CN104650301A - Acrylamide copolymer and its preparation method and use - Google Patents
Acrylamide copolymer and its preparation method and use Download PDFInfo
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- CN104650301A CN104650301A CN201310574918.2A CN201310574918A CN104650301A CN 104650301 A CN104650301 A CN 104650301A CN 201310574918 A CN201310574918 A CN 201310574918A CN 104650301 A CN104650301 A CN 104650301A
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- 229920006322 acrylamide copolymer Polymers 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims description 16
- 239000000178 monomer Substances 0.000 claims description 93
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 238000006460 hydrolysis reaction Methods 0.000 claims description 25
- 239000003999 initiator Substances 0.000 claims description 25
- 230000007062 hydrolysis Effects 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 125000001118 alkylidene group Chemical group 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 9
- 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 claims description 9
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 230000002829 reductive effect Effects 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- 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 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-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
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 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
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 2
- 235000019252 potassium sulphite Nutrition 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 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
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 2
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 31
- 239000000243 solution Substances 0.000 description 27
- 239000000693 micelle Substances 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 230000001404 mediated effect Effects 0.000 description 8
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 7
- 150000003926 acrylamides Chemical class 0.000 description 7
- 238000006392 deoxygenation reaction Methods 0.000 description 7
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- -1 isobutyl- Chemical group 0.000 description 7
- 238000012216 screening Methods 0.000 description 7
- 238000009818 secondary granulation Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 239000012267 brine Substances 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 5
- 229920002401 polyacrylamide Polymers 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 229940048053 acrylate Drugs 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 0 CC*(C)C(C(C)(*)C(*C)NC)=C Chemical compound CC*(C)C(C(C)(*)C(*C)NC)=C 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- QFHMNFAUXJAINK-UHFFFAOYSA-N [1-(carbamoylamino)-2-methylpropyl]urea Chemical group NC(=O)NC(C(C)C)NC(N)=O QFHMNFAUXJAINK-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000007601 warm air drying Methods 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses an acrylamide copolymer. The acrylamide copolymer contains a structural unit A, a structural unit B and a structural unit C. The structural unit A has a structure shown in the formula (1). The structural unit B has at least one structure shown in the formulas (1), (2), (3), (4) or (5). The structural unit C has a structure shown in the formula (6). A mass ratio of the structural unit A, B to C is 1: 0.001-3: 0.001-0.5. The viscosity-average molecular weight of the acrylamide copolymer is in a range of 27 million to 32 million. The acrylamide copolymer has high molecular weight and apparent viscosity and can be used as a high-temperature high-salt oil reservoir tertiary recovery oil displacement agent.
Description
Technical field
The present invention relates to a kind of acrylamide copolymer and its preparation method and application.
Background technology
Polymer flooding mainly by injecting the polymers soln of certain scale, increases displacing fluid viscosity, reduces oil-reservoir water phase permeability and reduces mobility ratio, adjustment intake profile, to reach the object improving sweeping phase volume, and then improve recovery ratio.As main polymer oil-displacing agent, partially hydrolyzed polyacrylamide (HPAM), in conventional oil reservoir tertiary oil recovery (EOB) technology, has obtained large-scale promotion and application, for oilfield stable production and volume increase have played vital role.Along with the minimizing of conventional reservoir reserve, high temperature and high salt oil deposit makes the application of HPAM be faced with many difficult problems, the compound action that in high temperature, high salt and solution when being mainly reflected in exploitation high temperature and high salt oil deposit, dissolved oxygen produces makes HPAM soltion viscosity significantly reduce, and causes HPAM oil displacement efficiency not remarkable.Research shows, when temperature is higher than 70 DEG C, the amido hydrolysis reaction of HPAM generates carboxyl significantly to be aggravated, and when degree of hydrolysis reaches more than 40%, carboxyl is just easy to and Ca in solution
2+, Mg
2+ion generates precipitation, and soltion viscosity is lost.In addition, at high temperature, when there is dissolved oxygen in oxygen and solution in air, main polymer chain also can be caused to rupture soltion viscosity is significantly declined.
In order to improve the temperature resistant antisalt performance of polyacrylamide, carry out a large amount of tackling key problem research both at home and abroad, the main chain yardstick around polymkeric substance, chain size distribution, construction unit composition, micro-sequential structure carry out a large amount of correlative study work, as temperature resistant antisalt monomer-polymer, hydrophobic associated polymer, amphiphilic polymers, composite polymer, comb shaped polymer, template polymer and surface-active polymer etc.As being entitled as " the low temperature synthesis of AMPS/AM multipolymer and performance " (Chang Zhiying, polymer material science and engineering, 1997,13,16) with acrylamide (AM) and heat-resistant salt-resistant monomer 2-acrylamide-2-methylpro panesulfonic acid (AMPS) copolymerization copolymer in article; CN200810015349.7 discloses a kind of comb-type structure activity polymer and preparation technology thereof and application, is synthesized have tackifying and reduce interfacial tension target product by monomer copolymerizations such as polyurethanes surface-active macromonomer and acrylamides.Its feature of each tool of polymkeric substance that above-mentioned two kinds of methods obtain, in some performance as more traditional polyacrylamide in temperature tolerance, salt resistance, shear resistant and surfactivity index increases really, but it obtains molecular weight of product little (being no more than 2,000 ten thousand), causes the use of polymkeric substance to be restricted.
Summary of the invention
The object of the invention is to the above-mentioned defect overcoming prior art, a kind of acrylamide copolymer and its preparation method and application is provided.
The invention provides a kind of acrylamide copolymer, this acrylamide copolymer contains structural unit A, structural unit B and structural unit C, wherein, described structural unit A is for having the unit of structure shown in formula (1), described structural unit B is for having at least one in the unit of structure shown in formula (2)-Shi (5), described structural unit C is for having the unit of structure shown in formula (6), and the mass ratio of described structural unit A, described structural unit B and described structural unit C is 1:0.001-3:0.001-0.5, be preferably 1:0.01-1.5:0.01-0.2; The viscosity-average molecular weight of described acrylamide copolymer is 2,700 ten thousand-3,200 ten thousand, is preferably 2,900 ten thousand-3,100 ten thousand,
Wherein, R
1, R
2, R
6, R
7, R
10and R
11be the alkyl of hydrogen or C1-C4 independently of one another, R
3for the alkylidene group of C1-C14; R
4, R
5, R
8and R
9be the alkyl of C1-C4 independently of one another, R
12for the alkyl of C1-C14, M
1for at least one in H, Na and K, n is arbitrary integer in 1-20, and x, y and z are the arbitrary integer in 1-5 independently of one another.
Present invention also offers a kind of preparation method of acrylamide copolymer, this preparation method comprises the following steps, under solution polymerization condition, under initiator exists, a kind of monomer mixture is made to carry out polyreaction in water, wherein, described monomer mixture contains monomer E, monomer F and monomer G, described monomer E is for having the monomer of structure shown in formula (8), described monomer F is for having at least one in the monomer of structure shown in formula (9)-Shi (12), described monomer G is for having the monomer of structure shown in formula (13), and described monomer E, the mass ratio of described monomer F and described monomer G is 1:0.001-3:0.001-0.5, be preferably 1:0.01-1.5:0.01-0.2, after described solution polymerization condition makes polyreaction, the viscosity-average molecular weight of resulting polymers is 2,700 ten thousand-3,200 ten thousand, is preferably 2,900 ten thousand-3,100 ten thousand,
Wherein, R
1', R
2', R
6', R
7', R
10' and R
11' be the alkyl of hydrogen or C1-C4 independently of one another, R
3' be the alkylidene group of C1-C14; R
4', R
5', R
8' and R
9' be the alkyl of C1-C4 independently of one another, R
12' be the alkyl of C1-C14, M
3for at least one in H, Na and K, n ' is integer arbitrary in 1-20, and x ', y ' and z ' are the arbitrary integer in 1-5 independently of one another.
The main chain of the molecular chain of acrylamide copolymer of the present invention is formed primarily of acrylamide and temperature resistant antisalt monomeric building blocks, at guarantee polymeric water-soluble simultaneously, temperature resistant antisalt and the anti-shear performance of polymer molecule can be improved.Multipolymer side chain is made up of surface active function monomer, has and produces Interpolymer Association effect, increases the time of relaxation of molecular motion, improves solution visco-elasticity and reduces oil water interfacial tension effect.
The temperature resistant antisalt product of acrylamide based copolymer of the present invention is adopted to have good water solubility, residual monomer content is low and molecular weight is high feature.Acrylamide copolymer molecular weight of the present invention can reach more than 3,000 ten thousand, particularly under salinity 32000mg/L, the hot conditions of 95 DEG C, the apparent viscosity of solution can reach more than 22mPa.s, and the molecular weight of commercially available high molecular weight polyacrylamide is only about 2,000 ten thousand, the apparent viscosity of solution is only 8.9mPa.s, comparatively commercially available prod, acrylamide copolymer of the present invention has significantly thickening advantage, can as high temperature and high salt oil deposit Flooding Agent for EOR.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of acrylamide copolymer, this acrylamide copolymer contains structural unit A, structural unit B and structural unit C, wherein, described structural unit A is for having the unit of structure shown in formula (1), described structural unit B is for having at least one in the unit of structure shown in formula (2)-Shi (5), described structural unit C is for having the unit of structure shown in formula (6), and the mass ratio of described structural unit A, described structural unit B and described structural unit C is 1:0.001-3:0.001-0.5, be preferably 1:0.01-1.5:0.01-0.2; The viscosity-average molecular weight of described acrylamide copolymer is 2,700 ten thousand-3,200 ten thousand, is preferably 2,900 ten thousand-3,100 ten thousand,
Wherein, R
1, R
2, R
6, R
7, R
10and R
11be the alkyl of hydrogen or C1-C4 independently of one another, R
3for the alkylidene group of C1-C14; R
4, R
5, R
8and R
9be the alkyl of C1-C4 independently of one another, R
12for the alkyl of C1-C14, M
1for at least one in H, Na and K, n is arbitrary integer in 1-20, and x, y and z are the arbitrary integer in 1-5 independently of one another.
In the present invention, the alkyl of described C1-C4 can be straight chain, also can be side chain.The example of the alkyl of described C1-C4 can comprise: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-and the tertiary butyl.
In the present invention, the alkyl of described C1-C14 can be straight chain, also can be side chain.The example of the alkyl of described C1-C14 can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, positive undecyl, positive dodecyl, positive tridecyl and positive tetradecyl.
In the present invention, the alkylidene group of described C1-C14 can be straight or branched, and the example of the alkylidene group of described C1-C14 can include but not limited to: methylene radical, ethylidene, sub-n-propyl, isopropylidene, sub-normal-butyl, sub-sec-butyl, isobutylidene and the sub-tertiary butyl, sub-n-pentyl, isopentylidene, sub-tert-pentyl, sub-neo-pentyl, sub-n-hexyl, sub-n-heptyl, sub-n-octyl, sub-n-nonyl, sub-positive decyl, sub-positive undecyl, sub-positive dodecyl, sub-positive tridecyl and the positive tetradecyl in Asia.Described alkylidene group refer to alkane lose two hydrogen atoms after residue, described two hydrogen atoms can be two hydrogen atoms on same carbon atom, also can two hydrogen atoms on different carbon atom, it can be straight chain, also can be side chain, such as, described ethylidene can be-CH
2cH
2-or-CH (CH
3)-.
In the present invention, although can realize object of the present invention as long as contain structural unit A, structural unit B and structural unit C and meet aforementioned proportion relation, under preferable case, the amount of structural unit A accounts for the 30-99 % by weight of described acrylamide copolymer.
According to the present invention, described acrylamide copolymer also contains structural unit D, described structural unit D for having the unit of structure shown in formula (7):
Wherein, M
2for potassium or sodium, be preferably sodium.
The quality of the present invention to structural unit D does not specially require, such as, preferably, the mass ratio of described structural unit A, described structural unit B, described structural unit C and described structural unit D is 1:0.001-3:0.001-0.5:0.1-1, more preferably 1:0.01-1.5:0.01-0.2:0.1-1.
The present inventor finds under study for action, can obtain good oil displacement efficiency good specific structural unit A, structural unit B, structural unit C and structural unit D when the quadripolymer be made up of is used for oil-displacing agent.Such as, preferably, described structural unit B is for having at least one in the unit of structure shown in formula (2) and (4), and R
2and R
7be hydrogen or methyl independently of one another; In described structural unit C, R
12for the alkyl of C5-C10, n is the arbitrary integer in 5-20, when x, y and z are the arbitrary integer in 1-3 independently of one another, can obtain good oil displacement efficiency when the quadripolymer of composition is used for oil-displacing agent.Still more preferably, described structural unit C is for having the unit of structure shown in formula (14):
Wherein, n is preferably the arbitrary integer in 8-12.
Present invention also offers a kind of preparation method of acrylamide copolymer, the method comprises the following steps, under solution polymerization condition, under initiator exists, a kind of monomer mixture is made to carry out polyreaction in water, wherein, described monomer mixture contains monomer E, monomer F and monomer G, described monomer E is for having the monomer of structure shown in formula (8), described monomer F is for having at least one in the monomer of structure shown in formula (9)-Shi (12), described monomer G is for having the monomer of structure shown in formula (13), and described monomer E, the mass ratio of described monomer F and described monomer G is 1:0.001-3:0.001-0.5, be preferably 1:0.01-1.5:0.01-0.2, after described solution polymerization condition makes polyreaction, the viscosity-average molecular weight of resulting polymers is 2,700 ten thousand-3,200 ten thousand, is preferably 2,900 ten thousand-3,100 ten thousand,
Wherein, R
1', R
2', R
6', R
7', R
10' and R
11' be the alkyl of hydrogen or C1-C4 independently of one another, R
3' be the alkylidene group of C1-C14; R
4', R
5', R
8' and R
9' be the alkyl of C1-C4 independently of one another, R
12' be the alkyl of C1-C14, M
3for at least one in H, Na and K, n ' is integer arbitrary in 1-20, and x ', y ' and z ' are the arbitrary integer in 1-5 independently of one another.
The alkyl of described C1-C4, the alkylidene group of C1-C14 are all identical with foregoing description with the alkyl of C1-C14.
In the present invention, monomer E is preferably the 40-99 % by weight of monomer mixture total mass.
The present inventor finds under study for action, when selecting specific monomer E, monomer F and monomer G to react, can improve the oil displacement efficiency of the polymkeric substance of gained further.Such as, preferably, when described monomer F is for having at least one in the monomer of structure shown in formula (9) and formula (11), and R
2' and R
7' be hydrogen or methyl independently of one another; In described monomer G, R
12' be the alkyl of C5-C10, n ' is the arbitrary integer in 5-20, and when x ', y ' and z ' are the arbitrary integer in 1-3 independently of one another, the polymkeric substance of synthesis has higher oil displacement efficiency, still more preferably, described monomer G is for having the monomer of structure shown in formula (15):
Wherein, n ' is preferably the arbitrary integer in 8-12.
According to the present invention, described solution polymerization carries out in water, when described solution polymerization starts, there is no particular limitation for the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture, can change in wider scope, under preferable case, the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture is 0.15-0.4:1, more preferably 0.2-0.3:1.
In the present invention, described initiator can be the various initiator in this area.Such as, described initiator can be selected from azo series initiators and/or redox body class initiator, is preferably azo series initiators and redox body class initiator.The consumption of described azo series initiators is the 0.0001-0.1 % by weight of the gross weight of monomer mixture, is preferably 0.001-0.05 % by weight; The consumption of described redox series initiators is the 0.0002-0.3 % by weight of the gross weight of monomer mixture, is preferably 0.002-0.15 % by weight.Described azo series initiators is preferably water-soluble azo series initiators, described redox series initiators comprises Oxidizing and Reducing Agents, described reductive agent is inorganic reducing agent and/or organic reducing agent, and the weight ratio of described oxygenant and described reductive agent is 0.1-1:1.
In the present invention, described water-soluble azo series initiators is preferably 2,2'-azo diisobutyl amidine dihydrochloride, 2,2'-azo [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride and 4, at least one in 4'-azo two (4-cyanopentanoic acid), more preferably 2,2'-azo diisobutyl amidine dihydrochlorides.
In the present invention, described oxygenant can be selected from least one in acyl peroxide, hydroperoxide and persulphate, be preferably benzoyl peroxide, hydrogen peroxide, tertbutyl peroxide, 2,5-dimethyl-2, at least one in 5 pairs of (hydrogen peroxide) hexanes, ammonium persulphate, Sodium Persulfate and Potassium Persulphates, is further preferably ammonium persulphate and/or Potassium Persulphate.
In the present invention, described reductive agent can be inorganic reducing agent and/or organic reducing agent, is preferably inorganic reducing agent and organic reducing agent.Described inorganic reducing agent can be selected from least one in ferrous sulfate, ferrous ammonium sulphate, cuprous chloride, potassium sulfite, S-WAT, ammonium bisulfite, Potassium hydrogen sulfite, Sulfothiorine, Potassium Thiosulphate, rongalite and sodium bisulfite, is preferably sodium bisulfite; Described organic reducing agent is preferably amine reductive agent, described amine reductive agent is preferably N, N-dimethylethanolamine, N, N-lupetazin, tetramethyl-urea, N, N – dimethyl-ethylenediamine and N, N, N ', at least one in N '-Tetramethyl Ethylene Diamine, more preferably N, N, N ', N '-Tetramethyl Ethylene Diamine.
According to the present invention, the condition of described solution polymerization can be the condition of this area routine.Such as, described solution polymerization carries out in the presence of an inert gas, and described polymeric reaction condition can comprise: temperature is-10 DEG C to 20 DEG C, preferably 5 DEG C to 15 DEG C; Time is 2-12 hour, preferred 4-8 hour; PH value is 4-12, is preferably 5-10.
Described rare gas element is the gas do not reacted with raw material and product, such as, can be at least one in the nitrogen of this area routine or the periodic table of elements in neutral element gas, be preferably nitrogen.
According to the present invention, described method also comprises and to be hydrolyzed by resulting polymers after polyreaction and dry.Those skilled in the art can know, and the process of hydrolysis comprises hydrolytic reagent and polymer reaction.By hydrolysis, some acrylamide structural unit and the structural unit shown in formula (1) are transformed into acrylate structural unit, that is, the structural unit shown in Chinese style of the present invention (7).
In the present invention, the condition of described hydrolysis is not particularly limited, and under preferable case, the condition of described hydrolysis comprises: temperature is 50-110 DEG C, is preferably 70-90 DEG C; Time is 0.5-6 hour, is preferably 1-4 hour; After described hydrolysis makes polyreaction, the degree of hydrolysis of resulting polymers can be 10-30%.
In the present invention, described degree of hydrolysis refers to that the mole number of acrylate structural unit accounts for the per-cent of the total mole number of the structural unit of acrylamide copolymer of the present invention.Described degree of hydrolysis is determined by the consumption of hydrolytic reagent of the present invention.
In the present invention, hydrolytic reagent is the various inorganic alkaline compounds that can realize above-mentioned purpose that this area is commonly used, and can be selected from least one in sodium hydroxide, potassium hydroxide and sodium carbonate.The consumption of described hydrolytic reagent can carry out appropriate selection according to the degree of hydrolysis of acrylamide copolymer, meet service requirements to make the degree of hydrolysis of acrylamide copolymer to be as the criterion, preferred inorganic alkaline compound consumption makes the degree of hydrolysis of acrylamide copolymer be 10-30%.
Those skilled in the art can know, and by regulating the consumption of inorganic alkaline compound, can obtain the acrylamide copolymer of different degree of hydrolysis.
In the present invention, the mole number of described inorganic alkaline compound equals the mole number of acrylate structural unit.
According to the present invention, the present invention is to drying conditions without particular requirement, and described drying means can adopt hot air seasoning, and described warm air drying temperature can be 40-120 DEG C, is preferably 70-90 DEG C; Time is 0.2-4 hour, is preferably 0.5-2 hour.
One of the present invention preferred embodiment in, the preparation method of described acrylamide copolymer comprises the steps:
(1) acrylamide monomer, temperature resistant antisalt monomer, surface active function monomer and water are mixed to form the comonomer aqueous solution, regulate pH to 5-10 with inorganic alkaline compound, control solution temperature-10 DEG C to 20 DEG C;
(2) in the comonomer aqueous solution, logical nitrogen carries out deoxygenation, controls oxygen level in solution and is less than 1mg/L, be preferably less than 0.2mg/L;
(3) under logical condition of nitrogen gas, add composite initiation system to monomer solution, carry out adiabatic polymerisation, obtain copolymer gel;
(4) copolymer gel is carried out the acrylamide copolymer product that granulation, hydrolysis, secondary granulation, drying, pulverizing and a screening obtain temperature resistant antisalt.
According to the present invention, in step (1), described temperature resistant antisalt monomer is monomer F of the present invention, and described surface active function monomer is monomer G of the present invention, and described inorganic alkaline compound is for regulating the pH value of acrylamide and temperature resistant antisalt monomer solution.Described inorganic alkaline compound can be at least one in sodium hydroxide, potassium hydroxide and sodium carbonate, is preferably sodium hydroxide.
Present invention also offers the acrylamide copolymer obtained according to aforesaid method.
In addition, present invention also offers the application of described acrylamide copolymer in oil-displacing agent.
Below, by following examples, the present invention will be described in more detail
In following examples, the performance test of product adopts following methods to carry out:
1, the solid content of polymkeric substance, dissolution time, filtration ratio, insolubles content, AM residual monomer content and intrinsic viscosity is measured according to the method specified in People's Republic of China (PRC) oil and gas industry standard SY/T5862-2008.
2, polymkeric substance viscosity-average molecular weight is according to the method specified in SY/T5862-2008, adopts formula M=([η]/0.000373)
1.515calculate, wherein, M is viscosity-average molecular weight, and [η] is intrinsic viscosity.
3, the apparent viscosity of polymers soln is the solution with the salt solution of salinity 32000mg/L, polymkeric substance being made into 1500mg/L, with Brookfield viscometer at 95 DEG C, and 7.34s
-1measure under condition.
In following examples, acrylamide is purchased from Bao Mo biochemical industry limited-liability company, and 2-acrylamide-2-methylpro panesulfonic acid is purchased from Xiamen Changtian Enterprise Co., Ltd., 2,2'-azo diisobutyl amidine dihydrochloride business available from Aldrich Co.The surface active function monomer (allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether ammonium sulfate) of structure shown in formula (15) is purchased from Foshan Kodi Gas Chemical Industry Co., Ltd., and the trade mark is respectively SE-10, SE-15 and SE-20(" 10 ", " 15 " and " 20 " represent the numerical value of n ' respectively.）
Embodiment 1
The present embodiment is for illustration of the preparation method of acrylamide copolymer provided by the invention
1000 grams of acrylamides, 10 grams of 2-acrylamide-2-methylpro panesulfonic acids, 10 grams of the surface active function monomer (n ' be 10) of structure and 4080 grams of deionized waters are as the formula (15) added in beaker, under whipped state, control solution temperature 5 DEG C with chilled brine, add sodium hydroxide and regulate pH to 7.Monomer solution is transferred in polymerization bottle, add 10.2 milligram 2,2'-azo diisobutyl amidine dihydrochloride and 10.2 milligrams of N, N, N ', N '-Tetramethyl Ethylene Diamine, logical high pure nitrogen deoxygenation 0.5 hour, add 10.2 milligrams of sodium bisulfites and 10.2 milligrams of ammonium persulphates, continue logical nitrogen until thermopair starts to heat up in polymerization bottle, 8 hours reaction times.Colloid is taken out, is become the multipolymer micelle of 4-6 millimeter by granulator granulation.By degree of hydrolysis 20%, the multipolymer micelle obtained is mediated with the sodium hydroxide grain alkali of respective amount and contacts, at temperature 90 DEG C, be hydrolyzed 0.5 hour, after secondary granulation, carry out drying, as shown in table 1 by crushing and screening the performance obtaining 20-80 object acrylamide copolymer product P 1, P1.Calculate according to charging capacity and determine, in acrylamide copolymer, the mass ratio of structural unit A, structural unit B, structural unit C and structural unit D is 1:0.013:0.013:0.333.
Comparative example 1
Adopt and embodiment 1 same process condition, difference is, do not add the surface active function monomer (n ' be 10) such as formula (15) structure, thus obtain acrylamide copolymer product DP1, the performance of DP1 is as shown in table 1.
Embodiment 2
The present embodiment is for illustration of the preparation method of acrylamide copolymer provided by the invention
1000 grams of acrylamides, 1000 grams of 2-acrylamide-2-methylpro panesulfonic acids, 100 grams of the surface active function monomer (n ' be 10) of structure and 4900 grams of deionized waters are as the formula (15) added in beaker, under whipped state, control solution temperature 15 DEG C with chilled brine, add sodium hydroxide and regulate pH to 7.Monomer solution is transferred in polymerization bottle, add 1.05 gram 2,2'-azo diisobutyl amidine dihydrochloride and 1.05 grams of N, N, N ', N '-Tetramethyl Ethylene Diamine, logical high pure nitrogen deoxygenation 0.5 hour, add 1.05 grams of sodium bisulfites and 1.05 grams of ammonium persulphates, continue logical nitrogen until thermopair starts to heat up in polymerization bottle, 4 hours reaction times.Colloid is taken out, is become the multipolymer micelle of 4-6 millimeter by granulator granulation.By degree of hydrolysis 20%, the multipolymer micelle obtained is mediated with the sodium hydroxide grain alkali of respective amount and contacts, under temperature 70 C, be hydrolyzed 4 hours, after secondary granulation, carry out drying, as shown in table 1 by crushing and screening the performance obtaining 20-80 object acrylamide copolymer product P 2, P2.Calculate according to charging capacity and determine, in acrylamide copolymer, the mass ratio of structural unit A, structural unit B, structural unit C and structural unit D is 1:1.370:0.137:0.489.
Embodiment 3
The present embodiment is for illustration of the preparation method of acrylamide copolymer provided by the invention
1000 grams of acrylamides, 100 grams of 2-acrylamide-2-methylpro panesulfonic acids, 50 grams of the surface active function monomer (n ' be 10) of structure and 3450 grams of deionized waters are as the formula (15) added in beaker, under whipped state, control solution temperature 10 DEG C with chilled brine, add sodium hydroxide and regulate pH to 7.Monomer solution is transferred in polymerization bottle, add 115 milligram 2,2'-azo diisobutyl amidine dihydrochloride and 115 milligrams of N, N, N ', N '-Tetramethyl Ethylene Diamine, logical high pure nitrogen deoxygenation 0.5 hour, add 115 milligrams of sodium bisulfites and 115 milligrams of ammonium persulphates, continue logical nitrogen until thermopair starts to heat up in polymerization bottle, 6 hours reaction times.Colloid is taken out, is become the multipolymer micelle of 4-6 millimeter by granulator granulation.By degree of hydrolysis 20%, the multipolymer micelle obtained is mediated with the sodium hydroxide grain alkali of respective amount and contacts, at temperature 80 DEG C, be hydrolyzed 2 hours, after secondary granulation, carry out drying, as shown in table 1 by crushing and screening the performance obtaining 20-80 object acrylamide copolymer product P 3, P3.Calculate according to charging capacity and determine, in acrylamide copolymer, the mass ratio of structural unit A, structural unit B, structural unit C and structural unit D is 1:0.126:0.063:0.347.
Embodiment 4
The present embodiment is for illustration of the preparation method of acrylamide copolymer provided by the invention
1000 grams of acrylamides, 100 grams of 2-acrylamide-2-methylpro panesulfonic acids, 50 grams of the surface active function monomer (n ' be 15) of structure and 3450 grams of deionized waters are as the formula (15) added in beaker, under whipped state, control solution temperature 10 DEG C with chilled brine, add sodium hydroxide and regulate pH to 7.Monomer solution is transferred in polymerization bottle, add 115 milligram 2,2'-azo diisobutyl amidine dihydrochloride and 115 milligrams of N, N, N ', N '-Tetramethyl Ethylene Diamine, logical high pure nitrogen deoxygenation 0.5 hour, add 115 milligrams of sodium bisulfites and 115 milligrams of ammonium persulphates, continue logical nitrogen until thermopair starts to heat up in polymerization bottle, 6 hours reaction times.Colloid is taken out, is become the multipolymer micelle of 4-6 millimeter by granulator granulation.By degree of hydrolysis 20%, the multipolymer micelle obtained is mediated with the sodium hydroxide grain alkali of respective amount and contacts, at temperature 80 DEG C, be hydrolyzed 2 hours, after secondary granulation, carry out drying, as shown in table 1 by crushing and screening the performance obtaining 20-80 object acrylamide copolymer product P 4, P4.Calculate according to charging capacity and determine, in acrylamide copolymer, the mass ratio of structural unit A, structural unit B, structural unit C and structural unit D is 1:0.126:0.063:0.346.
Embodiment 5
The present embodiment is for illustration of the preparation method of acrylamide copolymer provided by the invention
1000 grams of acrylamides, 100 grams of 2-acrylamide-2-methylpro panesulfonic acids, 50 grams of surface active function monomers such as formula (15) described structure (n ' be 20) and 3450 grams of deionized waters are added in beaker, under whipped state, control solution temperature 10 DEG C with chilled brine, add sodium hydroxide and regulate pH to 7.Monomer solution is transferred in polymerization bottle, add 115 milligram 2,2'-azo diisobutyl amidine dihydrochloride and 115 milligrams of N, N, N ', N '-Tetramethyl Ethylene Diamine, logical high pure nitrogen deoxygenation 0.5 hour, add 115 milligrams of sodium bisulfites and 115 milligrams of ammonium persulphates, continue logical nitrogen until thermopair starts to heat up in polymerization bottle, 6 hours reaction times.Colloid is taken out, is become the multipolymer micelle of 4-6 millimeter by granulator granulation.By degree of hydrolysis 20%, the multipolymer micelle obtained is mediated with the sodium hydroxide grain alkali of respective amount and contacts, at temperature 80 DEG C, be hydrolyzed 2 hours, after secondary granulation, carry out drying, as shown in table 1 by crushing and screening the performance obtaining 20-80 object acrylamide copolymer product P 5, P5.Calculate according to charging capacity and determine, in acrylamide copolymer, the mass ratio of structural unit A, structural unit B, structural unit C and structural unit D is 1:0.126:0.063:0.346.
Embodiment 6
1000 grams of acrylamides, 50 grams of 2-acrylamide-2-methylpro panesulfonic acids, 50 grams of N are added in beaker, N-DMAA, 50 grams of the surface active function monomer (n ' be 10) of structure and 3450 grams of deionized waters as the formula (15), under whipped state, control solution temperature 10 DEG C with chilled brine, add sodium hydroxide and regulate pH to 7.Monomer solution is transferred in polymerization bottle, add 115 milligram 2,2'-azo diisobutyl amidine dihydrochloride and 115 milligrams of N, N, N ', N '-Tetramethyl Ethylene Diamine, logical high pure nitrogen deoxygenation 0.5 hour, add 115 milligrams of sodium bisulfites and 115 milligrams of ammonium persulphates, continue logical nitrogen until thermopair starts to heat up in polymerization bottle, 6 hours reaction times.Colloid is taken out, is become the multipolymer micelle of 4-6 millimeter by granulator granulation.By degree of hydrolysis 20%, the multipolymer micelle obtained is mediated with the sodium hydroxide grain alkali of respective amount and contacts, at temperature 80 DEG C, be hydrolyzed 2 hours, after secondary granulation, carry out drying, as shown in table 1 by crushing and screening the performance obtaining 20-80 object acrylamide copolymer product P 6, P6.Calculate according to charging capacity and determine, in acrylamide copolymer, the mass ratio of structural unit A, structural unit B, structural unit C and structural unit D is 1:0.127:0.063:0.355.
Embodiment 7
Adopt the processing condition identical with embodiment 6, difference is, replaces N,N-DMAA with the vinyl pyrrolidone of equal mass, thus the performance of obtained acrylamide copolymer product P 7, P7 is as shown in table 1.Calculate according to charging capacity and determine, in acrylamide copolymer, the mass ratio of structural unit A, structural unit B, structural unit C and structural unit D is 1:0.127:0.063:0.354.
Embodiment 8
Adopt and embodiment 2 same process condition, difference is, 2-acrylamide-2-methylpro panesulfonic acid is replaced with the vinylformic acid of equal mass, and without hydrolysis, namely do not carry out being mediated with sodium hydroxide grain alkali by the multipolymer micelle obtained in embodiment 2 to contact, at 80 DEG C, be hydrolyzed the step of 2 hours, thus the performance obtaining acrylamide copolymer product P 8, P8 is as shown in table 1.Calculate according to charging capacity and determine, in acrylamide copolymer, the mass ratio of structural unit A, structural unit B and structural unit C is 1:1:0.1.
Embodiment 9
Adopt and embodiment 2 same process condition, difference is, without hydrolysis, namely do not carry out being mediated with sodium hydroxide grain alkali by the multipolymer micelle obtained in embodiment 2 to contact, the step of 2 hours is hydrolyzed at 80 DEG C, thus the performance obtaining acrylamide copolymer product P 9, P9 is as shown in table 1.Calculate according to charging capacity and determine, in acrylamide copolymer, the mass ratio of structural unit A, structural unit B and structural unit C is 1:1:0.1.
Table 1
In conjunction with the embodiments known with comparative example data, the molecular weight of the acrylamide copolymer product that embodiment 1 obtains can reach 3,080 ten thousand, and the molecular weight that comparative example 1 obtains acrylamide copolymer product is only 2,610 ten thousand, the molecular weight of copolymer that embodiment 1 obtains compared with comparative example 1 improves nearly 4,700,000, and corresponding 95 DEG C of apparent viscosity improve 9.8mPas.Illustrate that the introducing of surface active function monomer in the present invention is more conducive to improving the apparent viscosity of copolymer solution under the molecular weight of multipolymer and hot conditions.
By embodiment 2 compared with embodiment 9, the molecular weight obtaining acrylamide copolymer product in embodiment 9 is 2,700 ten thousand, 95 DEG C of apparent viscosity 14.9mPas, and both are all lower than the result of embodiment 2 products obtained therefrom.The apparent viscosity suitably introduced sodium acrylate structural unit and be more conducive to improving the copolymer solution under the molecular weight of multipolymer and hot conditions is described in copolymer structure.
For embodiment 1, the temperature resistant antisalt acrylamide copolymer that the present invention obtains is at high salinity 32000mg/L, under high temperature 95 DEG C of conditions, the apparent viscosity of solution can reach 22.9mPas, and commercially available high molecular weight polyacrylamide solution apparent viscosity is only 8.9mPas, comparatively contrast commercially available prod, acrylamide copolymer of the present invention has significantly thickening advantage.Accordingly, known acrylamide copolymer provided by the invention has good temperature resistant antisalt performance.
Claims (15)
1. an acrylamide copolymer, it is characterized in that, this acrylamide copolymer contains structural unit A, structural unit B and structural unit C, wherein, described structural unit A is for having the unit of structure shown in formula (1), described structural unit B is for having at least one in the unit of structure shown in formula (2)-Shi (5), described structural unit C is for having the unit of structure shown in formula (6), and the mass ratio of described structural unit A, described structural unit B and described structural unit C is 1:0.001-3:0.001-0.5, be preferably 1:0.01-1.5:0.01-0.2; The viscosity-average molecular weight of described acrylamide copolymer is 2,700 ten thousand-3,200 ten thousand, is preferably 2,900 ten thousand-3,100 ten thousand,
Wherein, R
1, R
2, R
6, R
7, R
10and R
11be the alkyl of hydrogen or C1-C4 independently of one another, R
3for the alkylidene group of C1-C14; R
4, R
5, R
8and R
9be the alkyl of C1-C4 independently of one another, R
12for the alkyl of C1-C14, M
1for at least one in H, Na and K, n is arbitrary integer in 1-20, and x, y and z are the arbitrary integer in 1-5 independently of one another.
2. acrylamide copolymer according to claim 1, wherein, described acrylamide copolymer also contains structural unit D, described structural unit D for having the unit of structure shown in formula (7):
Wherein, M
2for potassium or sodium.
3. acrylamide copolymer according to claim 2, wherein, the mass ratio of described structural unit A, described structural unit B, described structural unit C and described structural unit D is 1:0.001-3:0.001-0.5:0.1-1, is preferably 1:0.01-1.5:0.01-0.2:0.1-1.
4. according to the acrylamide copolymer in claim 1-3 described in any one, wherein, described structural unit B is for having at least one in the unit of structure shown in formula (2) and (4), and R
2and R
7be hydrogen or methyl independently of one another; In described structural unit C, R
12for the alkyl of C5-C10, n is the arbitrary integer in 5-20, and x, y and z are the arbitrary integer in 1-3 independently of one another.
5. the preparation method of an acrylamide copolymer, this preparation method comprises the following steps, under solution polymerization condition, under initiator exists, a kind of monomer mixture is made to carry out polyreaction in water, it is characterized in that, described monomer mixture contains monomer E, monomer F and monomer G, described monomer E is for having the monomer of structure shown in formula (8), described monomer F is for having at least one in the monomer of structure shown in formula (9)-Shi (12), described monomer G is for having the monomer of structure shown in formula (13), and described monomer E, the mass ratio of described monomer F and described monomer G is 1:0.001-3:0.001-0.5, be preferably 1:0.01-1.5:0.01-0.2, after described solution polymerization condition makes polyreaction, the viscosity-average molecular weight of resulting polymers is 2,700 ten thousand-3,200 ten thousand, is preferably 2,900 ten thousand-3,100 ten thousand,
Wherein, R
1', R
2', R
6', R
7', R
10' and R
11' be the alkyl of hydrogen or C1-C4 independently of one another, R
3' be the alkylidene group of C1-C14; R
4', R
5', R
8' and R
9' be the alkyl of C1-C4 independently of one another, R
12' be the alkyl of C1-C14, M
3for at least one in H, Na and K, n ' is integer arbitrary in 1-20, and x ', y ' and z ' are the arbitrary integer in 1-5 independently of one another.
6. method according to claim 5, wherein, described monomer F is for having at least one in the monomer of structure shown in formula (9) and formula (11), and R
2' and R
7' be hydrogen or methyl independently of one another; In described monomer G, R
12' be the alkyl of C5-C10, n ' is the arbitrary integer in 5-20, and x ', y ' and z ' they are the arbitrary integer in 1-3 independently of one another.
7. method according to claim 5, wherein, when described solution polymerization starts, the ratio of the gross weight of the weight of described monomer mixture and water and monomer mixture is 0.15-0.4:1, is preferably 0.2-0.3:1.
8. method according to claim 5, wherein, described initiator is selected from azo series initiators and redox series initiators, the consumption of described azo series initiators is the 0.0001-0.1 % by weight of the gross weight of monomer mixture, and the consumption of described redox series initiators is the 0.0002-0.3 % by weight of the gross weight of monomer mixture; Described azo series initiators is water-soluble azo series initiators, and described redox series initiators comprises Oxidizing and Reducing Agents, and described reductive agent is inorganic reducing agent and/or organic reducing agent, and the weight ratio of described oxygenant and described reductive agent is 0.1-1:1.
9. method according to claim 8, wherein, described water-soluble azo series initiators is selected from 2,2'-azo diisobutyl amidine dihydrochloride, 2, at least one in 2'-azo [2-(2-tetrahydroglyoxaline-2-base) propane] dihydrochloride and 4,4'-azo two (4-cyanopentanoic acid); Described oxygenant is selected from least one in benzoyl peroxide, hydrogen peroxide, tertbutyl peroxide, 2,5-dimethyl-2,5 pairs of (hydrogen peroxide) hexanes, ammonium persulphate, Sodium Persulfate and Potassium Persulphates; Described inorganic reducing agent is selected from least one in ferrous sulfate, ferrous ammonium sulphate, cuprous chloride, potassium sulfite, S-WAT, ammonium bisulfite, Potassium hydrogen sulfite, Sulfothiorine, Potassium Thiosulphate, rongalite and sodium bisulfite; Described organic reducing agent is selected from N, N-dimethylethanolamine, N, N-lupetazin, tetramethyl-urea, N, N – dimethyl-ethylenediamine and N, N, N ', at least one in N '-Tetramethyl Ethylene Diamine.
10. method according to claim 5, wherein, described solution polymerization carries out in the presence of an inert gas, and described polymeric reaction condition comprises: temperature is-10 DEG C to 20 DEG C, is preferably 5 DEG C to 15 DEG C; Time is 2-12 hour, preferred 4-8 hour; PH value is 4-12, is preferably 5-10.
11. according to the method in claim 5-10 described in any one, and wherein, described method also comprises and to be hydrolyzed to resulting polymers after polyreaction and dry.
12. methods according to claim 11, wherein, described hydrolysising condition comprises: temperature is 50-110 DEG C, is preferably 70-90 DEG C; Time is 0.5-6 hour, is preferably 1-4 hour; After described hydrolysis makes polyreaction, the degree of hydrolysis of resulting polymers is 10-30%.
13. methods according to claim 11, wherein, the condition of described drying comprises: temperature is 40-120 DEG C, is preferably 70-90 DEG C; Time is 0.2-4 hour, is preferably 0.5-2 hour.
The acrylamide copolymer that method in 14. claim 5-13 described in any one is obtained.
Acrylamide copolymer in 15. claim 1-4 and 14 described in any one is as the application of oil-displacing agent.
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