CN115703723B - Acrylamide compound, heat-resistant salt-resistant polyacrylamide for oil displacement, and preparation method and application thereof - Google Patents
Acrylamide compound, heat-resistant salt-resistant polyacrylamide for oil displacement, and preparation method and application thereof Download PDFInfo
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- CN115703723B CN115703723B CN202110908666.7A CN202110908666A CN115703723B CN 115703723 B CN115703723 B CN 115703723B CN 202110908666 A CN202110908666 A CN 202110908666A CN 115703723 B CN115703723 B CN 115703723B
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- -1 Acrylamide compound Chemical class 0.000 title claims abstract description 56
- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 47
- 150000003839 salts Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000011549 displacement method Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 239000002738 chelating agent Substances 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 238000006073 displacement reaction Methods 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 81
- 229920000642 polymer Polymers 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 28
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 18
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 150000007514 bases Chemical class 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 2
- DXTIKTAIYCJTII-UHFFFAOYSA-N guanidine acetate Chemical compound CC([O-])=O.NC([NH3+])=N DXTIKTAIYCJTII-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229960003330 pentetic acid Drugs 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- VLDHWMAJBNWALQ-UHFFFAOYSA-M sodium;1,3-benzothiazol-3-ide-2-thione Chemical compound [Na+].C1=CC=C2SC([S-])=NC2=C1 VLDHWMAJBNWALQ-UHFFFAOYSA-M 0.000 claims description 2
- UDYFLDICVHJSOY-UHFFFAOYSA-N sulfur trioxide pyridine complex Chemical compound O=S(=O)=O.C1=CC=NC=C1 UDYFLDICVHJSOY-UHFFFAOYSA-N 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 125000000468 ketone group Chemical group 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 42
- 239000000178 monomer Substances 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 239000003921 oil Substances 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 238000007873 sieving Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000003814 drug Substances 0.000 description 7
- 229920006322 acrylamide copolymer Polymers 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- SZUDEHNEMMJTCQ-UHFFFAOYSA-N prop-2-enenitrile;hydrate Chemical compound O.C=CC#N SZUDEHNEMMJTCQ-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000230 xanthan gum Substances 0.000 description 3
- 229920001285 xanthan gum Polymers 0.000 description 3
- 235000010493 xanthan gum Nutrition 0.000 description 3
- 229940082509 xanthan gum Drugs 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- 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 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 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
- 229920001046 Nanocellulose Polymers 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a novel acrylamide compound, a temperature-resistant salt-resistant polyacrylamide for oil displacement, and a preparation method and application thereof. The invention adds initiator, oxidant, reducer, stabilizer and chelating agent into the reaction system of acrylamide compound and acrylamide to react, and the product obtained by hydrolysis reaction after reaction is the heat-resistant salt-resistant polyacrylamide for oil displacement. According to the temperature-resistant salt-resistant polyacrylamide provided by the invention, the rigid side chain is introduced into the side chain of the acrylamide, so that the chain link strength is improved, and the temperature-resistant salt-resistant capability of the polyacrylamide is enhanced; meanwhile, the ketone group at the tail end of the chain and the branched alkyl have certain effects of inhibiting hydrolysis and improving stability, so that the temperature resistance and the salt resistance are further improved.
Description
Technical Field
The invention belongs to the field of oilfield chemicals, and particularly relates to an acrylamide compound, a temperature-resistant salt-resistant polyacrylamide for oil displacement, and a preparation method and application thereof.
Background
The principle of polymer flooding to increase recovery is to increase the viscosity of the aqueous phase and thereby reduce the fluidity ratio of the oil to water, (which is defined as (k) rw /u w )/(k ro /u o )，k ro Oil permeability, k rw Water permeability, u o Viscosity of oil, u w The viscosity of water) to increase the "swept" volume of the displacement fluid. The successful application of polymer flooding can improve the recovery ratio of crude oil by 5-15%. Currently, in oil and gas exploitation, many polymers are studied, including partially Hydrolyzed Polyacrylamide (HPAM), acrylamide copolymers, biopolymers (xanthan gum), cellulose ether compounds, polyvinylpyrrolidone, and the like. But HPAM products have poor shear stability and poor temperature resistance and salt resistance; the xanthan gum has good salt resistance and shearing resistance, but has poor temperature resistance and high price. HPAM and xanthan gum are both difficult to meet the needs of high temperature and high salt reservoirs. Therefore, developing a temperature-resistant and salt-resistant acrylamide copolymer system has important significance for polymer oil displacement technology.
The method for improving the performance of the polymer mainly comprises the following steps: improving the thermal stability of the main chain of the polymer molecule; introducing a large side group or a rigid side group; introducing a structural unit with a special function; introducing lipophilic groups and hydrophilic groups on the polymer chains by utilizing the interaction between the polymer chains; graft-copolymerizing with natural polymer, etc.
The acrylamide copolymer prepared by the conventional method generally improves the temperature resistance and salt resistance of the polymer by copolymerizing a novel functional monomer, for example, chinese patent CN110272519A uses acrylamide, acrylic acid and KH570 to carry out ternary polymerization, and introduces a large side chain group on the side chain of the acrylamide, thereby increasing the steric hindrance and improving the temperature resistance and salt resistance. Also, as in chinese patent CN107987820a, modified nanocellulose, acrylamide and sodium 2-acrylamido-2-methylpropanesulfonate are copolymerized, and a large side chain group is introduced into the side chain of acrylamide, so as to improve the rigidity of polymer molecules and form a good intermolecular network structure of polymer, thereby producing excellent performances of temperature resistance, salt resistance, aging resistance, etc. The acrylamide copolymer prepared by the method is limited in application in high-temperature and high-salt oil reservoirs, and the generally synthesized copolymer has poor salt tolerance and certain limitation in practical application.
Disclosure of Invention
Aiming at the problem that the conventional acrylamide copolymer has poor temperature resistance and salt resistance, the invention provides a novel acrylamide compound, the polyacrylamide for temperature resistance and salt resistance oil displacement and a synthesis method thereof, and the obtained polyacrylamide can achieve good oil displacement effect at higher temperature and higher salinity. According to the invention, the temperature-resistant salt-resistant polyacrylamide is synthesized, so that a rigid side chain is obtained on the side chain of the acrylamide, and the temperature-resistant salt-resistant performance is improved; meanwhile, the ketone group at the tail end of the chain and the branched alkyl have certain effects of inhibiting hydrolysis and improving stability, so that the temperature resistance and the salt resistance are further improved.
The invention aims to provide an acrylamide compound, which has the following structural formula:
the second purpose of the invention is to provide a preparation method of the acrylamide compound, which comprises the step of reacting a component comprising a compound shown in a formula (II), acrylonitrile and a sulfonating agent to obtain the acrylamide compound.
Specifically, the molar ratio of the compound of formula (II), acrylonitrile and sulfonating agent is (0.5-3): (4-15): 1, preferably (0.8 to 1.2): (6-10): 1, a step of;
the chemical name of the compound of the formula (II) is 4, 4-dimethyl-2-phenyl-1-pentene-3-one;
the sulfonating agent is at least one selected from fuming sulfuric acid, sulfur trioxide, chlorosulfonic acid, sulfur dioxide and chlorine gas, sulfur dioxide and oxygen, sulfur trioxide pyridine, and preferably fuming sulfuric acid with the concentration of 10-40%;
the reaction conditions are as follows: reacting for 0.5-5 h at the temperature of-5-10 ℃, and heating to 30-60 ℃ for reacting for 1-24 h; preferably, the reaction is carried out for 1 to 2 hours at the temperature of between 0 and 5 ℃, and the reaction is carried out for 5 to 10 hours after the temperature is raised to between 40 and 50 ℃;
an anhydride compound and a catalyst are also added in the reaction, wherein the anhydride compound is selected from acetic anhydride, and the catalyst is selected from at least one of p-toluenesulfonic acid and phosphoric acid; the amount of the anhydride compound is 1 to 50 parts, preferably 1 to 25 parts, based on 100 parts by mass of the sulfonating agent; the catalyst is used in an amount of 1 to 25 parts, preferably 1 to 15 parts, based on 100 parts by weight of the total mass of the compound of formula (II) and acrylonitrile;
the product obtained by the reaction also needs to be subjected to standing, washing and drying treatment, wherein the standing condition is that the product is subjected to standing for 3-48 hours at 10-40 ℃, preferably, the product is subjected to standing for 8-24 hours at 20-35 ℃; the solvent used for washing is at least one selected from acrylonitrile, acetone, N-dimethylformamide, anhydrous methanol and water, preferably at least one selected from acrylonitrile-water and acetone; the drying temperature is 20-60 ℃, preferably 40-55 ℃; the drying time is 3 to 24 hours, preferably 4 to 10 hours.
In a preferred embodiment of the above process for producing an acrylamide compound: adding acrylonitrile, a compound of formula (II), a dehydrating agent acetic anhydride and a catalyst p-toluenesulfonic acid into a reaction bottle provided with a mechanical stirrer, a thermometer, a constant pressure funnel and a reflux condenser at normal temperature. Slowly adding fuming sulfuric acid at low temperature (0-5 ℃), maintaining the low temperature for reaction for 1-2 h, then heating to 40-50 ℃ for reaction for 5-10 h, generating white solid, stopping the reaction, standing for 8-24 h, filtering, washing 2 times with acrylonitrile-water, washing 2 times with acetone, and drying in a vacuum oven at 40-55 ℃ for 4-10 h.
In the invention, acetic anhydride and fuming sulfuric acid are mixed to form mixed anhydride, HO separated from the mixed anhydride 3 S + Has electrophilic activity, reacts with a compound (4, 4-dimethyl-2-phenyl-1-pentene-3-ketone) of a formula (II) to form a carbonium ion with a sulfonic group, and then reacts with acrylonitrile under the action of fuming sulfuric acid to form the acrylamide compound, wherein the reaction equation is shown as follows:
the third object of the present invention is to provide a polyacrylamide prepared from the above acrylamide compound or an acrylamide compound obtained by the above preparation method.
The fourth object of the invention is to provide a preparation method of the polyacrylamide, which comprises the steps of reacting the components comprising the acrylamide compound and the acrylamide to obtain the polyacrylamide. Preferably, the preparation method specifically comprises the following steps:
step 1) dissolving the acrylamide compound into water, and adding acrylamide;
step 2) adding a pH regulator;
step 3) adding an initiator, an oxidant, a reducing agent, a chelating agent and a stabilizing agent into the solution obtained in the step 2), and then heating for reaction;
and step 4) crushing the solid obtained in the reaction in the step 3), adding an alkaline compound, and heating for reaction to obtain the polyacrylamide.
In particular, the method comprises the steps of,
the pH regulator is selected from alkaline compounds, preferably at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium acetate and ammonia water;
the initiator is selected from azo compounds, preferably at least one of azo diisobutylamidine hydrochloride (V-50 initiator), azo diiso Ding Mi hydrochloride (VA-044 initiator) and azo diisopropyl imidazoline (VA-061 initiator);
the oxidant is at least one selected from persulfates and peroxides, preferably at least one selected from potassium persulfate, sodium persulfate, ammonium persulfate and tert-butyl hydroperoxide;
the reducing agent is at least one selected from sulfite compounds and sulfate compounds, preferably at least one selected from sodium sulfite, sodium bisulfite and ferrous ammonium sulfate;
the stabilizer is at least one selected from thiourea, sodium dithionite, guanidine acetate, sodium sulfite and sodium 2-mercaptobenzothiazole;
the chelating agent is at least one selected from disodium ethylenediamine tetraacetate, ethylenediamine, 2-bipyridine, diethylenetriamine pentaacetic acid and salts thereof, preferably disodium ethylenediamine tetraacetate;
the basic compound in the step 4) is selected from inorganic basic compounds, preferably at least one selected from sodium hydroxide, sodium carbonate and potassium hydroxide.
In the preparation method, the added azo initiator, oxidant and reducing agent can initiate the free radical reaction of the system, so as to promote the reaction of the sulfonic acid compound and the acrylamide; the stabilizer is added to ensure that the polymer can keep better stability at high temperature and improve the temperature resistance of the polymer; the added chelating agent can chelate metal ions in the reaction system, and the influence of the metal ions on the reaction is reduced.
The preparation method comprises the following steps:
in the step 1), the mass ratio of the acrylamide compound to the acrylamide to the water is 1: (3-30): (10 to 90), preferably 1: (5-20): (20-90);
the pH regulator is added in the step 2) to regulate the pH to 5-10, preferably 7-9;
the reaction temperature in the step 3) is 10-40 ℃, preferably 15-25 ℃; the reaction time is 1 to 12 hours, preferably 6 to 10 hours;
the reaction in step 3) is carried out in an inert gas atmosphere, which may optionally be a common inert gas such as nitrogen;
in the step 3), the initiator is added in an amount of 0.01 to 0.5 part, the oxidant is added in an amount of 0.001 to 0.05 part, the reducing agent is added in an amount of 0.001 to 0.05 part, the stabilizer is added in an amount of 0.1 to 3 parts, and the chelating agent is added in an amount of 0.001 to 0.03 part, based on 100 parts by weight of the acrylamide compound and the acrylamide; preferably, the initiator is added in an amount of 0.01 to 0.2 part, the oxidant is added in an amount of 0.002 to 0.02 part, the reducing agent is added in an amount of 0.001 to 0.01 part, the stabilizer is added in an amount of 0.5 to 2 parts, and the chelating agent is added in an amount of 0.001 to 0.01 part;
the alkaline compound in the step 4) is added in an amount of 5 to 20 parts by weight, preferably 10 to 16 parts by weight, based on 100 parts by weight of the acrylamide;
the reaction temperature in the step 4) is 60-90 ℃, preferably 80-90 ℃; the reaction time is 2 to 12 hours, preferably 2 to 6 hours;
the polyacrylamide obtained in the step 4) also needs drying treatment, preferably, the drying temperature is 30-70 ℃, preferably 40-55 ℃; the drying time is 1 to 12 hours, preferably 4 to 9 hours.
In a preferred embodiment of the above method for producing polyacrylamide: and (3) completely dissolving a certain amount of acrylamide compound with water, adding acrylamide, slowly stirring, adjusting the pH value to about 7-9 after the acrylamide is completely dissolved, and adjusting the temperature of the solution to 15-25 ℃. Pouring the solution into a polymerization bottle, introducing nitrogen for 30min, adding an initiator, an oxidant, a reducing agent, a stabilizer and a chelating agent, and reacting for 6-10 h. After the reaction is completed, the reaction sample is crushed and added with alkaline compound, and the temperature is raised to 80-90 ℃ for reaction for 2-6 h. Taking out the product obtained by the reaction, and then drying, crushing and sieving the product to obtain a white powdery polymer sample, wherein the structure of the white powdery polymer sample is shown as a formula (III).
In the formula (III), n is 75000-230000, m is 19000-74000, p is 1000-4000, n, m and p are integers.
The fifth purpose of the invention is to provide an application of the polyacrylamide or the polyacrylamide obtained by the preparation method in a polymer oil displacement agent.
The invention has the following beneficial effects:
according to the preparation method of the heat-resistant and salt-resistant polyacrylamide for oil displacement, provided by the invention, the heat-resistant and salt-resistant performance of the polyacrylamide for oil displacement is improved by introducing new functional monomers, auxiliary agents and optimizing a polymerization process. According to the invention, the benzene ring is introduced into the side chain of the polyacrylamide, so that the chain link strength is improved, and the temperature resistance and salt resistance of the polymer are enhanced; meanwhile, the introduced anionic group sulfonic acid group and polar group amide group increase the water solubility of the polymer, and the sulfonic acid group also enhances the temperature resistance and salt resistance; meanwhile, the ketone group and the alkyl group at the tail end of the chain have the functions of inhibiting hydrolysis and improving stability, so that the temperature resistance and the salt resistance are further improved. The apparent viscosity of the polymer solution is more than 14 mPa.s at 90 ℃ and 10000-50000 mg/L of salt concentration. The polyacrylamide provided by the invention has excellent temperature resistance and salt resistance, and lays a good foundation for realizing the use in a high-temperature and high-salt oil reservoir.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The test instruments and test conditions used in the examples are as follows:
apparent viscosity test: the polymer was dissolved with different concentrations of mineralized water to prepare a 1500mg/mL solution. After the solution is fully dissolved, taking a part of the solution, carrying out polymer solution viscosity measurement by using a DV-III Ultra type programmable rheometer, shaking the solution to be measured uniformly, opening an instrument water bath device, constantly stabilizing the temperature by 90 ℃, taking 20mL by a dosage cylinder approximately, pouring the solution into a cleaned and dried cylindrical sample container, starting measurement after the solution is completely soaked and bubbles in the sample container are removed, and taking the average value of three measurements. The fixed rotation speed is 6r/min.
Solubility test: a polymer solution with a polymer concentration of 1500mg/L was prepared with 5000mg/L mineralized water and stirred with an IKARW20 mechanical stirrer until it was sufficiently dissolved, without any significant particles in the solution. The dissolution time was recorded. The stirring speed was 500r/min.
The sources of the raw materials used in the examples are as follows:
4, 4-dimethyl-2-phenyl-1-penten-3-one, chongqing FuTENG medical Co Ltd
Acrylonitrile, beijing Enoka technology Co.Ltd
Acetic anhydride, nanjing chemical reagent Co., ltd
Para-toluene sulfonic acid, beijing Enoka technology Co., ltd
Oleum, lubao Chemicals Co.Ltd
Sodium carbonate, national medicine group chemical reagent Co., ltd
Sodium hydroxide, national medicine group chemical Co., ltd
Acetone, national medicine group chemical reagent Co., ltd
Acrylamide, shandong Ten thousand Chenghe New Material Co., ltd
Azodiisobutyl hydrochloride VA-044, guangzhou Heda New Material Co., ltd
Ammonium persulfate, national medicine group chemical reagent Co., ltd
Sodium bisulphite, national medicine group chemical reagent Co., ltd
Thiourea, national medicine group chemical reagent Co., ltd
Disodium ethylenediamine tetraacetate EDTA-2Na, national medicine group chemical Co., ltd.
Example 1
Preparation of acrylamide compound:
42.4g of acrylonitrile, 18.8g of 4, 4-dimethyl-2-phenyl-1-penten-3-one, 4g of acetic anhydride and 4.89g of p-toluenesulfonic acid were charged at room temperature in a four-necked flask equipped with a mechanical stirrer, thermometer, constant pressure funnel and reflux condenser. 12.2g oleum (20%) was slowly added at 3℃and kept at low temperature for 1h, then warmed to 50℃for 6h. A white solid formed, the reaction was stopped and allowed to stand for 24h. After filtration, the mixture was washed 2 times with acrylonitrile-water and 2 times with acetone. Drying in a vacuum oven at 50 ℃ for 6 hours to obtain a white powdery sample, and analyzing by infrared spectrum and nuclear magnetic resonance hydrogen spectrum test results to obtain a sample with the structural formula:
preparation of polyacrylamide:
2g of the synthesized functional acrylamide compound monomer is completely dissolved by 78g of water in a beaker, 20g of Acrylamide (AM) is added, and after the AM is slowly stirred and completely dissolved, a NaOH solution with the mass percent concentration of 20% is adopted to adjust the pH value to 7.5. Pouring the solution into a polymerization bottle, introducing nitrogen for 30min, adding 6.6mgVA-044 and 0.66mgNaHSO 3 、1.1mg(NH 4 ) 2 S 2 O 8 1.1mg EDTA-2Na and 0.22g thiourea, the reaction was initiated at 15℃for 8h. After the reaction was completed, the reaction sample was crushed and 2.815g of NaOH (prepared as a 30% by mass aqueous solution and then added) was added thereto, and the temperature was raised to 90℃for 2 hours. The product obtained by the reaction is taken out and dried in an oven at 50 ℃ for 9 hours. Then crushing and sieving to obtain a white powdery polymer sample, and testing the infrared spectrum and the nuclear magnetic resonance hydrogen spectrum to obtain the polyacrylamide with the structural formula:
wherein n is 75000 to 230000, m is 19000 to 74000, p is 1000 to 4000, and n, m and p are integers.
Example 2
The monomer synthesis was the same as in example 1.
Then, 1g of the synthesized acrylamide functional monomer (temperature-resistant and salt-resistant monomer) is completely dissolved in a beaker by 79g of water, 20g of acrylamide is added, and after AM is slowly stirred and completely dissolved, a NaOH solution with the mass percent concentration of 20% is adopted to adjust the pH value to 7.5. Pouring the solution into a polymerization bottle, introducing nitrogen for 30min, adding 6.6mgVA-044 and 0.66mgNaHSO 3 、1.1mg(NH 4 ) 2 S 2 O 8 1.1mg EDTA-2Na and 0.22g thiourea, the reaction was initiated at 15℃for 8h. After the reaction was completed, the reaction sample was crushed and 2.815g of NaOH (prepared as a 30% by mass aqueous solution and then added) was added thereto, and the temperature was raised to 90℃for 2 hours. The product obtained by the reaction is taken out and dried in an oven at 50 ℃ for 9 hours. Then crushing and sieving to obtain a white powdery polymer sample, wherein the structural formula of the obtained polyacrylamide is the same as that of the example 1.
Example 3
The monomer synthesis was the same as in example 1.
And then, 3g of the synthesized functional acrylamide compound monomer is completely dissolved by 77g of water in a beaker, 20g of acrylamide is added, and after AM is slowly stirred and completely dissolved, a NaOH solution with the mass percent concentration of 20% is adopted to adjust the pH value to 9. Pouring the solution into a polymerization bottle, introducing nitrogen for 30min, adding 6.6mgVA-044 and 0.66mgNaHSO 3 、1.1mg(NH 4 ) 2 S 2 O 8 1.1mg EDTA-2Na and 0.22g thiourea, the reaction was initiated at 15℃for 6h. After the reaction was completed, the reaction sample was crushed and 2.815g of NaOH (prepared as a 30% by mass aqueous solution and then added) was added thereto, and the temperature was raised to 90℃for 2 hours. The product obtained by the reaction is taken out and dried in an oven at 50 ℃ for 9 hours. Then crushing and sieving to obtain a white powdery polymer sample, wherein the structural formula of the obtained polyacrylamide is the same as that of the example 1.
Example 4
The monomer synthesis was the same as in example 1.
Then 2g of the synthesized functional acrylamide compound monomer (temperature-resistant and salt-resistant monomer)Body) was completely dissolved with 79g of water, 20g of acrylamide was added, and after complete dissolution of AM was achieved by slow stirring, the pH was adjusted to 8 with a 20% NaOH solution in mass percent. Pouring the solution into a polymerization bottle, introducing nitrogen for 30min, adding 6.6mgVA-044 and 0.44mgNaHSO 3 、0.88mg(NH 4 ) 2 S 2 O 8 (0.004% wt), 1.1mg EDTA-2Na and 0.22g thiourea, the temperature at which the reaction was initiated was 15℃and reacted for 8 hours. After the reaction was completed, the reaction sample was crushed and 2.815g of NaOH (prepared as a 30% by mass aqueous solution and then added) was added thereto, and the temperature was raised to 90℃for 2 hours. The product obtained by the reaction is taken out and dried in an oven at 50 ℃ for 9 hours. Then crushing and sieving to obtain a white powdery polymer sample, wherein the structural formula of the obtained polyacrylamide is the same as that of the example 1.
Example 5
The monomer synthesis was the same as in example 1.
Then 2g of the synthesized functional monomer of the acrylamide compound (heat-resistant and salt-resistant monomer) is completely dissolved by 78g of water in a beaker, 20g of acrylamide is added, and after AM is completely dissolved by slow stirring, the pH value is regulated to 7 by adopting a NaOH solution with the mass percentage concentration of 20%. Pouring the solution into a polymerization bottle, introducing nitrogen for 30min, adding 4.4mgVA-044 and 0.22mgNaHSO 3 、0.44mg(NH 4 ) 2 S 2 O 8 1.1mg EDTA-2Na and 0.22g thiourea, the reaction was initiated at 15℃for 10h. After the reaction was completed, the reaction sample was crushed and 2.815g of NaOH (prepared as a 30% by mass aqueous solution and then added) was added thereto, and the temperature was raised to 90℃for 2 hours. The product obtained by the reaction is taken out and dried in an oven at 50 ℃ for 9 hours. Then crushing and sieving to obtain a white powdery polymer sample, wherein the structural formula of the obtained polyacrylamide is the same as that of the example 1.
Example 6
The monomer synthesis was the same as in example 1.
Then 2g of the synthesized functional monomer of the acrylamide compound (heat-resistant and salt-resistant monomer) is completely dissolved by 78g of water in a beaker, 20g of acrylamide is added, and after AM is completely dissolved by slow stirring, the pH value is regulated to 7.5 by adopting a NaOH solution with the mass percentage concentration of 20 percent. The above-mentioned materials are mixedPouring the solution into a polymerization bottle, introducing nitrogen for 30min, adding 6.6mgVA-044 and 0.66mgNaHSO 3 、1.1mg(NH 4 ) 2 S 2 O 8 1.1mg EDTA-2Na and 0.22g thiourea, the reaction was initiated at 20℃for 8h. After the reaction was completed, the reaction sample was crushed and 2.815g of NaOH (prepared as a 30% by mass aqueous solution and then added) was added thereto, and the temperature was raised to 90℃for 2 hours. The product obtained by the reaction is taken out and dried in an oven at 50 ℃ for 9 hours. Then crushing and sieving to obtain a white powdery polymer sample, wherein the structural formula of the obtained polyacrylamide is the same as that of the example 1.
Example 7
The monomer synthesis was the same as in example 1.
Then 2g of the synthesized functional monomer of the acrylamide compound (heat-resistant and salt-resistant monomer) is completely dissolved by 78g of water in a beaker, 20g of acrylamide is added, and after AM is completely dissolved by slow stirring, the pH value is regulated to 7.5 by adopting a NaOH solution with the mass percentage concentration of 20 percent. Pouring the solution into a polymerization bottle, introducing nitrogen for 30min, adding 8.8mgVA-044 and 0.66mgNaHSO 3 、1.1mg(NH 4 ) 2 S 2 O 8 1.1mg EDTA-2Na and 0.22g thiourea, the reaction temperature was 25℃and the reaction time was 8 hours. After the reaction was completed, the reaction sample was crushed and 3.04g of NaOH (prepared as a 30% by mass aqueous solution and then added) was added thereto, and the temperature was raised to 90℃for 2 hours. The product obtained by the reaction is taken out and dried in an oven at 50 ℃ for 9 hours. Then crushing and sieving to obtain a white powdery polymer sample, wherein the structural formula of the obtained polyacrylamide is the same as that of the example 1.
Example 8
The monomer synthesis was the same as in example 1.
Then 2g of the synthesized functional monomer of the acrylamide compound (heat-resistant and salt-resistant monomer) is completely dissolved by 78g of water in a beaker, 20g of acrylamide is added, and after AM is completely dissolved by slow stirring, the pH value is regulated to 7.5 by adopting a NaOH solution with the mass percentage concentration of 20 percent. Pouring the solution into a polymerization bottle, introducing nitrogen for 30min, adding 6.6mgVA-044 and 0.66mgNaHSO 3 、1.1mg(NH 4 ) 2 S 2 O 8 1.1mg EDTA-2Na and 0.22g of thiourea, the initiation reaction temperature is 20 ℃, and the reaction time is 8 hours. After the reaction was completed, the reaction sample was crushed and 2.575g of NaOH (prepared as a 30% by mass aqueous solution and then added) was added thereto, and the temperature was raised to 90℃for 2 hours. The product obtained by the reaction is taken out and dried in an oven at 50 ℃ for 9 hours. Then crushing and sieving to obtain a white powdery polymer sample, wherein the structural formula of the obtained polyacrylamide is the same as that of the example 1.
Example 9
The monomer synthesis was the same as in example 1.
Then 2g of the synthesized functional monomer of the acrylamide compound (heat-resistant and salt-resistant monomer) is completely dissolved by 78g of water in a beaker, 20g of acrylamide is added, and after AM is completely dissolved by slow stirring, saturated Na is adopted 2 CO 3 The pH of the solution was adjusted to 7.5. Pouring the solution into a polymerization bottle, introducing nitrogen for 30min, adding 6.6mgVA-044 and 1.1mgNaHSO 3 、2.2mg(NH 4 ) 2 S 2 O 8 1.1mg EDTA-2Na and 0.22g thiourea, the reaction temperature was brought to 20℃and the reaction was carried out for 8 hours. After the reaction was completed, the reaction sample was crushed and 2.815g of NaOH (prepared as a 30% by mass aqueous solution and then added) was added thereto, and the temperature was raised to 90℃for 2 hours. The product obtained by the reaction is taken out and dried in an oven at 50 ℃ for 9 hours. And then crushing and sieving to obtain a white powdery polymer sample, wherein the structural formula of the obtained polyacrylamide is the same as that of example 1, and the structural formula of the obtained polyacrylamide is the same as that of example 1.
Example 10
The monomer synthesis was the same as in example 1.
Then 2g of the synthesized functional monomer of the acrylamide compound (temperature-resistant and salt-resistant monomer) is completely dissolved by 78g of water in a beaker, 20g of acrylamide is added, and after AM is completely dissolved by slow stirring, the pH value is regulated to 7.5 by adopting saturated sodium bicarbonate solution. Pouring the solution into a polymerization bottle, introducing nitrogen for 30min, adding 6.6-mgV-50 and 0.66mgNa 2 SO 3 、1.1mgNa 2 S 2 O 8 1.1mg EDTA-2Na and 0.22g sodium dithionite, the initiation reaction temperature was 20℃and the reaction time was 8 hours. After the reaction was completed, the reaction sample was crushed and 2.815g of NaOH was added (prepared to a mass concentrationAfter 30% aqueous solution), the temperature was raised to 90℃and the reaction was carried out for 2 hours. The product obtained by the reaction is taken out and dried in an oven at 50 ℃ for 9 hours. Then crushing and sieving to obtain a white powdery polymer sample, wherein the structural formula of the obtained polyacrylamide is the same as that of the example 1.
Comparative example 1
2g of AMPS (2-acrylamido-2-methylpropanesulfonic acid) are completely dissolved in a beaker with 78g of water, 20g of acrylamide are added, after slow stirring until AM is completely dissolved, the pH value is adjusted to 7.5 by using a NaOH solution with the mass percentage concentration of 20%. Pouring the solution into a polymerization bottle, introducing nitrogen for 30min, adding 6.6mgVA-044 and 0.66mgNaHSO 3 No. 1.1mg (NH) 4 ) 2 S 2 O 8 1.1mg EDTA-2Na and 0.22g thiourea, the reaction was initiated at 15℃for 8h. After the reaction was completed, the reaction sample was crushed and 2.815g of NaOH (prepared as a 30% by mass aqueous solution and then added) was added thereto, and the temperature was raised to 90℃for 2 hours. The product obtained by the reaction is taken out and dried in an oven at 50 ℃ for 9 hours. And then crushing and sieving to obtain a white powdery polymer sample.
Comparative example 2
After adding 20g of acrylamide and 80g of water in a reflux condenser equipped with a mechanical stirrer, a thermometer and slowly stirring until AM is completely dissolved, the pH value is adjusted to 7.5 by adopting a NaOH solution with the mass percent concentration of 20%. Pouring the solution into a polymerization bottle, introducing nitrogen for 30min, adding 6.6mgVA-044 and 0.66mgNaHSO 3 、1.1mg(NH 4 ) 2 S 2 O 8 1.1mg EDTA-2Na and 0.22g thiourea, the reaction was initiated at 15℃for 8h. After the reaction was completed, the reaction sample was crushed and 2.815g of NaOH (prepared as a 30% by mass aqueous solution and then added) was added thereto, and the temperature was raised to 90℃for 2 hours. The product obtained by the reaction is taken out and dried in an oven at 50 ℃ for 9 hours. And then crushing and sieving to obtain a white powdery polymer sample.
Preparing polymer solution with polymer concentration of 1500mg/L by mineralized water with different concentrations (the concentration is 10000mg/L to 50000 mg/L); the apparent viscosity of the polymer solution was measured at 90℃and the viscosity retention was calculated. A polymer solution having a polymer concentration of 1500mg/L was prepared with 5000mg/L of mineralized water, and the dissolution rate of the polymer was measured at 30℃and the test results are shown in Table 1.
TABLE 1 test results of polyacrylamide obtained in examples and comparative examples
As can be seen from the results in Table 1, the apparent viscosity of the polymer solution of the polyacrylamide provided by the invention is at least 14.2 mPas at 90 ℃ and with a salt concentration of 50000mg/L, which is far greater than that of the polyacrylamide provided by comparative examples 1 and 2, and the polyacrylamide provided by the invention has more excellent temperature resistance and salt resistance. In addition, the dissolution time of the polymers obtained in examples 1-10 is less than or equal to 2h, and the technical requirements specified in polyacrylamide Q/SH1020 1572 2017 for oil displacement are met.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (17)
1. The acrylamide compound is characterized by having the following structural formula:
formula (I)
The acrylamide compound is obtained after the components comprising the compound of the formula (II), the acrylonitrile and the sulfonating agent react; acid anhydride compounds are also added in the reaction;
formula (II).
2. A process for producing an acrylamide compound as defined in claim 1, which comprises reacting a compound comprising the formula (II), acrylonitrile and a sulfonating agent to give said acrylamide compound
Formula (II).
3. The method according to claim 2, wherein,
the molar ratio of the compound of the formula (II), the acrylonitrile and the sulfonating agent is (0.5-3): (4-15): 1, a step of; and/or the number of the groups of groups,
the sulfonating agent is at least one selected from fuming sulfuric acid, sulfur trioxide, chlorosulfonic acid, sulfur dioxide and chlorine gas, sulfur dioxide and oxygen, and sulfur trioxide pyridine; and/or the number of the groups of groups,
the reaction conditions are as follows: reacting for 0.5-5 h at the temperature of 5-10 ℃, and heating to 30-60 ℃ for reacting for 1-24 h; and/or the number of the groups of groups,
an anhydride compound and a catalyst are also added in the reaction; and/or the number of the groups of groups,
the product obtained by the reaction also needs to be subjected to standing, washing and drying treatment.
4. A process according to claim 3, wherein,
the molar ratio of the compound of the formula (II), the acrylonitrile and the sulfonating agent is (0.8-1.2): (6-10): 1, a step of; and/or the number of the groups of groups,
the sulfonating agent is fuming sulfuric acid with the concentration of 10-40%; and/or the number of the groups of groups,
the reaction conditions are as follows: reacting for 1-2 hours at 0-5 ℃, and heating to 40-50 ℃ for reacting for 5-10 hours.
5. A process according to claim 3, wherein,
the anhydride compound is selected from acetic anhydride; and/or the number of the groups of groups,
the catalyst is at least one selected from p-toluenesulfonic acid and phosphoric acid; and/or the number of the groups of groups,
the amount of the anhydride compound is 1-50 parts by weight based on 100 parts by weight of the sulfonating agent; and/or the number of the groups of groups,
the catalyst is used in an amount of 1-25 parts by weight based on 100 parts by weight of the total mass of the compound shown in the formula (II) and acrylonitrile; and/or the number of the groups of groups,
the standing condition is that the standing is carried out for 3-48 hours at the temperature of 10-40 ℃; and/or the number of the groups of groups,
the solvent used for washing is at least one selected from acrylonitrile, acetone, N-dimethylformamide, anhydrous methanol and water; and/or the number of the groups of groups,
the drying temperature is 20-60 ℃; the drying time is 3-24 hours.
6. The method according to claim 5, wherein,
the amount of the anhydride compound is 1-25 parts by weight based on 100 parts by weight of the sulfonating agent; and/or the number of the groups of groups,
the catalyst is used in an amount of 1-15 parts by weight based on 100 parts by weight of the total mass of the compound shown in the formula (II) and acrylonitrile; and/or the number of the groups of groups,
the standing condition is that the standing is carried out for 8-24 hours at 20-35 ℃; and/or the number of the groups of groups,
the solvent used for washing is at least one selected from acrylonitrile/water and acetone; and/or the number of the groups of groups,
the drying temperature is 40-55 ℃; the drying time is 4-10 h.
7. A polyacrylamide prepared from the acrylamide compound according to claim 1 or the acrylamide compound and the acrylamide obtained by the preparation method according to any one of claims 2 to 6.
8. A method for preparing the polyacrylamide according to claim 7, which comprises the steps of reacting the components comprising the acrylamide compound and the acrylamide to obtain the polyacrylamide.
9. The preparation method according to claim 8, characterized in that the preparation method specifically comprises the following steps:
step 1) dissolving the acrylamide compound into water, and adding acrylamide;
step 2) adding a pH regulator;
step 3) adding an initiator, an oxidant, a reducing agent, a chelating agent and a stabilizing agent into the solution obtained in the step 2), and then heating for reaction;
and step 4) crushing the solid obtained in the reaction in the step 3), adding an alkaline compound, and heating for reaction to obtain the polyacrylamide.
10. The method according to claim 9, wherein,
the pH regulator is selected from alkaline compounds; and/or the number of the groups of groups,
the initiator is selected from azo compounds; and/or the number of the groups of groups,
the oxidant is at least one selected from persulfates and peroxides; and/or the number of the groups of groups,
the reducing agent is at least one selected from sulfite compounds and sulfate compounds; and/or the number of the groups of groups,
the stabilizer is at least one selected from thiourea, sodium dithionite, guanidine acetate, sodium sulfite and sodium 2-mercaptobenzothiazole; and/or the number of the groups of groups,
the chelating agent is at least one selected from disodium ethylenediamine tetraacetate, ethylenediamine, 2-bipyridine, diethylenetriamine pentaacetic acid and salts thereof; and/or the number of the groups of groups,
the basic compound in step 4) is selected from inorganic basic compounds.
11. The method according to claim 9, wherein,
the pH regulator is at least one selected from sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium acetate and ammonia water; and/or the number of the groups of groups,
the initiator is at least one selected from azodiisobutylamidine hydrochloride, azodiiso Ding Mi hydrochloride and azodiisopropyl imidazoline; and/or the number of the groups of groups,
the oxidant is at least one selected from potassium persulfate, sodium persulfate, ammonium persulfate and tert-butyl hydroperoxide; and/or the number of the groups of groups,
the reducing agent is at least one selected from sodium sulfite, sodium bisulphite and ferrous ammonium sulfate; and/or the number of the groups of groups,
the chelating agent is disodium ethylenediamine tetraacetate; and/or the number of the groups of groups,
the alkaline compound in the step 4) is at least one selected from sodium hydroxide, sodium carbonate and potassium hydroxide.
12. The method according to claim 9, wherein,
in the step 1), the mass ratio of the acrylamide compound to the acrylamide to the water is 1: (3-30): (10-90); and/or the number of the groups of groups,
in the step 3), the initiator is added in an amount of 0.01-0.5 part, the oxidant is added in an amount of 0.001-0.05 part, the reducing agent is added in an amount of 0.001-0.05 part, the stabilizer is added in an amount of 0.1-3 parts, and the chelating agent is added in an amount of 0.001-0.03 part based on 100 parts by weight of the acrylamide compound and the acrylamide; and/or the number of the groups of groups,
and 5-20 parts of the alkaline compound in the step 4) based on 100 parts by weight of the acrylamide.
13. The method according to claim 12, wherein,
in the step 1), the mass ratio of the acrylamide compound to the acrylamide to the water is 1: (5-20): (20-90); and/or the number of the groups of groups,
in the step 3), the initiator is added in an amount of 0.01-0.2 part, the oxidant is added in an amount of 0.002-0.02 part, the reducing agent is added in an amount of 0.001-0.01 part, the stabilizer is added in an amount of 0.5-2 parts, and the chelating agent is added in an amount of 0.001-0.01 part based on 100 parts by weight of the acrylamide compound and the acrylamide; and/or the number of the groups of groups,
and based on 100 parts by weight of the acrylamide, the addition amount of the alkaline compound in the step 4) is 10-16 parts.
14. The method according to claim 9, wherein,
adding a pH regulator into the step 2) to regulate the pH to 5-10; and/or the number of the groups of groups,
the reaction temperature in the step 3) is 10-40 ℃; the reaction time is 1-12 h; and/or the number of the groups of groups,
the reaction in the step 3) is carried out in an inert gas environment; and/or the number of the groups of groups,
the reaction temperature in the step 4) is 60-90 ℃; the reaction time is 2-12 h; and/or the number of the groups of groups,
the polyacrylamide obtained in step 4) also requires a drying treatment.
15. The method of claim 14, wherein the process comprises,
adding a pH regulator into the step 2) to regulate the pH to 7-9; and/or the number of the groups of groups,
the reaction temperature in the step 3) is 15-25 ℃; the reaction time is 6-10 h; and/or the number of the groups of groups,
the reaction temperature in the step 4) is 80-90 ℃; the reaction time is 2-6 hours; and/or the number of the groups of groups,
the drying temperature is 30-70 ℃; the drying time is 1-12 h.
16. The method according to claim 15, wherein,
the drying temperature is 40-55 ℃; the drying time is 4-9 h.
17. Use of the polyacrylamide according to claim 7 or the polyacrylamide obtained by the preparation method according to any one of claims 8 to 16 in a polymer oil displacement agent.
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| CN1470504A (en) * | 2003-06-07 | 2004-01-28 | 石油大学(华东) | Functional monomer compound for preparing acrylamide derivatives |
| CN102050913A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Temperature and salt resistant grafted polyacrylamide and preparation method thereof |
| CN102304201A (en) * | 2011-05-27 | 2012-01-04 | 中国海洋石油总公司 | Hydrophobic association crosslinked polymer coil and preparation method thereof |
| CN104628942A (en) * | 2013-11-15 | 2015-05-20 | 中国石油化工股份有限公司 | Acrylamide copolymer, as well as preparation method and application thereof |
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| CN1470504A (en) * | 2003-06-07 | 2004-01-28 | 石油大学(华东) | Functional monomer compound for preparing acrylamide derivatives |
| CN102050913A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Temperature and salt resistant grafted polyacrylamide and preparation method thereof |
| CN102304201A (en) * | 2011-05-27 | 2012-01-04 | 中国海洋石油总公司 | Hydrophobic association crosslinked polymer coil and preparation method thereof |
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