CONHC (CH)3)2CH2SO3Any one of H; in the formula (5), R is H or CH3N1 is 2 or 3, and n2 is an integer of 4 to 18.
Preferably, in formula (5), R is H, n1 is 2, and n2 is an integer of 6 to 12; or R is CH3N1 is 2, n2 is an integer from 6 to 12; or R is H, n1 is 3, n2 is 6-12An integer number; or R is CH3N1 is 3, and n2 is an integer of 6 to 12.
The content of the structural units B is generally from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, and more preferably from 5 to 9% by weight, based on the copolymer, of the surface-active adhesion-promoting copolymer according to the invention; the molar ratio of the structural unit A to the structural unit B is generally from 30 to 1000: 1, preferably from 40 to 800: 1, and more preferably from 50 to 650: 1.
According to the surface-active adhesion-promoting copolymers of the invention, the intrinsic viscosity [ eta ] of said copolymers may be from 1200 to 2600mL/g, preferably from 1800 to 2600mL/g, more preferably from 2200 to 2600 mL/g.
The surface active thickening copolymer of the invention has an apparent viscosity at 75 ℃ of 12 to 20 mPas, preferably 15 to 20 mPas, of an aqueous solution of the surface active polymer with a concentration of 1500mg/L and a mineralization degree of 30000 mg/L. In the present invention, the degree of mineralization is the sum of the inorganic ion contents of the aqueous solution, the inorganic ions generally including Na+，K+，Ca2+，Mg2+，C1-，SO4 2-，CO3 2-And the like.
The invention also provides a preparation method of the surface active tackifying copolymer, wherein the method comprises the following steps: polymerizing a monomer mixture in water in the presence of an initiator under polymerization conditions, the monomer mixture containing the monomer represented by the formula (6) and the above surface-active polymerizable monomer according to the present invention, and the surface-active polymerizable monomer being used in an amount of 0.1 to 20% by weight based on the monomer mixture, the molar ratio of the monomer represented by the formula (6) to the surface-active polymerizable monomer being 30 to 1000: 1, the polymerization conditions being such that the intrinsic viscosity [. eta. ] of the resulting copolymer is 1200 to 2600mL/g,
formula (6)
Wherein,in the formula (6), R1’、R2' and R3' are each independently hydrogen or alkyl of 1 to 3 carbon atoms, R4' is selected from-CONH2-COOH and-CONHC (CH)3)2CH2SO3Any one of H.
The monomer mixture may contain one monomer represented by formula (6) or a plurality of monomers represented by formula (6).
According to the present invention, the surface-active polymerizable monomer is used in an amount of generally 0.1 to 20% by weight, preferably 0.5 to 10% by weight, and more preferably 5 to 9% by weight, based on the monomer mixture; the molar ratio of the monomer represented by the formula (6) to the surface-active polymerizable monomer of the present invention is generally 30 to 1000: 1, preferably 40 to 800: 1, and more preferably 50 to 650: 1.
In the preparation method of the surface active tackifying copolymer, the monomer shown in the formula (6) can be one or more of acrylic acid, methacrylic acid, acrylamide, methacrylamide and 2-acrylamido-2-methylpropanesulfonic acid.
In the method of preparing the surface active tackifying copolymer of the present invention, the amount of the initiator may be used in an amount of 0.0001 to 0.1% by weight, based on the monomer mixture. The initiator may be any initiator known in the art. For example, the initiator may be a peroxide initiator such as potassium persulfate, sodium persulfate, ammonium persulfate and the like, a redox system initiator such as potassium persulfate-sodium sulfite, sodium persulfate-sodium sulfite, ammonium persulfate-sodium sulfite, potassium persulfate-sodium bisulfite, sodium persulfate-sodium bisulfite, ammonium persulfate-sodium bisulfite and the like, an azo initiator such as azobisisobutylamidine hydrochloride and the like, in the present invention, the initiator is further preferably one or more of complex initiators consisting of potassium persulfate, sodium persulfate, ammonium persulfate, potassium persulfate-sodium sulfite, sodium persulfate-sodium sulfite, ammonium persulfate-sodium sulfite, potassium persulfate-sodium bisulfite, sodium persulfate-sodium bisulfite or ammonium persulfate-sodium bisulfite and azobisisobutylamidine hydrochloride. When the composite initiator is used as a polymerization initiator, the copolymerization reaction between the acrylic acid and/or acrylamide monomer and the surface active polymerizable monomer is initiated more favorably.
In the method for preparing the surface active tackifying copolymer, the polymerization conditions can be various conditions which can cause the polymerization reaction between the monomer shown in the formula (6) and the surface active polymerizable monomer, and preferably, the polymerization reaction comprises a first polymerization reaction section and a second polymerization reaction section which are sequentially performed, wherein the conditions of the first polymerization reaction section comprise that the polymerization temperature is 5-30 ℃, and preferably 5-15 ℃; the polymerization time may be 2 to 16 hours, preferably 8 to 16 hours, and the conditions of the second polymerization reaction zone may include a polymerization temperature of 40 to 55 ℃, preferably 45 to 55 ℃; the polymerization time may be 1 to 8 hours, preferably 2 to 6 hours, and more preferably 2 to 4 hours.
In the method for producing a surface-active tackifying copolymer of the present invention, in order to further accelerate the progress of the polymerization reaction, the reaction system is preferably controlled to be alkaline, and for example, the pH of the reaction system can be adjusted using sodium hydroxide, sodium carbonate, potassium carbonate, aqueous ammonia or an aqueous solution thereof, and more preferably, the pH of the reaction system is controlled to be within a range of 7.1 to 10.5, and preferably, 7.4 to 9.0.
In the method for producing a surface-active tackifying copolymer of the present invention, in order to suppress the occurrence of side reactions and to increase the conversion rate of the reaction, the polymerization reaction is preferably carried out under inert conditions, and for example, the polymerization reaction system can be kept in an inert atmosphere by introducing an inert gas such as nitrogen or argon into the reaction system.
In the method for producing a surface-active tackifying copolymer of the present invention, more preferably, the monomer mixture consists only of the monomer represented by formula (6) and the surface-active polymerizable monomer of the present invention.
According to the application of the surface active tackifying copolymer in the polymer oil-displacing agent, the surface active tackifying copolymer can be used as the polymer oil-displacing agent and is suitable for high-temperature and high-salt oil reservoirs and polymer post-flooding oil reservoirs, and the crude oil recovery rate is further improved in tertiary oil recovery.
In the present invention, the polymer oil-displacing agent may contain various tackifying polymers having an oil-displacing effect, such as polyacrylamide, etc., which are commonly used in the art, in addition to the surface active tackifying copolymer of the present invention.
The present invention is described in further detail below by way of specific examples.
The aliphatic or aromatic amines used in the examples below were obtained from Beijing Chemicals, an alkali metal salt of a haloalkylsulfonic acid, acrylamide, acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid from Allantin; initiators were purchased from the national pharmaceutical group chemical agents corporation.
The dissolution time of the copolymer was determined according to GB 12005.8-89; intrinsic viscosity [ eta ] of the copolymer]The determination is carried out according to the determination method of the intrinsic viscosity number of the polyacrylamide in GB 12005.1-89: measured at 25 ℃ with an Ubbelohde viscometer (10% by weight NaCl solution); the apparent viscosity of the copolymer was measured with a Brookfield DV-III viscometer at a concentration of 1500mg/L, a degree of mineralization of 30000mg/L at 80 ℃ and a rotation speed of 6 r.min-1Under the conditions of (1).
Example 1
This example serves to illustrate the surface-active polymerizable monomers and surface-active tackifying copolymers of the present invention and their methods of preparation.
(1) Preparation of surface-active polymerizable monomers:
adding 1mol of N, N-dimethylaminopropyl acrylamide, 0.85mol of 6-chlorohexyl sodium sulfonate, 300mL of ethanol and 20g of sodium hydroxide into a 1L three-necked bottle, reacting at 25 ℃ for 12 hours under the condition that the pH value of the solution in the reactor is 10.2, cooling, filtering to obtain a solid, and determining the solid to be the surface active polymerizable monomer BH-1 with the characteristics of R being H, N1 being 3 and N2 being 6 in the formula (1) by nuclear magnetic resonance analysis.
(2) Preparation of copolymer PS-1:
adding 13.2g of acrylamide, 5.6g of acrylic acid and 11.6g of the obtained monomer BH-11 into a polymerization reactor, adding 55ml of deionized water, adjusting the pH value to 7.4 by using 20% sodium hydroxide solution, and then introducing high-purity nitrogen for bubbling and deoxidizing; after half an hour, 2.6mg of composite initiator consisting of potassium persulfate, sodium sulfite and azodiisobutyl amidine hydrochloride in the molar ratio of 1: 0.5 is added, polymerization is carried out for 10 hours at 6 ℃, then the temperature is raised to 45 ℃, reaction is continued for 2 hours, a colloidal polymer is obtained, and the surface active tackifying copolymer PS-1 is obtained after slicing, drying and crushing, wherein the parameters are shown in Table 1.
Comparative example 1
A copolymer AM-AA of Acrylamide (AM) and Acrylic Acid (AA) was prepared according to the procedure for preparing a tackifying copolymer PS-1 in example 1, except that no BH-1 was added to obtain a copolymer DB of acrylamide and acrylic acid, the parameters of which are shown in Table 1.
Example 2
This example serves to illustrate the surface-active polymerizable monomers and surface-active tackifying copolymers of the present invention and their methods of preparation.
(1) Preparation of surface-active polymerizable monomers:
adding 1mol of N, N-dimethylaminoethyl acrylamide, 0.90mol of 8-chlorooctyl sodium sulfonate, 300mL of ethanol and 20g of sodium hydroxide into a 1L three-necked bottle, wherein the pH value of the solution in the reactor is 10.2, reacting at the temperature of 25 ℃ for 10 hours, cooling and filtering to obtain a solid, and determining that the solid is the surface active polymerizable monomer BH-2 with the characteristics of R being H, N1 being 3 and N2 being 8 in the formula (1) by nuclear magnetic resonance analysis.
(2) Preparation of copolymer PS-2:
adding 13.2g of acrylamide, 5.6g of acrylic acid and 21.2g of the obtained monomer BH-21 to a polymerization reactor, adding 55ml of deionized water, adjusting the pH value to 7.6 by using 20% sodium hydroxide solution, and then introducing high-purity nitrogen for bubbling and deoxidizing; after half an hour, 2.6mg of a composite initiator consisting of potassium persulfate, sodium sulfite and azodiisobutyl amidine hydrochloride in a molar ratio of 1: 0.5 is added, polymerization is carried out for 14 hours at 5 ℃, then the temperature is raised to 45 ℃, reaction is continued for 3 hours to obtain a colloidal polymer, and the colloidal polymer is sliced, dried and crushed to obtain the surface active tackifying copolymer PS-2, wherein the parameters are shown in Table 1.
Example 3
This example serves to illustrate the surface-active polymerizable monomers and surface-active tackifying copolymers of the present invention and their methods of preparation.
(1) Preparation of surface-active polymerizable monomers:
adding 1mol of N, N-dimethylaminopropyl acrylamide, 0.95mol of 8-bromooctyl sodium sulfonate, 300mL of ethanol and 18g of sodium hydroxide into a 1L three-necked bottle, reacting at 35 ℃ for 10 hours under the condition that the pH value of the solution in the reactor is 10.2, cooling, filtering to obtain a solid, and determining the solid to be the surface active polymerizable monomer BH-3 with the characteristics of R being H, N1 being 3 and N2 being 8 in the formula (1) of the invention through nuclear magnetic resonance analysis.
(2) Preparation of copolymer PS-3:
adding 13.2g of acrylamide, 5.6g of acrylic acid and 31.2g of the monomer BH-31 obtained in the polymerization reactor, adding 55ml of deionized water, adjusting the pH value to 7.6 by using 20% sodium hydroxide solution, and then introducing high-purity nitrogen for bubbling and deoxidizing; after half an hour, 2.6mg of a composite initiator consisting of potassium persulfate, sodium sulfite and azodiisobutyl amidine hydrochloride in a molar ratio of 1: 0.5 is added, polymerization is carried out for 9 hours at the temperature of 8 ℃, then the temperature is raised to 45 ℃, the reaction is continued for 3 hours, a colloidal polymer is obtained, and the surface active tackifying copolymer PS-3 is obtained after slicing, drying and crushing, wherein the parameters are shown in Table 1.
Example 4
(1) Preparation of surface-active polymerizable monomers:
a surface-active monomer was prepared by following the procedure for preparing a surface-active monomer as in example 3, except that N, N-dimethylaminopropylacrylamide was replaced by N, N-dimethylaminopropylmethacrylamide and the solvent ethanol was replaced by methanol, to obtain a surface-active monomer of the present invention, wherein R in formula (1) is CH3N1 is 3 and n2 is 8.
(2) Preparation of tackifier PS-4:
a tackifier was prepared by the method of example 3, except that BH-3 was replaced with 40.2g of the surface-active monomer BH-4 obtained in example 4, to give a surface-active tackifier copolymer PS-4, the parameters of which are shown in Table 1.
Example 5
(1) Preparation of surface-active polymerizable monomers:
adding 1mol of N, N-dimethylaminopropyl methacrylamide, 1.25mol of 12-bromododecyl sodium sulfate, 350mL of ethanol and 22g of sodium hydroxide into a 1L three-necked bottle, wherein the pH value of the solution in the reactor is 10.8, reacting at the temperature of 40 ℃ for 12 hours, cooling and filtering to obtain a solid, and determining the solid to be the surface active polymerizable monomer BH-5 with the R of the formula (1) of the invention as H, N1 as 3 and N2 as 12 through nuclear magnetic resonance analysis.
(2) Preparation of copolymer PS-5:
adding 13.2g of acrylamide, 5.6g of acrylic acid and 51.8g of the obtained monomer BH-51 into a polymerization reactor, adding 55ml of deionized water, adjusting the pH value to 7.8 by using 20% sodium hydroxide solution, and then introducing high-purity nitrogen for bubbling and deoxidizing; after half an hour, 2.6mg of composite initiator consisting of potassium persulfate, sodium sulfite and azodiisobutyl amidine hydrochloride in the molar ratio of 1: 0.5 is added, polymerization is carried out for 8 hours at 15 ℃, then the temperature is raised to 55 ℃, reaction is continued for 2 hours, a colloidal polymer is obtained, and the surface active tackifying copolymer PS-5 is obtained after slicing, drying and crushing, wherein the parameters are shown in Table 1.
Example 6
This example illustrates the surface active tackifying copolymers and the process for making the same of the present invention.
Preparation of copolymer PS-6:
adding 13.2g of acrylamide, 6.0g of 2-acrylamido-2-methylpropanesulfonic acid and 31.2g of the monomer BH-31 obtained in example 3 into a polymerization reactor, adding 55ml of deionized water, adjusting the pH to 7.8 by using a 20% sodium hydroxide solution, and then introducing high-purity nitrogen gas for bubbling and deoxidizing; after half an hour, 2.6mg of a composite initiator consisting of potassium persulfate, sodium sulfite and azodiisobutyl amidine hydrochloride in a molar ratio of 1: 0.5 is added, polymerization is carried out for 10 hours at 6 ℃, then the temperature is raised to 45 ℃, reaction is continued for 3 hours to obtain a colloidal polymer, and the colloidal polymer is sliced, dried and crushed to obtain the surface active tackifying copolymer PS-6, wherein the parameters are shown in Table 1.
Example 7
This example serves to illustrate the surface-active polymerizable monomers and surface-active tackifying copolymers of the present invention and their methods of preparation.
Preparation of copolymer PS-7:
adding 13.2g of acrylamide, 6.0g of 2-acrylamido-2-methylpropanesulfonic acid and 51.8g of the monomer BH-51 obtained in example 3 into a polymerization reactor, adding 55ml of deionized water, adjusting the pH to 8.0 by using a 20% sodium hydroxide solution, and then introducing high-purity nitrogen gas for bubbling and deoxidizing; after half an hour, 2.6mg of a composite initiator consisting of potassium persulfate, sodium sulfite and azodiisobutyl amidine hydrochloride in a molar ratio of 1: 0.5 is added, polymerization is carried out for 8 hours at 10 ℃, then the temperature is raised to 45 ℃, reaction is continued for 4 hours, a colloidal polymer is obtained, and the surface active tackifying copolymer PS-7 is obtained after slicing, drying and crushing, wherein the parameters are shown in Table 1.
TABLE 1 solution Properties of amphiphilic Polyacrylamide tackifier PS
Experimental example 1
The surface-active tackifying copolymers (PS-1) to (PS-7) prepared in examples 1 to 7 of the present invention and the copolymer DB prepared in comparative example 1 were each prepared with 1000mg/L of mineralized saline to polymer tackifier solutions having concentrations of 200mg/L, 500mg/L, 1000mg/L, 1500mg/L, 2000mg/L, 2500mg/L, and 3000mg/L, respectively, at 75 ℃ at a rotation speed of 6 r.min-1The apparent viscosities of the polymer tackifier solutions at different concentrations were measured. The relationship between the apparent viscosity at different concentrations of the surface active tackifying copolymer of the present invention and the tackifying copolymer of comparative example 1 is shown in FIG. 1.
As can be seen from FIG. 1, the apparent viscosity of the surface-active tackifying copolymers of the present invention is higher at each concentration than the apparent viscosity of copolymer DB at each concentration.
Experimental example 2
The surface active tackifier copolymers (PS-1) to (PS-7) prepared in examples 1 to 7 of the present invention and the copolymer DB prepared in comparative example 1 were each prepared using 30000mg/L of salinity brine to prepare a polymer tackifier solution having a concentration of 1500mg/L at 6 r.min-1The apparent viscosity of each polymer tackifier solution at 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ and 90 ℃ is detected at the rotating speed of (1). The relationship between the apparent viscosity at different temperatures of the surface active tackifying copolymer of the present invention and the tackifying copolymer of comparative example 1 is shown in FIG. 2.
As can be seen from FIG. 2, the apparent viscosity of the surface active tackifying copolymer of the present invention is higher at each temperature and high salt than that of copolymer DB, and further the apparent viscosity of the surface active tackifying copolymer of the present invention is higher at high temperature and high salt than that of copolymer DB.
Claims (6)
1. A method of preparing a surface active tackifying copolymer, comprising: polymerizing a monomer mixture in water under polymerization conditions in the presence of an initiator, wherein the monomer mixture contains a monomer represented by the formula (6) and a surface-active polymerizable monomer, and the surface-active polymerizable monomer is used in an amount of 0.1 to 20% by weight based on the monomer mixture, and the molar ratio of the monomer represented by the formula (6) to the surface-active polymerizable monomer is 30 to 1000: 1, the conditions of the polymerization reaction ensure that the intrinsic viscosity [ eta ] of the obtained copolymer is 1200-2600 mL/g; the initiator may be used in an amount of 0.0001 to 0.1 wt% based on the monomer mixture; the polymerization reaction comprises a first polymerization reaction section and a second polymerization reaction section which are sequentially carried out, wherein the polymerization temperature of the first polymerization reaction section is 5-30 ℃, and the polymerization temperature of the second polymerization reaction section is 45-55 ℃; the polymerization reaction is carried out under the condition that the pH value is 7.1-10.5;
formula (6)
Wherein, in the formula (6), R1’、R2' and R3' are each independently hydrogen or alkyl of 1 to 3 carbon atoms, R4' is selected from-CONH2-COOH and-CONHC (CH)3)2CH2SO3Any one of H;
wherein the surface active polymerizable monomer has a structure represented by formula (1),
formula (1)
Wherein R is H or CH3N1 is 2 or 3, and n2 is an integer of 4 to 18.
2. The process for preparing a surface-active tackifying copolymer according to claim 1, wherein in formula (1), R is H, n1 is 2, n2 is an integer from 6 to 12; or R is CH3N1 is 2, n2 is an integer from 6 to 12; or R is H, n1 is 3, n2 is an integer from 6 to 12; or R is CH3N1 is 3, and n2 is an integer of 6 to 12.
3. The method of claim 1, wherein the surface-active polymerizable monomer is used in an amount of 0.5 to 10 wt%; the molar ratio of the monomer represented by the formula (6) to the surface-active polymerizable monomer is 40 to 800: 1.
4. the method of claim 1, wherein the monomer of formula (6) is one or more of acrylic acid, methacrylic acid, acrylamide, methacrylamide, and 2-acrylamido-2-methylpropanesulfonic acid.
5. The method of claim 1, wherein the polymerization time in the first polymerization stage is 2-16 hours and the polymerization time in the second polymerization stage is 1-8 hours.
6. Use of a surface active viscosifying copolymer prepared according to the method of any of claims 1 to 5 in an oil displacing agent.
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| CN104403052A (en) * | 2014-11-07 | 2015-03-11 | 西南石油大学 | Acrylamide copolymer oil-dispelling agent with sulfitobetaine structure and synthesis method |
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